KR101824944B1 - Colored photosensitive resin composition, pattern forming method, method of producing color filter, color filter, and display device having the same - Google Patents

Abstract

(A) a colorant, (B-1) a binder resin represented by the general formula (I) and having an acidic group, (B-2) a binder containing a structural unit represented by the general formula (II) (B-1) :( B-2) in a ratio of 3: 7 to 7: 3, wherein the photosensitive resin composition (B) Resin composition. In the formula (I), R ³ represents an organic linking group of (m + n), and R ⁴ and R ⁵ represent a single bond or a divalent organic linking group. A ² represents a monovalent organic group including an adsorptive group such as an organic dye structure or an acidic group. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ² represents a polymer skeleton. In the formula (II), R ¹¹ to R ¹⁵ 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.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a pattern forming method, a method of manufacturing a color filter, a color filter, and a display device having the color filter.

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

In recent years, the development of a liquid crystal display device has been developed for use in televisions in which a screen is large and a high image quality is required, from the use of a parser computer and a monitor whose screen is relatively small.

In the case of television applications, it is required to improve image quality, that is, contrast and color purity, in comparison with the conventional monitor applications. In order to improve the contrast, the colorant (organic pigment or the like) used in the colored photosensitive resin composition used for forming the color filter is required to have a smaller particle size. In order to improve the color purity, the content of the colorant (organic pigment) in the solid content of the colored photosensitive resin composition is required to be higher.

With respect to the above-mentioned requirement, a pigment dispersion composition having a smaller particle diameter of the pigment and a higher dispersibility is required. In order to improve the dispersibility of the pigment, it is usually necessary to modify the surface of the pigment with the derivative compound on the surface of the phthalocyanine pigment, and use a dispersing agent such as a low-molecular-weight resin having a polar functional group, A surface modifier, and a dispersing agent while obtaining dispersibility and dispersibility of the pigment. Then, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and other components are further contained in the obtained pigment dispersion composition to obtain a photosensitive composition, and a color filter is obtained by photolithography or the like using the photosensitive composition.

If the pigment becomes finer and the content of the pigment becomes higher, there is a problem that when the image pattern is formed by the photolithography method, the line width sensitivity is lowered (line width becomes narrow). It is required to provide a color filter at a particularly low cost in TV applications. However, there is a need to increase the amount of exposure in the exposure process, that is, to increase the exposure time, due to the problem centering on the above-described development process. As a result, the yield is lowered and the productivity is deteriorated, so that improvement has been demanded.

In order to solve the above problems, many attempts have been made to improve the line width sensitivity by improving the photopolymerization initiator used in the photosensitive resin composition for a color filter. For example, a photopolymerizable composition using a triazine-based compound having a specific structure (see, for example, Patent Document 1), a benzophenone-based compound, an acetophenone-based compound, and a thioxanthone compound- And a photo-resist for a color filter (see, for example, Patent Document 2).

As another proposal, the average double bond equivalent in the organic compound which is the total of the binder resin and the polymerizable compound in the colored photosensitive resin composition is specified, and the molecular weight of the binder resin is specified, thereby forming a net taper shape by firing (See Patent Document 3).

Further, although not a colored photosensitive resin composition for exposure by an ultraviolet laser, it has been proposed to prepare a colored resin composition with high sensitivity and wide latitude of development by using a binder resin containing an allyl group (see, for example, Patent Document 4, 5). It has also been proposed to provide a radiation sensitive composition for a blue color filter having good color reproducibility by using an N-phenylmaleimide copolymer as a binder resin (for example, refer to Patent Document 6). However, in these techniques, the productivity in the exposure process and the development process by the ultraviolet laser is reduced, so that sufficient productivity can not be ensured, and therefore, the cost of the color filter can not be reduced.

In order to improve the productivity of the exposure process and the development process, it has been proposed to expose with laser light and perform pattern formation (see, for example, Patent Document 7). Unlike mercury lamps which are generally used, lasers are expected to have high linearity, high output, narrow focus, and no mask for pattern formation in the exposure process. However, even when the above-described prior art is employed, the surface of the pixel becomes rough in the developing process, the line width sensitivity of the pattern is insufficient, and the like, which does not satisfy the characteristics required for the colored photosensitive resin composition. In addition, it has been proposed that a large photomask is not used as an exposure apparatus in terms of lowering the cost as a total of color filters (see, for example, Patent Documents 8 and 9). However, there is no specific material presentation, and a proposal of a material suitable for these devices has been desired.

Particularly, in a blue colored photosensitive resin composition, there is a problem that the binder resin which is inherently transparent to visible light after post baking due to the binder resin develops color, and when the binder resin is used for the coloring pattern of the color filter, A binder resin having no coloring has been desired.

Further, the blue colorant has a large absorption at 355 nm or 365 nm. When exposed by an ultraviolet laser, the photopolymerization does not progress sufficiently to the deep portion of the colored layer, and wrinkles occur after postbaking. There has been a desire for a blue-colored photosensitive resin composition which is sufficiently cured to a deep portion and has good curing sensitivity.

Japanese Patent Application Laid-Open No. 6-289611 Japanese Patent Application Laid-Open No. 9-80225 Japanese Patent Application Laid-Open No. 2007-93811 Japanese Patent Laid-Open No. 10-20496 International Publication No. 2007/29871 Japanese Patent No. 3632532 Japanese Patent Application Laid-Open No. 2003-287614 Japanese Patent Application Laid-Open No. 2008-76709 Japanese Patent Application Laid-Open No. 2008-51866

The present invention relates to a color photographic light-sensitive material which is high in line width sensitivity, excellent in linearity and heat resistance of a formed color pattern, capable of forming a colored pattern in which the occurrence of color development or wrinkling is suppressed even after post- It is an object of the present invention to provide a resin composition.

A new object of the present invention is to provide a method of forming a pattern in which a colored pattern excellent in shape and luminance is formed using the colored photosensitive resin composition of the present invention and a method of producing a color filter and a method of forming a coloring pattern And a display device including the color filter.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following methods.

(B-1) a binder resin represented by the following general formula (I) and having an acidic group in the molecule, (B-2) a resin composition comprising a structural unit represented by the following general formula (II) (B-1) binder resin and (B-2) a binder resin containing a structural unit having a group (B-1), a polymerizable compound (D), an oxime-based photopolymerization initiator, and By weight based on the weight of the photosensitive resin composition is 3: 7 to 7: 3.

In the general formula (I), R ³ represents an organic linking group of (m + n), and R ⁴ and R ⁵ each independently represent a single bond or a divalent organic linking group. A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, And a monovalent organic group containing at least one partial structure selected from a hydroxyl group. n A ² and R ⁴ may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ² represents a polymer skeleton. m P ² and R ⁵ may be the same or different.

In the general 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 colored photosensitive resin composition according to <1>, wherein the oxime-based photopolymerization initiator (D) is a ketoxime-based photopolymerization initiator represented by the following general formula (III).

In the general 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 of 0 to 5; When a plurality of Xs exist, a plurality of Xs each independently represents a monovalent substituent, and may be the same or different.

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

&Lt; 4 > A process for producing a colored layer, comprising the steps of: forming a colored layer by applying a colored photosensitive resin composition according to any one of < 1 > And a developing step of removing the un-hardened portion of the colored layer by development to form a pattern.

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

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

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

&Lt; 8 > A color filter produced by the manufacturing method according to < 7 >.

<9> A display device comprising the color filter according to <8>.

(Effects of the Invention)

According to the present invention, it is possible to provide a coloring pattern which is high in line width sensitivity, excellent in the linearity and heat resistance of the formed coloring pattern and capable of forming a colored pattern in which color development and wrinkling are suppressed even after post- A photosensitive resin composition can be provided.

Further, a method of forming a pattern in which a colored pattern having excellent shape and luminance is formed by using the colored photosensitive resin composition of the present invention, a method of manufacturing a color filter, a color filter having a pattern shape and a coloring pattern with good luminance, A display device provided with a filter can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

«Colored photosensitive resin composition»

The colored photosensitive resin composition of the present invention comprises at least (A) a colorant, (B-1) a binder resin represented by the following general formula (I) and having an acidic group in the molecule (hereinafter appropriately referred to as (B- , (B-2) a binder resin comprising a structural unit represented by the following general formula (II) and a structural unit having an acidic group [hereinafter referred to as "binder resin (B-2) (B-1) binder resin and (B-2) binder resin, based on the mass of the binder resin, of from 3: 7 to 7: 3 .

Each constituent component of the colored photosensitive resin composition of the present invention will be described in detail below.

<(A) Colorant>

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

The content of the colorant (A) in the colored photosensitive resin composition of the present invention is preferably 15 mass% to 60 mass% with respect to the solid content of the colored photosensitive resin composition. If the content of the colorant (A) is less than 15% by mass, it is necessary to set the film thickness to be large in order to achieve a desired hue, which makes it difficult to develop the film, or the tact time may increase. On the other hand, when the content of the colorant (A) exceeds 60% by mass, the development time becomes longer and the profile shape also becomes an inverted edge shape, which is not preferable.

The term "solid content" of the colored photosensitive resin composition in the present invention refers to the amount of residual heating after 1 g of the colored photosensitive resin composition is weighed in an aluminum container and dried at 160 ° C. for 60 minutes. In the colored photosensitive resin composition of the present invention E) solvent. &Lt; / RTI &gt;

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

As the colorant (A), a dye and a pigment can be suitably selected and used. From the viewpoint of heat resistance and the like, a pigment is more preferable.

The pigment used as the (A) coloring agent may be either an inorganic pigment or an organic pigment, but from the viewpoint of high transmittance, it is preferable to use a pigment having a small particle size. The average of the primary particle diameter is preferably 0.01 탆 to 0.1 탆, more preferably 0.01 탆 to 0.05 탆.

In the colored photosensitive resin composition of the present invention, by using the polymer dispersant described later, even when the size of the pigment is small, the pigment dispersibility and the dispersion stability become good, so that a colored pixel excellent in color purity can be formed even if the film thickness is thin .

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

The ratio of the pigment having a primary particle diameter of less than 0.02 占 퐉 is less than 10%, heat resistance is good and chromaticity change can be prevented, and the ratio of the pigment whose primary particle diameter exceeds 0.08 占 퐉 is less than 5% Good stability with time of the colored photosensitive resin composition, and prevention of foreign matter breakage.

From the viewpoint of heat resistance and prevention of chromaticity change, it is more preferable that the proportion of the pigment having a primary particle diameter of less than 0.02 탆 is less than 5%.

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

The primary particle diameter of the pigment can be measured using a TEM (transmission electron microscope). That is, it is possible to investigate the particle size distribution by image analysis of the TEM photograph. For example, the particle size distribution can be grasped by measuring the total number of particles in an observation sample at 3 to 100,000 times, and the number of particles of less than 0.02 占 퐉 and 0.08 占 퐉. More specifically, the pigment powder was observed by a transmission electron microscope at a magnification of 3 to 1000000 and photographed. The long diameter of 1000 primary particles was measured to find that the ratio of the primary particles exceeding 0.02 탆 and exceeding 0.08 탆 . This operation is carried out for three portions in total by changing the portions of the pigment powder, and the results are averaged.

Examples of the inorganic pigments that can be used as the colorant (A) include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, An oxide of a metal of the above metal, and a composite oxide of the above metal.

As the organic pigment, for example,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: , 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: , 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, 12,13,14,15,16,17,18,20,24,31,32,34,35,35,136 , 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 ,

C. I. 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, Things, 80,

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,

C. I. Pigment Brown 25, 28, and the like.

Among them, the following pigments can be preferably used. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C. I. Pigment Orange 36, 71,

C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C. I. Pigment Violet 19, 23, 32, 58

C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C. I. Pigment Green 7, 36, 37.

These organic pigments may be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.

For example, as the pigment for the red layer (R), an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one thereof and a disazo pigment, an isoindoline pigment, a quinophthalone pigment Or a mixture of at least one of an anthraquinone pigment, a perylene pigment and a diketopyrrolopyrrole pigment with a yellow pigment such as a perylene pigment, an anthraquinone pigment, a condensed disc pigment, a diketopyrrolopyrrole pigment And the like may be used. Examples of the anthraquinone-based pigment include CI Pigment Red 177, the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224, and the condensed-disintegrative red pigment includes CI Pigment Red 242 And diketopyrrolopyrrole pigments include CI Pigment Red 254. From the viewpoint of color reproducibility, a mixture of CI Pigment Red 254 and CI Pigment Yellow 139 or CI Pigment Red 177 is preferable.

The mass ratio of the red pigment and the other pigment (red pigment: other pigment) is preferably 100: 5 to 100: 80. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and the color purity may not be increased. In addition, the coloring power may be lowered at a ratio of 100: 81 or more. Particularly, the mass ratio is preferably in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

As the pigment for the green layer (G), a halogenated phthalocyanine pigment may be used singly or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment Can be used. For example, a mixture of CI Pigment Green 7, 36, 37, 58 and CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI Pigment Yellow 185, desirable.

The mass ratio of the green pigment to the yellow pigment is preferably from 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As the pigment for the blue layer (B), a phthalocyanine-based pigment may be used alone, or a mixture of the phthalocyanine-based pigment and a dioxazine-based purple pigment may be used. For example, a mixture of C. I. Pigment Blue 15: 6 and C. I. Pigment Violet 23 is preferred. The mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 50, and more preferably 100: 5 to 100: 30.

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

In the present invention, it is particularly preferable to use an organic pigment as a coloring agent and a pigment coated with a polymer compound in a step of finishing or dispersing the pigment. A coated pigment having improved dispersibility and capable of being dispersed in the state of primary particles while suppressing the formation of secondary agglomerates even in a finely dispersed pigment by coating the pigment with a polymer compound, It is more preferable to use a coating pigment excellent in stability.

The coated pigment, which is a preferable form in the present invention, is a pigment coated with a polymer compound. In the coating, a strong coat of the polymer compound is formed on the new interface of the pigment having a high surface activity caused by micronization by a strong electrostatic action with the polymer compound It is considered that a coating pigment having higher dispersion stability can be obtained. That is, in the present invention, the coated polymer is hardly released when the coated pigment is washed with an organic solvent dissolving the polymer compound.

The coating pigment referred to in the present invention is a pigment in which pigment particles such as organic pigments are coated with a polymer compound having a polar group such as a heterocycle on the side chain and the polymer compound strongly covers a part or all of the surface of the pigment particle, Stability effect, and is different from a case where a general polymer dispersant is adsorbed on a pigment. This coated state can be confirmed by measuring the amount of the polymer (free ratio) by washing with the organic solvent shown below. That is, most of the polymer compounds formed by just adsorption are removed by cleaning with an organic solvent, specifically, at least 65% of the glass is removed. However, in the case of the surface-coated pigment as in the present invention, to be.

The amount of the glass (the glass ratio) is calculated by washing the pigment after the coating treatment with 1-methoxy-2-propanol. That is, 10 g of the pigment was added to 100 ml of 1-methoxy-2-propanol, shaken at room temperature for 3 hours using a shaker, and then the pigment was precipitated at 80,000 rpm for 8 hours in a centrifugal separator. The mass is determined by the drying method. The free ratio (%) is calculated from the ratio of the mass of the solid content to the mass of the polymer compound used in the coating process of the pigment.

The above-mentioned amount of free glass (free ratio) for commercially available pigments can be measured by the following method. That is, after the entire pigment is dissolved with a solvent (for example, dimethylsulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.) dissolving the pigment, the pigment is separated into an organic solvent using a difference in solubility between the polymer and the pigment, Quot; mass of the polymer compound used in the coating process &quot; Separately, the glass ratio (%) is obtained by dividing the glass amount of the polymer compound obtained by washing the pigment with 1-methoxy-2-propanol by the "mass of the polymer compound used for coating the pigment".

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

The coating treatment is preferably carried out simultaneously with the fineness of the pigment, and concretely, it is preferable that the coating treatment is carried out simultaneously with (i) a pigment, (ii) a water-soluble inorganic salt, (iii) a small amount of a water-soluble organic solvent which does not substantially dissolve (Iv) a step of adding a polymer compound, mechanically kneading the mixture with a kneader to obtain a mixture (referred to as a salt milling step), putting this mixture into water and stirring it with a high speed mixer or the like to form a slurry, The slurry is filtered, washed with water, and dried if necessary.

The above-mentioned salt milling will be described in more detail. First, a small amount of (iii) water-soluble organic solvent is added as a wetting agent to a mixture of (i) an organic pigment and (ii) a water-soluble inorganic salt, and the mixture is strongly kneaded with a kneader or the like, Or the like to obtain a slurry. Subsequently, this slurry is filtered, washed with water, and dried as necessary to obtain a finely divided pigment. In addition, when dispersed and used in an oil-based varnish, it is also possible to disperse the treated pigment (called a filter cake) before drying in a solvent-based varnish while removing water by a method commonly called flashing. In the case of dispersing in the varnish of the water system, the treated pigment does not need to be dried, and the filter cake can be directly dispersed in the varnish.

When (iii) a resin which is at least partially soluble in (iii) an organic solvent is used in combination with the above-mentioned (iv) polymer compound during salt milling, it is obtained that the surface is coated with the resin and the aggregation of the pigment during drying is small.

Further, (iv) the polymer compound may be added all at the beginning of the salt milling step or may be added in portions. It is also possible to add it in a dispersion process.

The polymer compound used for covering the pigment may be any as long as it has an adsorptive group to the pigment. Particularly, a polymer compound having a heterocycle in its side chain is preferable. The binder resin (B-1) described later in the present invention is also preferable as a polymer compound used for coating a pigment.

Examples of polymer compounds that can be used for coating pigments include those described in paragraphs [0029] to [0030] of JP-A No. 2008-83089 and paragraphs [0044] to [0044] of JP-A No. 2009-62457 ] Can be used.

Even when the above-mentioned coated pigment is used, it is more preferable to disperse the pigment using at least one kind of dispersant and use it as a pigment dispersion composition. The dispersibility of the pigment can be further improved by the inclusion of the dispersant.

As the dispersant, for example, a known pigment dispersant or a surfactant can be suitably selected and used.

Specifically, many kinds of compounds can be used, and examples thereof include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 cationic surfactant such as [manufactured by Kyoeisha Kagaku Kogyo K.K. and W001 (manufactured by Yuso Co., Ltd.); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005 and W017 (manufactured by Yuso Co., Ltd.); EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse AID 6, Disperse AID 8, Disperse A 15, EFKA-47, EFKA-47, EFKA-47EA, EFKA Polymer 100, , Disperse Aid 9100 (all available from Sanofco), and the like;

(Manufactured by Nippon Lubrizol Corporation) such as Sol Spurs 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000 and 28000; (Manufactured by Asahi Denka Kogyo K.K.), and the like were added to the reaction mixture, and the reaction was carried out in the same manner as in Example 1, And 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 Big Chem Co., Ltd.). And an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

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

The pigment derivative is one of the polymer compounds used for covering the pigment, and is added to the pigment dispersion composition as required. The pigment can be dispersed in the photosensitive resin composition as fine particles by adsorbing the pigment derivative having the affinity with the dispersing agent or the pigment derivative having the affinity with the dispersing agent to the surface of the pigment as the adsorption point of the dispersing agent, This is effective for forming a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound having an organic pigment as a parent skeleton and an acid group, a basic group and an aromatic group as substituents introduced into the side chain. Specific examples of the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzimidas A zeolite pigment and the like. The organic pigments also include pale yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based pigments, which are not generally referred to as pigments. As the pigment derivative, for example, JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP- 8-295810, 11-199796, 2005-234478, 2003-240938, 2001-356210, and the like can be used. .

The content of the pigment derivative in the pigment dispersion composition is preferably 1% by mass to 30% by mass, and more preferably 3% by mass to 20% by mass, based on the mass of the pigment. When the content is within the above range, dispersion can be satisfactorily performed while suppressing the viscosity to be low, dispersion stability after dispersion can be improved, high transmittance and excellent color characteristics can be obtained, and good color characteristics can be obtained Can be configured with high contrast.

The dispersing method can be carried out, for example, by finely dispersing a pigment and a dispersant in advance by mixing them in advance with a homogenizer or the like using a bead dispersing machine using zirconia beads or the like.

In the present invention, when a dye is used as the (A) coloring agent, a colored photosensitive resin composition that is uniformly dissolved can be obtained.

The dyes usable as the (A) coloring agent are not particularly limited, and known dyes conventionally used for color filters can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, JP-A-5-333207, JP-A-6-35183, and JP-A-6-51115 , Japanese Patent Application Laid-Open Nos. 6-194828, 8-211599, 4-249549, 10-123316, and 11-302283 , Japanese Patent Application Laid-Open Nos. 7-286107, 2001-4823, 8-15522, 8-29771, 8-146215, Japanese Patent Application Laid-Open No. 11-343437, Japanese Patent Application Laid-Open No. 8-62416, Japanese Unexamined Patent Application Publication No. 2002-14220, Japanese Unexamined Patent Application Publication No. 2002-14221, Japanese Unexamined Patent Application Publication No. 2002-14222, Japanese Unexamined Patent Publication No. 2002-14223, Japanese Unexamined Patent Publication No. 8-302224, 8-73758, JP-A-8-179120, JP-A-8-151531, etc.

Examples of the chemical structure include a pyrazole group, anilino group, triphenylmethane group, anthraquinone group, anthrapyridone group, benzilidene group, oxolin group, pyrazolotriazole group, pyridazo group, cyanine group, phenothiazine group, Dyes such as pyrazolomethane, xanthane, phthalocyanine, benzopyran, indigo and the like can be used.

&Lt; (B-1) Binder resin represented by the general formula (I) and having an acidic group in the molecule &

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

The binder resin (B-1) according to the present invention has at least one acidic group in the molecule. The acid group may be contained in the substituent A ² in the general formula (I) and may be contained in the polymer skeleton represented by P ² , but from the viewpoint of the effect, the acid group is preferably contained in the polymer skeleton represented by P ² , And it is more preferable that both of A ² and P ² contain an acidic group.

In the general formula (I), R ³ represents an organic linking group of (m + n), and R ⁴ and R ⁵ each independently represent a single bond or a divalent organic linking group. A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, And a monovalent organic group containing at least one partial structure selected from a hydroxyl group. n A ² and R ⁴ may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ² represents a polymer skeleton. m P ² and R ⁵ may be the same or different.

A ² in the general formula (I) represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, A silyl group, an epoxy group, an isocyanate group, and a hydroxyl group. n A ² may be the same or different.

That is, A ² is a structure having an adsorptive ability to a pigment such as an organic dye structure or a heterocyclic structure, a group having an acidic group, a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, Represents a monovalent organic group containing at least one functional group capable of adsorbing to a pigment such as a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group.

Hereinafter, the partial structure (structure and functional group) having adsorptivity to this pigment will be collectively referred to as &quot; adsorption site &quot;

The adsorption site may contain at least one of A ² , and may include two or more species.

In the present invention, the "monovalent organic group containing at least one adsorption site" is a monovalent organic group containing at least one selected from the group consisting of 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms , 1 to 400 hydrogen atoms, and 0 to 40 sulfur atom-forming organic linking groups. In addition, when the adsorption site itself can constitute a monovalent organic group, it may be a monovalent organic group in which the adsorption site is represented by A ² .

First, the adsorption sites constituting A ² will be described below.

Examples of the organic pigment structure include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone, indanthrone, Preferred examples of the dye structure of the phthalocyanine-based, azo lake-based, anthraquinone-based, dioxazine-based, and diketopyrrolopyrrole-based pigments are And a dye structure of phthalocyanine type, anthraquinone type, and diketopyrrolopyrrole type is particularly preferable.

Examples of the "heterocyclic structure" include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, Wherein the heterocyclic ring is selected from the group consisting of thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, Preferable examples include pyridine, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone and anthraquinone , Pyrrole, pyrrolidine, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, Indolinone, benzimadazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, Sol, acridine, acridine money, anthraquinone is more preferable.

The above "organic dye structure" or "heterocyclic structure" may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, An alkoxy group having 1 to 20 carbon atoms such as a methoxy group and an ethoxy group, such as a methoxy group, an ethoxy group and the like, an aryloxy group having 1 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, , Halogen atoms such as chlorine and bromine, carbonic ester groups such as an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a cyano group and t-butylcarbonate. Here, these substituents may be bonded to an organic pigment structure or a heterocyclic ring through a linking group composed of the following structural units or a combination of the structural units.

Preferable examples of the "acidic group" include a carboxylic acid group, a sulfonic acid group, a mono sulfuric acid ester group, a phosphoric acid group, a monophosphoric acid ester group and a boric acid group, A phosphoric acid group and a monophosphate ester group are more preferable, and a carboxylic acid group, a sulfonic acid group and a phosphoric acid group are particularly preferable.

Examples of the "group having a basic nitrogen atom" include an amino group (-NH ₂ ), a substituted amino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are A guanidyl group represented by the following formula (a1), an amidinyl group represented by the following formula (a2), or the like, As a preferable example.

In 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, or an aralkyl group having 7 or more carbon atoms.

In 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, or an aralkyl group having 7 or more carbon atoms.

Among them, an amino group (-NH ₂ ), a substituted amino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group. (Wherein R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group), the formula (a1) It indicated that an amidinyl group [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group, a phenyl group, a benzyl group of 1 to 10 carbon atoms.] and so this is more preferable.

Particularly, an amino group (-NH ₂ ), a substituted amino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group. (Wherein R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group), a compound represented by the formula (a1) (In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group], and the like are preferably used.

Examples of the "urea" include -NR ¹⁵ CONR ¹⁶ R ¹⁷ wherein R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, -NR ¹⁵ CONHR ¹⁷ wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, a carbon number And more preferably -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), particularly preferably an aralkyl group having 7 or more carbon atoms Do.

Examples of the "urethane group", for example, ^{-NHCOOR 18, -NR 19 COOR 20,} -OCONHR 21, -OCONR 22 R 23 ( where ^{R 18, R 19, R 20} , R 21, R 22 and R ²³ is Each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like are exemplified, and -NHCOOR ¹⁸ , -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ are An aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and more preferably -NHCOOR ¹⁸ , -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 20 carbon atoms, An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms).

Examples of the "group having a radial oxygen atom" include an acetylacetonate group and a crown ether.

Examples of the "hydrocarbon group having 4 or more carbon atoms" include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, More preferably an alkyl group having from 4 to 15 carbon atoms (e.g., an octyl group or a dodecyl group), an aryl group having from 6 to 15 carbon atoms (e.g., a phenyl group or a naphthyl group) An aralkyl group having 7 to 15 carbon atoms (e.g., benzyl group) and the like are particularly preferable.

Examples of the "alkoxysilyl group" include a trimethoxysilyl group, a triethoxysilyl group, and the like.

The organic linking group when the adsorption site binds to the organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 An organic linking group formed from up to 20 sulfur atoms is preferable, and the organic linking group may be unsubstituted or may further have a substituent.

Specific examples of the organic linking group include the following structural units or groups in which the structural units are combined.

When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as methyl and ethyl, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, , An N-sulfonylamide group and an acetoxy group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a halogen atom such as chlorine or bromine; a methoxycarbonyl group; Alkoxycarbonyl groups having 2 to 7 carbon atoms such as a methoxycarbonyl group and a cyclohexyloxycarbonyl group, carbonic ester groups such as cyano group and t-butylcarbonate, and the like.

Among them, A ² is a monovalent organic group containing at least one site selected from 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 desirable.

The A ² is more preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ represents an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, And R &lt; ²⁴ &gt; represents a single bond or an organic linking group of (a + 1) valency. a represents an integer of 1 to 10, a B ¹ may be the same or different.

The adsorption site represented by B ¹ may be the same as the adsorption site constituting A ² in the above-mentioned general formula (1), and preferable examples are also the same.

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

R ²⁴ represents a single bond or (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.

(a + 1) -valent organic linking groups may be selected from 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 Or a group to be formed, and may be unsubstituted or may further have a substituent.

Specific examples of the (a + 1) -valent organic linking group include the following structural units, or groups formed by combining the structural units (which may form a ring structure).

R ^{24 is a} single bond or a monovalent organic group consisting of 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 (a + 1), and is preferably a single bond, or a single bond, or a single bond, or a single bond, or an alkylene group having 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, More preferably 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 5 carbon atoms, (A + 1) -valent organic linking group formed from 1 to 30 hydrogen atoms and 0 to 5 sulfur atoms is particularly preferable.

When the (a + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, An alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

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

Examples of the divalent organic linking group include a group formed from 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 And may be unsubstituted or may further have a substituent.

Specific examples of the divalent organic linking group include groups in which the following structural units or the structural units are combined.

R ⁴ and R ^{5 are each a} single bond or a single bond or an alkylene group having 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 A divalent organic linking group formed from an atom is preferable and a single bond or a divalent organic linking group consisting of 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 More preferably 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, And most preferably a divalent organic connecting group formed from 0 to 5 sulfur atoms.

When the divalent organic connecting group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, An alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as chlorine or bromine, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as a carboxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

In the general formula (I), R ³ represents (m + n) an organic linking group. m + n satisfies 3 to 10.

The (m + n) organic linking group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 Or a group formed from two to twenty sulfur atoms, and may be unsubstituted or may further have a substituent.

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

(m + n) is an organic linking group having 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 sulfur atoms And a group formed from 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur atoms More preferably a group formed from 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 Do.

When the (m + n) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, An alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

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

Of the above specific examples, the most preferable (m + n) organic linking groups from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents are as follows.

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

In the general 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 can be selected from known polymers and the like according to the purpose. The m &lt; ² &gt; P &lt; ² &gt; may be the same or different.

In order to form a polymer skeleton among the polymers, a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer and their modified products or copolymers , A polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer (any of random copolymers, block copolymers and graft copolymers), etc.) And more preferably at least one member selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof, Copolymers are particularly preferred.

The polymer is preferably soluble in an organic solvent. When the affinity with an organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium becomes weak, and it may become impossible to secure a sufficient adsorption layer for dispersion stabilization.

In the present invention, it is preferable that the polymer skeleton represented by P ² has at least one acidic group.

The means for introducing an acidic group into the polymer skeleton is not particularly limited and means can be taken by means of a vinyl monomer having an acidic group or a means of introducing an acidic group by using a crosslinkable side chain. The structure in which the skeleton is composed of a structural unit derived from a vinyl monomer having an acidic group and thus an acidic group is introduced is preferable from the viewpoint of ease of control of the amount of introduction of the acidic group and synthesis cost.

Here, the &quot; acidic group &quot; includes those exemplified as &quot; acidic group &quot; in the description of A ² above, and is preferably a carboxyl group.

Examples of the vinyl monomer include, but not limited to, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, Acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, and vinyl monomers having an acidic group.

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

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (Meth) acrylic acid dodecyl, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ) 2- (2-methoxyethoxy) ethyl acrylate, 3-phenoxy-2-hydroxypropyl (meth) Methacrylic acid-2-chloroethyl, glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, (meth) acrylate, Acrylate, propyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylate, (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, nonylphenyl (meth) acrylate, (Meth) acrylate, trifluorobutyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl Oxyethyl, (meth) acrylic acid-gamma -butyrolactone, and the like.

Examples of the crotonic acid esters include butyl crotonate, hexyl crotonate, and the like.

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

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

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

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (Meth) acrylamide, N, N-butyl (meth) acrylamide, Nt-butyl Acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N- (Meth) acryloylmorpholine, diacetone acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, (Meth) acrylamide, and the like.

Examples of the styrene include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromo Styrene, chloromethylstyrene, hydroxystyrene protected with a group capable of being deprotected by an acidic substance (e.g., t-Boc), methyl vinylbenzoate, and? -Methylstyrene.

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

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

Examples of the olefins include ethylene, propylene, isobutylene, butadiene, and isoprene.

Examples of the maleimide include maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide and the like.

(Meth) acrylonitrile, a vinyl group-substituted heterocyclic group (e.g., vinylpyridine, N-vinylpyrrolidone, vinylcarbazole and the like), N-vinylformamide, N-vinylacetamide, Dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and the like.

In addition to the above compounds, vinyl monomers having functional groups such as urethane groups, urea groups, sulfonamide groups, phenol groups and imide groups can also be used. Such a urethane group or urea group-containing monomer can be suitably synthesized, for example, by using an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction of an isocyanate group-containing monomer with a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or an addition reaction between a hydroxyl group-containing monomer or a monomer containing a primary or secondary amino group and a monoisocyanate And can be suitably synthesized by an addition reaction or the like.

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

Examples of the vinyl monomer having an acidic group include vinyl monomers having a carboxyl group and vinyl monomers having a sulfonic acid group.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone mono Methacrylate) can also be used. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as a precursor of the carboxyl group. Among them, (meth) acrylic acid is particularly preferable from the viewpoint of copolymerization, cost, solubility and the like.

As vinyl monomers having sulfonic acid group, 2-acrylamide-2-methylpropane sulfonic acid and the like can be given. As vinyl monomers having a phosphoric acid group, mono (2-acryloyloxyethyl ester) phosphate, mono (1- 2-acryloyloxyethyl ester) and the like.

As the vinyl monomer having an acidic group, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group may also be used.

When the polymer skeleton P ² contains a structural unit derived from a vinyl monomer containing an acidic group, the content of the structural unit derived from a vinyl monomer having an acidic group in the polymer skeleton is preferably from 3 mol% to 40 mol%, more preferably from 5 mol% By mole to 20% by mole.

Most preferably all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below among the polymer compounds represented by the general formula (I).

R ³ : In the above Examples (1), (2), (10), (11), (16)

R ^{4 represents a} single bond or a "single bond consisting of 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 carbon atoms, (Which may have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, etc.) having 1 to 20 carbon atoms An aryl group having 6 to 16 carbon atoms, an acyloxy group having 1 to 6 carbon atoms such as a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, etc., You can.

R ^{5 represents a} single bond, an ethylene group, a propylene group, the following group (a), or the following group (b)

In the following groups, R ¹² represents a hydrogen atom or a methyl group, and 1 represents 1 or 2.

P ² : a copolymer of a vinyl monomer having a carboxyl group and another vinyl monomer; Polymers or copolymers of vinyl monomers without acid groups; A polymer which is selected from ester polymers, ether polymers, urethane polymers and modified products thereof and which may contain at least one acidic group

m: 1-3

n: 3 to 6

The content of the acidic group in the binder resin (B-1) in the present invention is suitably determined by the acid value of the (B-1) binder resin. The acid value of the binder resin (B-1) is preferably from 30 to 200 (mgKOH / g), more preferably from 40 to 160 (mgKOH / g) and most 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 exceeds 200 (mgKOH / g), (A) when the pigment is used as the colorant, There is a possibility that the dispersibility and the dispersion stability of the resin composition may be adversely affected.

The molecular weight of the binder resin (B-1) is preferably from 3,000 to 100,000, more preferably from 5,000 to 80,000, and particularly preferably from 7,000 to 60,000 as the weight average molecular weight. When the weight average molecular weight is within the above range, the effect of a plurality of the adsorption sites introduced at the ends of the polymer is sufficiently exerted, and the adsorbent exhibits excellent adsorption on the solid surface, micelle formation ability, and surface activity.

Exemplary compounds of the binder resin (B-1) according to the present invention are exemplified below, but the present invention is not limited thereto, and any structure may be employed as long as it is included in the general formula (I).

The content ratio (p ¹ : p ² ) of the structural unit having a carboxylic acid ester and the structural unit having a carboxyl group in the polymer skeleton in the exemplified compounds of the binder resin (B-1) is 95: To 80: 20.

Among these exemplified compounds, the content ratio of the structural unit having a carboxylic acid ester and the structural unit having a carboxyl group in the polymer skeleton is 90:10 in terms of mass, and the molecular weight is 20,000, Compounds having an acid value of 82 are particularly preferred.

The binder resin (B-1) represented by the general formula (I) can be synthesized by referring to the method described in, for example, Japanese Patent Application Laid-Open No. 2006-278118.

The content of the binder resin (B-1) in the colored photosensitive resin composition of the present invention is preferably in the range of 5% by mass to 70% by mass, more preferably in the range of 10% by mass to 50% by mass relative to the solid content of the colored photosensitive resin composition Is more preferable.

&Lt; (B-2) Binder resin comprising 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) a binder resin comprising a structural unit represented by the following general formula (II) and a structural unit having an acidic group.

[Structural unit represented by general formula (II)

In the general 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.

In the general formula (II), R ¹¹ to R ¹⁵ are each independently preferably 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, , 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. The substituent may be linear, branched or cyclic, and examples thereof include a methyl group, an n-propyl group, an isopropyl group, and a t-butyl group. An alkyl group having 1 to 7 carbon atoms is preferable Do. The aryl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 7 carbon atoms or an aryl group having 5 to 14 carbon atoms, preferably a phenyl group, a furyl group or a naphthyl group.

Of these, preferred as the general formula (II) are those wherein 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.

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

The structural unit represented by the formula (II) in the binder resin (B-2) is preferably contained in the molecule in an amount of 20 mol% or more and 90 mol% or less, more preferably 50 mol% or more and 80 mol% or less , And more preferably from 60 mol% to 80 mol%. When the total amount of the respective structural units in the binder resin is within the above range, the development latitude is improved, the reduction of the film at the time of development after exposure is reduced, and the surface smoothness of the obtained cured film becomes good.

[Structural unit having an acidic group]

The binder resin (B-2) has a structural unit having an acidic group in the molecule.

Examples of the structural unit having an acidic group include a structural unit derived from a carboxyl group-containing unsaturated monomer. Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; An unsaturated polycarboxylic acid having three valencies or more or anhydrides thereof; Mono [(meth) acryloyloxyalkyl] monovalent monocarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] Esters; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate, and the like.

Of these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are each referred to as M-5300 and M-5400 [manufactured by Doagosei Co., And is commercially available.

The carboxyl group-containing unsaturated monomer may be contained singly or two or more kinds in the resin.

Among these structural units, preferable structural units having an acidic group include carboxylic acid, a chalcogen analog of a carboxylic acid, a carbohydralic acid [RC (= NNH ₂ ) OH], a carboximide acid [RC (= NH) acid _{[RS (O) 2 OH]} , sulfinic acid [RS (O) OH], alcohol pensan [RSOH], celecoxib acid _{[RSe (O) 2 OH]} , cell renin acid [RSe (O) OH], celecoxib nensan [RSeOH], structural units derived from phosphoric acid and its acid-related compounds, silicic acid and boric acid analogs, and 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 binder resin (B-2) is preferably from 5 mol% to 50 mol%, more preferably from 10 mol% to 30 mol%. Within this range, the surface smoothness and heat resistance at the time of development are good.

(B-2) The binder resin may contain other structural units in addition to the structural units described above. Examples of other structural units include structural units derived from the following unsaturated monomers.

Styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyl compounds such as ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

Indene such as indene and 1-methylindene;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, methoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) (Meth) acrylate, methoxypropylene glycol (meth) acrylate, Messenger CD propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl Unsaturated carboxylic acid esters such as (meth) acrylate and glycerol mono (meth) acrylate;

Acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, Unsaturated carboxylic acid aminoalkyl esters such as 3-dimethylaminopropyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Unsaturated carboxylic acid oxetanyl esters such as oxetanyl (meth) acrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

(Meth) acrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide,? -Chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide;

Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

Macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane;

These structural units derived from unsaturated monomers may be used singly or in combination of two or more kinds.

Exemplary compounds 1-1 to 1-8 and 2 to 20 of the binder resin (B-2) are shown below. (B-2) The binder resin is not limited to these exemplified compounds.

The weight average molecular weight of the binder resin (B-2) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 50,000, and still more preferably in the range of 10,000 to 400,000. Within this range, developability and linearity of the formed pattern are improved.

The content of the binder resin (B-2) in the colored photosensitive resin composition of the present invention is preferably in the range of 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass relative to the solid content of the colored photosensitive resin composition The range is more preferable.

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

Therefore, the content ratio of the binder resin (B-1) and the binder resin (B-2) based on the mass basis is within the range of the content of each of the binder resins described above in the range of 3: 7 to 7: do.

The colored photosensitive resin composition of the present invention may contain a resin having a structure other than the above-mentioned (B-1) binder resin and (B-2) binder resin which are specific components in the present invention. The resin having a structure other than the binder resin (B-1) and the binder resin (B-2) is preferably a developer used as a binder for the colorant and used in the developing process when the color filter is produced, Is not particularly limited as far as it is soluble in an alkaline developing solution. However, an acrylic copolymer having a carboxyl group is preferable, and a copolymer of an ethylenically unsaturated monomer having at least one carboxyl group and a copolymerizable ethylenically unsaturated monomer desirable.

As specific examples of the resins usable in combination with the binder resin (B-1) and the binder resin (B-2) in the present invention,

(Meth) acrylic acid / methyl (meth) acrylate copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer.

Resins containing an epoxy ring and an oxetane ring as described below may also be used.

Styrene / methacrylic acid / methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / methacrylic acid glycidyl copolymer,

Styrene / acrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate / glycidyl acrylate copolymer,

Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) oxetane / t-butyl methacrylate copolymer,

Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) -3-ethyloxetane / styrene copolymer,

Butadiene / styrene / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / glycidyl methacrylate copolymer,

Butadiene / methacrylic acid / methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / methacrylic acid glycidyl copolymer,

Styrene / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / methacrylic acid-6,7-epoxyheptyl copolymer,

Styrene / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl copolymer,

t-butyl methacrylate / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl copolymer,

Styrene / methacrylic acid / methyl methacrylate / glycidyl methacrylate copolymer,

p-methoxystyrene / methacrylic acid / cyclohexyl acrylate / glycidyl methacrylate copolymer.

&Lt; (C) Polymerizable compound >

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

The polymerizable compound usable in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one terminal ethylenic unsaturated bond, preferably at least two terminal ethylenic unsaturated bonds. Such a group of compounds is widely known in the relevant industrial field, and in the present invention, these compounds can be used without any particular limitation. They have chemical forms such as, for example, monomers, prepolymers, i.e. dimers, trimer and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof and amides thereof, An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used.

Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxide, and a monofunctional or polyfunctional carboxyl A dehydration condensation reaction product with an acid, and the like are also suitably used. In addition, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of a monofunctional or polyfunctional alcohol, an amine or a thiol, or a halogen group, Unsaturated carboxylic acid esters or amides having a sex substituent and substitution reaction products of mono- or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a group of compounds using unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di Acrylate, trimethylol ethane tri (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di ) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol (Meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (Meth) acrylate oligomer, isocyanuric acid EO-modified tri (meth) acrylate, tri (meth) acryloyloxyethyl isocyanurate, polyester (meth)

(Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol propane tri (meth) acryloyloxypropyl ether, bisphenol A di (meth) acrylate, Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (metha) acrylate, pentaerythritol tri ) Acrylate, pentaerythritol tetraacrylate EO-modified product, and dipentaerythritol hexaacrylate EO-modified product.

Examples of itaconic acid esters include ethylene glycol diacetonate, propylene glycol diacetonate, 1,3-butanediol diacetonate, 1,4-butanediol diacetonate, tetramethylene glycol diacetonate, pentaerythritol diacetonate, sorbitol tetra- And Nate. Examples of the crotonic acid ester include ethylene glycol dichlonate, tetramethylene glycol dichlonate, pentaerythritol dichlonate, and sorbitol tetradecrhotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-A-51-47334 and JP-A-57-196231, JP-A 59-5240, JP-A- Those having an aromatic skeleton described in JP-A-59-5241, JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are preferably used.

Specific examples of the amide monomer of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebisacrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis- Methacrylamide, diethylenetriamintris acrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, and the like. Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726.

Also, urethane-based addition polymerizable compounds prepared by the addition reaction of isocyanate and hydroxyl group are also preferable. As specific examples thereof, there can be mentioned, for example, compounds having two or more isocyanate groups in one molecule described in Japanese Patent Publication No. 48-41708 , A vinyl urethane compound having two or more polymerizable vinyl groups in a molecule to which a vinyl monomer having a hydroxyl group represented by the following general formula (V) is added, and the like can be given.

In general formula (V)

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (V)

(Provided that R ⁴ and R ⁵ each independently represent H or CH ₃ )

Also, urethane acrylates described in JP-A-51-37193, JP-A-2-32293, JP-A-2-16765, JP-A-58-49860, The urethane compounds having an ethylene oxide skeleton described in JP-A-56-17654, JP-A-62-39417 and JP-A-62-39418 are also preferable. Further, addition-polymerizable compounds having an amino structure or sulfide structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 1-105238 A photopolymerizable composition having a very high sensitivity can be obtained.

Other examples include polyester acrylates, epoxy resins, and epoxy resins described in JP-A-48-64183, JP-A-49-43191, JP-A-52-30490 Epoxy acrylates obtained by reacting methacrylic acid with methacrylic acid, and the like. Specific unsaturated compounds described in JP-B-46-43946, JP-A-1-40337 and JP-A-1-40336, and those disclosed in JP-A-2-25493 Vinyl phosphonic acid-based compounds and the like. In addition, in either case, a structure containing the perfluoroalkyl group described in JP-A-61-22048 is preferably used.

UA-306, UA-306T, UA-306I, AH-600, T-600, UA- AI-600 (Kyocera Corporation) is preferred.

Also, 20, No. 7, pages 300 to 308 (1984), which are incorporated herein by reference, as photo-curable monomers and oligomers.

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

Examples of the compound containing 5 or more and 15 or less polymerizable groups in the molecule include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) , U-6HA, U-15HA, UA-32P, UA-7200 (manufactured by Shin Nakamura Kagaku Co., Ltd.) and TO-2248, 2349 and 1382 (manufactured by Doagosei Co., Ltd.). Further, it is also possible to use at least one monomer selected from the group consisting of neopentyl glycol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligomer (meth) acrylate, trimethylol propane oligo (Meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate. Examples of such oligomers include compounds having a molecular weight of 1000 To 5,000.

(Meth) acrylate, trimethylol propane PO (propylene oxide) modified tri (meth) acrylate, trimethylolpropane EO (ethylene oxide), and the like. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylol methane tetra Propane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (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 1 to 4 polymerizable groups in the molecule is used, a compound containing 5 or more and 15 or less polymerizable groups in the molecule and 1 Or more and 4 or less is preferably a compound containing 5 or more and 15 or less polymerizable groups in the molecule and a compound containing 1 to 4 or less polymerizable groups in the molecule in a ratio of 60:40 to 95: , And more preferably in the range of from 70:30 to 90:10.

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

When the curing temperature is in the range, the heat resistance of the cured film becomes good, and surface roughness after development and generation of wrinkles after post-baking are effectively suppressed.

In the colored photosensitive resin composition of the present invention, the mass ratio of the (D) photopolymerization initiator / (C) polymerizable compound to the polymerizable compound (C) and the oxime-based photopolymerization initiator (D) Preferably 0.1 or more and 1.0 or less, and particularly preferably 0.3 or more and 0.9 or less. Within the above range, the pattern forming property is good and the adhesion with the substrate is excellent. Further, the thickness of the mask after exposure and development is sufficient, and pattern separation is suppressed.

<(D) Oxime-based photopolymerization initiator>

As the oxime-based photopolymerization initiator (D) in the present invention, any of conventionally known compounds having an oxime ester structure and initiating and promoting polymerization of the above-mentioned (C) polymerizable compound can be used without any limitation, and oxime ester compounds and Keto oxime compounds and the like. Specific examples thereof include a ketoxime photopolymerization initiator represented by the following general formula (III), a oxime-based photopolymerization initiator represented by the following general formula (D-1) described in Japanese Patent Application Laid-Open No. 2005-220097, Oxime-based photopolymerization initiator described in JP-A-2006-516246, etc. From the viewpoint of curing sensitivity and inhibition of coloring after post-baking, a ketoxime photopolymerization initiator represented by the following general formula (III) is preferable.

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

In the general 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 of 0 to 5; When a plurality of X's are present, a plurality of X's each independently represent a monovalent substituent.

The monovalent substituent represented by R is preferably a monovalent non-metallic atom shown below.

Examples of the monovalent nonmetal atomic group represented by R include 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 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 acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, A carbonyl group, a phosphinoyl 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, And a dialkylaminothiocarbonyl group which may have a substituent.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, N-butyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, cyclopentyl, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluoro-4-methylphenacyl group, 4-methylphenoxyphenacyl group, Phenanthryl group, phenacyl group, 3-trifluoromethylphenacyl group and 3-nitrophenacyl group.

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-anthryl group, A naphthacenyl group, a 5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, o-, m- and p- , m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, teraphthanyl group, quaternaphthalenyl group, heptarenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, A phenanthryl group, a phenanthryl group, an anthryl group, a biantracenyl group, a teranthracenyl group, a quateranthracenyl group, an anthraquinolyl group, a phenanthryl group, a triphenylenyl group, A naphthacenyl group, a naphthacenyl group, a pheadenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexyl group Hexenyl group, ruby and the like hexenyl group, a co-Ro group, tri tilre naphthyl group, a heptadecyl group, a heptadecyl hexenyl group, a pyran group Trail, Oh ballet group.

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 and a styryl group.

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, and a propargyl group.

The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a hexylsulfinyl group, Hexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, A 2-methoxyphenylsulfinyl group, a 2-methoxyphenylsulfinyl group, a 3-chlorophenylsulfinyl group, a 3-trifluoromethylphenylsulfinyl group, a 3-cyanophenylsulfinyl group, a 3-nitrophenylsulfinyl group, Phenylphenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, Nylon and the like.

The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, A hexylsulfonyl group, an octylsulfonyl group, a 2-ethylhexylsulfonyl group, a decanoylsulfonyl group, a dodecanoylsulfonyl group, an octadecanoylsulfonyl group, a cyanomethylsulfonyl group, a methoxymethylsulfonyl group, a perfluoroalkylsulfonyl group And the like.

The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, A 2-methoxyphenylsulfonyl group, a 3-chlorophenylsulfonyl group, a 3-trifluoromethylphenylsulfonyl group, a 3-cyanophenylsulfonyl group, a 3-nitrophenylsulfone group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, Nylon and the like.

The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, and examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, A 2-chlorobenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2- A 2-butoxybenzoyl group, a 3-chlorobenzoyl group, a 3-trifluoromethylbenzoyl group, a 3-cyanobenzoyl group, a 3-nitrobenzoyl group, a 4-fluorobenzoyl group, Norbornyl group, 4-methoxybenzoyl group 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, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, An octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

Examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4- phenylsulfanylphenyloxycarbonyl group, Butoxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2- A 3-nitrophenyloxycarbonyl group, a 4-fluorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, a 4-methoxyphenyloxycarbonyl group and the like can be given .

As the phosphinoyl group which may have a substituent, a phosphinoyl group having 2 to 50 carbon atoms in total is preferable, and examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, a diphenylphosphinoyl group, A phosphinoyl group, a diethoxyphosphinoyl group, a dibenzoylphosphinoyl group, and a bis (2,4,6-trimethylphenyl) phosphinoyl group.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocycle including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. For example, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienyl, furyl, An imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group, an isoindolyl group, a 3H-indole group A quinolinyl group, a quinolinyl group, a quinolinyl group, a quinolinyl group, a quinolinyl group, a quinolyl group, a quinolyl group, a quinolyl group, a quinolyl group, , A pyrimidinyl group, a phenanthrolinyl group, a phenazinyl group, a phenarsaazinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, , Isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl , Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, And a trityl group.

Examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, a trifluoromethylthiocarbonyl group and the like .

Examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, a 4-phenylsulfanylphenylthiocarbonyl group, a 4-dimethylaminophenylthiocarbonyl group, A 2-chlorophenylthiocarbonyl group, a 2-chlorophenylthiocarbonyl group, a 2-methoxyphenylthiocarbonyl group, a 2-butoxyphenylthiocarbonyl group, a 3- chlorophenylthiocarbonyl group, Thiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group and 4-methoxyphenylthiocarbonyl group.

Examples of the dialkylaminocarbonyl group which may have a substituent include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group and a dibutylaminocarbonyl group.

Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group and a dibutylaminothiocarbonyl group.

The R is preferably an unsubstituted or substituted acyl group from the viewpoint of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group or a toluyl group having an unsubstituted or substituted group is preferable.

Examples of the substituent include groups represented by the following structural formulas, and among them, any one of (d-1), (d-4) and (d-5) is preferable.

Examples of the divalent organic group represented by A include alkylene having 1 to 12 carbon atoms, which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent.

Examples of the substituent that can be introduced into these groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, An alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group or an acyloxy group such as an aryloxycarbonyl group, an acetoxy group, a propionyloxy group or a benzoyloxy group, an acetyl group, a benzoyl group , An alkylsulfanyl group such as an isobutyryl group, an acryloyl group, a methacryloyl group or a methoxyl group, an alkylsulfanyl group such as a methylsulfanyl group or a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group or a p- An alkylamino group such as a methylamino group and a cyclohexylamino group, a dialkylamino group such as a dimethylamino group, a diethylamino group, a morpholino group and a piperidino group, a phenylamino group, a p-tolylamino group An alkyl group such as methyl group, ethyl group, tert-butyl group and dodecyl group, an aryl group such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, and phenanthryl group A hydroxyl group, a carboxy group, a formyl group, a mercapto group, a sulfo group, a mesyl group, a p-toluenesulfonyl group, an amino group, a nitro group, a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, A phosphono group, a trimethylammonium group, a dimethylsulfonium group, and a triphenylphenacylphosphonium group.

Above all, A is preferably an alkylene group substituted by an unsubstituted alkylene group, an alkyl group (e.g., methyl group, ethyl group, tert-butyl group or dodecyl group) from the viewpoint of increasing the sensitivity and inhibiting coloration by heating, An alkyl group substituted with a vinyl group (e.g., a vinyl group or an allyl group), an aryl group (e.g., a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group, ) Is preferable.

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

Specifically, Ar represents a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, An azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, o-, m- and p-tolyl groups, a xylyl group, o-, m-, and p- An acenaphthyl group, an acenaphthyl group, an acenaphthyl group, a phenanthrenyl group, a phenanthrenyl group, a phenanthrenyl group, an acenaphthyl group, a phenanthryl group, A phenanthryl group, a phenanthryl group, a pyrenyl group, a clicenyl group, a naphthacenyl group, a playadenyl group, a naphthacenyl group, a naphthacenyl group, a thienyl group, A phenanthryl group, a phenanthryl group, a perynyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, , And the like cyclohepta hexenyl group, a pyran group Trail, Oh ballet group. Of these, a substituted or unsubstituted phenyl group is preferred in view of increasing the sensitivity and inhibiting coloration due to heating over time.

When the phenyl group has a substituent, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a tert- Aryloxy groups such as methylthioxy, ethylthioxy and tert-butylthioxy, arylthioxy groups such as phenylthioxy, p-tolylthioxy and the like , An alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group, or an aryloxycarbonyl group, an acyloxy group such as an acetoxy group, a propionyloxy group or a benzoyloxy group, an acetyl group, a benzoyl group, an isobutyryl group, An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group, a methylamino group, a cyclopentyl group A dialkylamino group such as a dimethylamino group, a diethylamino group, a morpholino group and a piperidino group, an arylamino group such as a phenylamino group and a p-tolylamino group, an ethylamino group, an ethylamino group, a tert-butylamino group and a dodecylamino group An alkyl group, a hydroxyl group, a carboxy group, a formyl group, a mercapto group, a sulfo group, a mesyl group, a p-toluenesulfonyl group, an amino group, a nitro group, a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, , A phosphono group, a trimethylammonium group, a dimethylsulfonium group, and a triphenylphenacylphosphonium group.

In the general formula (III), the structure of "SAr" formed of S adjacent to Ar is preferable from the viewpoint of sensitivity as long as it has the structure shown below.

Examples of the monovalent substituent represented by X include 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 alkylthio group which may have a substituent, an arylthio group which may have a substituent, a halogenated alkyl group which may have a substituent, an amide group which may have a substituent on the N-atom, An alkylsulfinyl group which may have a substituent, an arylsulfinyl 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 acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, A carbonyl group which may have a substituent, a sulfamoyl group which may have a substituent, an amino group which may have a substituent, a phosphinoyl group which may have a substituent, a heterocyclic group which may have a substituent, .

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, Butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2- 4-methylphenacyl group, 2-methylphenacyl group, 3-fluoro-4-methylphenacyl group, 4-methylphenoxyphenacyl group, Phenanthryl group, phenacyl group, 3-trifluoromethylphenacyl group and 3-nitrophenacyl group.

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-anthryl group, A naphthacenyl group, a 5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, o-, m- and p- , m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, teraphthanyl group, quaternaphthalenyl group, heptarenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, A phenanthryl group, a phenanthryl group, an anthryl group, a biantracenyl group, a teranthracenyl group, a quateranthracenyl group, an anthraquinolyl group, a phenanthryl group, a triphenylenyl group, A naphthacenyl group, a naphthacenyl group, a pheadenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexyl group Hexenyl and the like groups, ruby hexenyl group, a nose Ro group, tri tilre naphthyl group, a heptadecyl group, a heptadecyl hexenyl group, a pyran group Trail, Oh ballet group.

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 and a styryl group.

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, and a propargyl group.

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, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec- A butoxy group, a butoxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, a dodecyloxy group, an octadecyloxy group, A 2-ethylhexyloxycarbonylmethyloxy group, an aminocarbonylmethyloxy group, an N, N-dibutylaminocarbonylmethyloxy group, an N-methylaminocarbonylmethyloxy group, An N-octylaminocarbonylmethyloxy group, an N-methyl-N-benzylaminocarbonylmethyloxy group, a benzyloxy group, and a cyanomethyloxy group.

The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, and examples thereof include a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, A 2-methoxyphenyloxy group, a 3-chlorophenyloxy group, a 3-trifluoromethylphenyloxy group, a 3-cyanophenyloxy group, a 3-nitrophenyloxy group, a 4 A 4-methoxyphenyloxy group, a 4-dimethylaminophenyloxy group, a 4-methylsulfanylphenyloxy group, a 4-phenylsulfanylphenyloxy group, or the like can be used. .

The alkylthioxy group which may have a substituent is preferably an alkylthioxy group having 1 to 30 carbon atoms, and examples thereof include a methylthioxy group, an ethylthioxy group, a propylthioxy group, an isopropylthioxy group, a butylthioxy group Butylthioxy group, a tert-butylthioxy group, a pentylthioxy group, an isopentylthioxy group, a hexylthioxy group, a heptylthioxy group, an octylthioxy group, a 2-ethyl Hexylthio group, decylthio group, dodecylthio group, octadecylthio group, benzylthio group and the like.

The arylthioxy group which may have a substituent is preferably an arylthioxy group having 6 to 30 carbon atoms, and examples thereof include a phenylthioxy group, a 1-naphthylthioxy group, a 2-naphthylthioxy group, A 2-methoxyphenylthioxy group, a 2-methoxyphenylthioxy group, a 3-chlorophenylthioxy group, a 3-trifluoromethylphenylthioxy group, a 3-cyano A 4-fluorophenylthioxy group, a 4-methoxyphenylthioxy group, a 4-dimethylaminophenylthioxy group, a 3-nitrophenylthioxy group, 4-methylsulfanylphenylthioxy group, 4-phenylsulfanylphenylthioxy group, and the like.

The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, and examples thereof include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, Oxo group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, Hexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, and examples thereof include phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2 A 2-methoxyphenylsulfanyl group, a 3-chlorophenylsulfanyl group, a 3-trifluoromethylphenylsulfanyl group, a 3-cyanophenylsulfanyl group, a 3-nitrophenylsulfanyl group, Phenylphenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, Nylon and the like.

The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a hexylsulfinyl group, Hexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, A 2-methoxyphenylsulfinyl group, a 2-methoxyphenylsulfinyl group, a 3-chlorophenylsulfinyl group, a 3-trifluoromethylphenylsulfinyl group, a 3-cyanophenylsulfinyl group, a 3-nitrophenylsulfinyl group, Phenylphenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, Nylon and the like.

The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, A hexylsulfonyl group, an octylsulfonyl group, a 2-ethylhexylsulfonyl group, a decanoylsulfonyl group, a dodecanoylsulfonyl group, an octadecanoylsulfonyl group, a cyanomethylsulfonyl group, and a methoxymethylsulfonyl group.

The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, A 2-methoxyphenylsulfonyl group, a 3-chlorophenylsulfonyl group, a 3-trifluoromethylphenylsulfonyl group, a 3-cyanophenylsulfonyl group, a 3-nitrophenylsulfone group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-fluorophenylsulfinyl group, Nylon and the like.

The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, and examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, A 2-chlorobenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2- A 2-butoxybenzoyl group, a 3-chlorobenzoyl group, a 3-trifluoromethylbenzoyl group, a 3-cyanobenzoyl group, a 3-nitrobenzoyl group, a 4-fluorobenzoyl group, Norbornyl group, 4-methoxybenzoyl group 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, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, A 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4-phenylsulfanyloxycarbonyl group, a 4-methylsulfanyloxycarbonyl group, a 4-methylsulfanyloxycarbonyl group, A 4-dimethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group, a 2-methoxyphenyloxycarbonyl group, a 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyl Oxycarbonyl group, and 3-cyano-phenyl-oxy group, a 3-nitrophenyl oxycarbonyl group, 4-fluoro-phenyl-oxy group, a 4-cyanophenyl-oxy group, a 4-methoxy phenyloxy group.

The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms in total, and examples thereof include N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2 (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N, N-diep And the like can be a carbamoyl group.

The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms in total, and examples thereof include sulfamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, N, A pamoyl group, an N, N-diarylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group and the like. More specifically, there may be mentioned N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-butylsulfamoyl, N-hexylsulfamoyl, N-cyclohexylsapamoyl, N- N-phenylsulfamoyl group, N-2-methylphenylsulfamoyl group, N-2-methylphenylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N- N-2-methoxyphenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3- N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanyl group Phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N - diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total and includes, for example, -NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N-sulfonylamino group, Dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, it is preferable to use N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N-tert- butylamino, N-hexylamino, N-cyclohexylamino, N N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N-2-ethylhexylamino group, N- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3- N-4-methylphenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylphenylamino group, N-4- Phenylamino group, an N, N-dimethylamino group, an N, N-dimethylamino group, N, N-dibenzylamino, N, N-dibutylcarbonylamino, N, N-dibenzylamino, (Dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, A 5-dimethyl morpholino group, and a carbazole group.

As the phosphinoyl group which may have a substituent, a phosphinoyl group having 2 to 50 carbon atoms in total is preferable, and examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, a diphenylphosphinoyl group, A phosphinoyl group, a diethoxyphosphinoyl group, a dibenzoylphosphinoyl group, and a bis (2,4,6-trimethylphenyl) phosphinoyl group.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocycle including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. For example, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienyl, furyl, An imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group, an isoindolyl group, a 3H-indole group A quinolinyl group, a quinolinyl group, a quinolinyl group, a quinolinyl group, a quinolinyl group, a quinolyl group, a quinolyl group, a quinolyl group, a quinolyl group, , A pyrimidinyl group, a phenanthrolinyl group, a phenazinyl group, a phenarsaazinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, , Isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl , Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, And a trityl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group.

Examples of the amide group which may have a substituent on the N-phase include an N, N-dimethyl amide group and an N, N-diethyl amide group.

Examples of the alkyl group which may have a substituent, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the alkoxy group which may have a substituent, An alkylthio group which may have a substituent, an arylthio group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl 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 acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent Or an aryloxycarbonyl group, a carbamoyl group which may have a substituent, a sulfamoyl group which may have a substituent, an amino which may have a substituent Or a heterocyclic group which may have a substituent may be substituted with another substituent.

Examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a tert-butoxy group, an aryloxy group such as a phenoxy group or a p- An alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group or an acyloxy group such as an aryloxycarbonyl group, an acetoxy group, a propionyloxy group or a benzoyloxy group, an acetyl group, a benzoyl group, An alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group, an alkylsulfinyl group such as a methylamino group, Alkylamino groups such as cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino group such as phenylamino group and p-tolylamino group , An alkyl group such as a methyl group, an ethyl group, a tert-butyl group or a dodecyl group, an aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group or a phenanthryl group, A sulfonyl group, a phosphino group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, A trimethylammonium group, a dimethylsulfonium group, a triphenylphenacylphosphonium group and the like.

Among them, X preferably has 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, a substituent An aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, an arylthioxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amino group which may have a substituent, or An amide group which may have a substituent on the N-phase is preferable, and among these, an alkyl group which may have a substituent is more preferable.

In the general formula (III), n represents an integer of 0 to 5, but from the viewpoint of ease of synthesis, an integer of 0 to 3 is preferable, and an integer of 0 to 2 is more preferable.

When a plurality of Xs exist in the general formula (III), the plurality of Xs may be the same or different.

Specific examples of the photopolymerization initiator represented by the above general 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 range of 250 nm to 500 nm. And more preferably an absorption wavelength in a wavelength range of 300 nm to 380 nm. Particularly, it is preferable that the absorbance at 308 nm and 355 nm is high.

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

The colored photosensitive resin composition of the present invention may contain, in addition to the oxime-based photopolymerization initiator (D) described above, another photopolymerization initiator (hereinafter referred to as (D) a photopolymerization initiator D-2) other photopolymerization initiator].

As the other photopolymerization initiator (D-2) having a different structure from the (D) oxime-based photopolymerization initiator, those conventionally known can be used as long as they are compounds which initiate and accelerate the polymerization of the polymerizable compound (C). Specifically, there may be mentioned, for example, a photopolymerization initiator such as a ropin type photopolymerization initiator, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a coumarin compound, , Metallocene compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide) compounds and the like.

(D-2) As the ropin-based photopolymerization initiator that can be used as another photopolymerization initiator, for example, a hexaaryl biimidazole compound can be mentioned. Examples of the hexaarylbimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2- (4-ethoxycarbonylphenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5 (4-phenoxycarbonylphenyl) imidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis , 6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-cyanophenyl) Bis (4-ethoxycarbonylphenyl) imidazole, 2,2'-bis (2-cyanophenyl) -4,4 ', 5,5'-tetrakis - phenoxycarbonylphenyl) biimidazole, (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis , 4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetrakis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) bimidazole, 2'- (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis 4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-phenylphenyl) (4-methoxycarbonylphenyl) imidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis , 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl)

Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra- (4-methoxyphenyl) biimidazole, 2,2'-bis , 4 ', 5,5'-tetra- (3-methoxyphenyl) imidazole, 2,2'-bis (2-chlorophenyl) 4-dimethoxyphenyl) bimidazole,

Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4' Bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dicyanophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-tricyanophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2 , 2'-bis (2,4-dimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-trimethylphenyl) ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-diethylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'- Bis (2,4,6-triethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-diphenylphenyl) Tetraphenylbiimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Bis (2-fluorophenyl) -4,4 ', 5,5'-tetra And the like can be mentioned phenyl biimidazole.

Particularly preferred compounds among them include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, B-CIM manufactured by Hodogaya Chemical Co., Ltd.) Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra- (3,4-dimethoxyphenyl) biimidazole (for example, HABI 1311 produced by Nihon Sibel Hegnana), 2 , 2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, Kurogane Kasei).

It is also possible to use organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Specific examples of the disulfonic acid compound, onium salt compound and acylphosphine (oxide) compound are described in Wakabayashi et al., "Bull Chem. Soc. Japanese Patent Publication No. 48-36281, Japanese Patent Application Laid-open No. Sho 55-32070, Japanese Patent Application Laid-open No. Hei 11 60-239736, 61-169835, 61-169837, 62-58241, 62-212401 and 62-212401, Japanese Patent Application Laid-Open JP-A-63-70243, JP-A-63-298339, MP Hutt "Journal of Heterocyclic Chemistry" 1 (No 3), (1970), Japanese Patent Publication No. 6-29285, US Pat. No. 3,479,185 4,311,783, 4,622,286, etc., JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686 JP-A-9-188710, JP-A-2000-131837, JP-A- And Japanese Patent Application No. 2000-310808 and Kunz, Martin, "Rad Tech'98. Proceeding April 19-22, 1998, Chicago &quot;, etc., , Japanese Patent Application Laid-Open Nos. 6-157623, 6-175564, 6-175561, 6-175554, 6-175553 , Japanese Patent Application Laid-Open Nos. 9-188710, 6-348011, 7-128785, 7-140589, and 7-306527 , JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP 2000-66385 JP-A-2000-80068, JP-A-2004-534797, etc., I can be given as specific examples.

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

When a specific polymerization initiator (D) or other photopolymerization initiator (D-2) is used as the photopolymerization initiator, a compound having absorption at the exposure wavelength is preferably used as the sensitizer. The sensitizer will be described later.

<(E) Solvent>

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

Examples of the solvent (E) include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, And examples thereof include methyl lactate, methyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, 3-oxypropionic acid alkyl esters (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate) , Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate and the like (For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, Ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate and the like;

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, di Ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, propylene glycol phenyl ether,

Methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol n- Butyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, dipropylene glycol n-butyl ether acetate, dipropylene glycol n-propyl ether acetate, Propylene glycol methyl ether acetate and the like;

Alkoxyalkyl acetates such as 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl- Methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl- , 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

Alcohols such as ethanol, isopropyl alcohol and the like;

Aromatic hydrocarbons such as toluene and xylene.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, , Ethylcarbitol 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 are preferable.

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

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

<(F) sensitizer>

In the colored photosensitive resin composition of the present invention, it is preferable to increase the initiation efficiency of the (D) oxime-based photopolymerization initiator by using a compound having absorption at the exposure wavelength as a sensitizer. The radical generation reaction of the oxime-based photopolymerization initiator component (D) and the polymerization reaction of the polymerizable compound thereby are promoted by the exposure of the wavelength capable of being absorbed by the sensitizer.

Such sensitizers include known spectral sensitizing dyes or dyes, or dyes or pigments which absorb light to interact with photopolymerization initiators.

Preferred spectral sensitizing dyes or dyes which can be used in the present invention include, but are not limited to, polynuclear aromatic compounds (e.g., pyrene, perylene, triphenylene), xanthines (such as fluorescein, eosine, erythrosine, (For example, meloxicans, carbomeric rings), thiazines (for example, thiocarbons such as thiocarbamates Naphthalene, naphthalene, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavine), phthalocyanines (e.g., phthalocyanine, metal phthalocyanine), porphyrins (Such as chloropyridine, central metal substituted chlorophyll), metal complexes, anthraquinones (for example, anthraquinone), squaryliums (for example, squarylium ), And among them, a thiol compound to be described in detail below is preferable.

The thiol compound has an action of further improving the sensitivity to the active radiation of the photopolymerization initiator or inhibiting polymerization inhibition of the polymerizable compound by oxygen.

Examples of the thiol compound include ethylene glycol bis (thio) propionate (EGTP), butanediol bisthiourethionate (BDTP), trimethylolpropane tris (thio) propionate (TMTP), pentaerythritol tetrakisthiopropionate (3H) -quinazoline,? -Mercaptonaphthalene,? - mercapto naphthalene, N-mercaptobenzothiazole, 2-mercaptobenzoimidazole, Phenyl-mercaptobenzimidazole, and the like.

Particularly, monofunctional thiol compounds are preferable from the viewpoints of stability with time and solubility in solvents.

The content of the thiol compound in the colored photosensitive resin composition of the present invention is preferably 0.5% by mass to 10% by mass, based on the total solid content of the photosensitive resin composition, from the viewpoint of improvement in the curing rate due to the polymerization growth rate and balance of chain transfer , And 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 necessary in addition to the essential components (A) to (E) and the preferred combination component (F). Hereinafter, optional additives will be described.

(Surfactants)

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

If the pigment concentration is increased, the tin-firing of the coating liquid generally becomes large, so that the colored photosensitive resin composition is applied or transferred onto the substrate, which tends to cause a film thickness deviation after formation of the colored photosensitive resin composition layer (colored layer coating film). Particularly, in forming the colored photosensitive resin composition layer (colored layer coating film) by the slit coating method, it is important that the coating liquid for forming the colored photosensitive resin composition layer is leveled to form a coating film having a uniform thickness until drying. Therefore, it is preferable to add a suitable surfactant to the colored photosensitive resin composition. As the surfactant, surfactants disclosed in JP-A-2003-337424 and JP-A-11-133600 are preferable.

As the surfactant for improving the coating property, a nonionic surfactant, a fluorinated surfactant, a silicon surfactant and the like are added.

Examples of the nonionic surfactant include polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers , Polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters.

Specific examples include polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; Polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether and polyoxyethylene nonyl phenyl ether; And nonionic surfactants such as polyoxyalkylene dialkyl esters such as polyoxyethylene distearate and polyoxyethylene distearate, sorbitan fatty acid esters and polyoxyalkylene sorbitan fatty acid esters.

Specific examples of these are, for example, adekafluronic series, adecanol series, Tetronic series (manufactured by ADEKA Co., Ltd.), Emulgen series, Leodol series (manufactured by Kao Corporation) (Manufactured by Sanyo Chemical Industries, Ltd.), Pionin series [manufactured by Takemoto Yushi Co., Ltd.], Nissan Nonion series [manufactured by Nippon Oil & Fats Co., Ltd. And so on. Those commercially available can be suitably used. The preferred HLB value is 8-20, more preferably 10-17.

As the fluorine-based surfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of a terminal, a main chain and a side chain may be suitably used.

Specific examples of commercially available products include Mega Pack F142D, Copper F172, Copper F173, Copper F176, Copper F177, Copper F183, Copper F780, Copper F781, Copper F782, Copper F784, Copper F552, Copper F554, Copper R30, (Manufactured by Sumitomo 3M Ltd.), SURFLON S-112, S-FC-431 (manufactured by Sumitomo 3M Ltd.), Fluorad FC-135, FC-170C, 113, S-131, S-141, S-145, S-382, SC-101, SC-102, 106 or more, manufactured by Asahi Glass Co., Ltd., Epson EF351, E 352, E 801, E 802 (manufactured by JEMCO Co., Ltd.).

Examples of the silicon-based surfactant include TORAY Silicon DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ- (Manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF- (Manufactured by Toshiba Silicone Co., Ltd.).

Among them, Megafac F780, F781, F782, F784, F552, and F554 [manufactured by DIC Corporation] are preferable surfactants for the present invention.

These surfactants are used in an amount of preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 0.5 parts by mass or less based on 100 parts by mass of the colored photosensitive resin composition. When the amount of the surfactant is more than 5 parts by mass, stripe or surface roughness in the coating and drying tends to occur, and smoothness tends to deteriorate.

(Thermosetting resin)

The colored photosensitive resin composition of the present invention may optionally contain a thermosetting resin such as an epoxy resin and an oxetane resin.

Examples of the epoxy resin include bisphenol A type, cresol novolak type, biphenyl type, and alicyclic epoxy compound.

Examples of the bisphenol A type include Eptotol YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF- (Manufactured by Nippon Kayaku Co., Ltd.), Fraxel GL-61, GL-62, G101 and G102 (manufactured by Daicel Chemical Industries, Ltd.), DENACOL EX-1101, EX-1102 and EX- ) And the like. In addition to these, bisphenol F-type and bisphenol-S-type resembles to these. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (available from Daicel Chemical Industries, Ltd.) can also be used.

Examples of the cresol novolak type include Epotho YDPN-638, YDPN-701, YDPN-702, YDPN-703 and YDPN-704 (manufactured by Toko Kasei Co., Examples of the biphenyl type include 3,5,3 ', 5'-tetramethyl-4,4'-diglycidylbiphenyl.

Examples of the alicyclic epoxy compounds include Celloxides 2021, 2081, 2083 and 2085, Epolide GT-301, GT-302, GT-401, GT-403 and EHPE- 3150 3000, ST-4000, ST-5080, ST-5100 and the like (manufactured by TOKO KASEI). In addition, epoxy type YH-434, YH-434L which is amine type epoxy resin, glycidyl ester which is modified with dimer acid of skeleton of bisphenol A type epoxy resin, and the like can also be used.

Of these epoxy resins, novolak-type epoxy compounds and alicyclic epoxy compounds are preferable, and epoxy equivalents of 180 to 250 are particularly preferable. Examples of such materials include Epiclon N-660, N-670, N-680, N-690 and YDCN-704L (manufactured by DIC Corporation) and EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.).

As the oxetane resin, Aromoxetane OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ and PNOX (available from Doagosei Co., Ltd.) can be used.

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

The content of the epoxy resin and the oxetane resin in the colored photosensitive resin composition according to the present invention is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total solid content of the colored photosensitive resin composition, And adhesion between the substrate and the substrate.

(Organic carboxylic acid)

When accelerating the alkali solubility of the uncured portion and improving the developability of the colored photosensitive resin composition, it is possible to add an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and caprylic acid; There may be mentioned oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, , Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemellitic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melotropic acid and pyromellitic acid; Other carboxylic acids such as phenylacetic acid, phenoxyacetic acid, methoxyphenoxyacetic acid, hydrathropic acid, hydrocipic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylideneacetic acid, .

(Silane coupling agent)

A silane coupling agent can be used in the colored photosensitive resin composition of the present invention from the viewpoint of better adhesion with a substrate.

The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group capable of chemically bonding with an inorganic material. (Meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group are preferable as such groups Among them, those having a (meth) acryloyl group or a glycidyl group are preferable.

That is, the silane coupling agent used in the present invention is preferably a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group, and more specifically, a (meth) acryloyl-trimethoxysilane compound having the following structure, Glycidyl-trimethoxysilane compounds, and the like.

When the silane coupling agent is used, the addition amount is preferably in the range of 0.2% by mass to 5.0% by mass, more preferably 0.5% by mass to 3.0% by mass in the total solid content in the colored photosensitive resin composition used in the present invention.

(Polymerization inhibitor)

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

Examples of the thermal polymerization inhibitor usable in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine cetylium salt, phenoxazine, phenothiazine And the like.

The addition amount of the thermal polymerization inhibitor is preferably 0.01% by mass to 5% by mass with respect to the colored photosensitive resin composition.

If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and it may be localized on the surface of the photosensitive layer during drying after application. The addition amount of the higher fatty acid derivative is preferably 0.5% by mass to 10% by mass of the colored photosensitive resin composition.

(Plasticizer)

In the present invention, an inorganic filler, a plasticizer and the like may be added to improve the physical properties of the colored photosensitive resin composition.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetyl glycerin. (C) Polymerization Based on the total mass of the positive-working compound and the binder resin, in an amount of 10 mass% or less.

The colored photosensitive resin composition of the present invention can be cured by conventionally known exposure means. Among them, the colored photosensitive resin composition cures with high sensitivity by exposure to ultraviolet light and exhibits high adhesion to the substrate. As the exposure means for the ultraviolet light, any of the laser exposure method and the proxyimate exposure method may be used, but from the viewpoint of suppressing the surface reticulation, the laser exposure method is preferable. The colored photosensitive resin composition of the present invention can be preferably used for forming a coloring pattern of a color filter.

«Pattern formation method, color filter and method of manufacturing the same»

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

The pattern forming method of the present invention comprises a colored layer forming step of applying a colored photosensitive resin composition of the present invention to a substrate to form a colored layer, a step of exposing the colored layer to ultraviolet light in a pattern shape, And a developing step of developing the colored layer on which the latent image is formed to form a pattern. If necessary, a step of baking the colored layer (prebaking step) and a step of baking the developed colored layer (baking step) may be formed. These processes may be collectively referred to as a pattern forming process.

[Coloring layer forming step]

The coloring layer forming step in the present invention is a step of forming a colored layer by providing the colored photosensitive resin composition of the present invention on a substrate.

Examples of the substrate include a non-alkali glass used for a liquid crystal display device, a soda glass, a borosilicate glass, a quartz glass and a photoelectric conversion element substrate to which a transparent conductive film is attached and a solid-state image pickup element. A plastic substrate can also be used. It is preferable that a black matrix is formed in a lattice shape or the like using these substrates, and a colored pattern is formed in a vacant portion of the lattice.

On the substrate, a subbing layer may be formed, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of the material, or planarize the substrate surface. It is preferable that the substrate is large (approximately 1 m or more on one side) in order to achieve the effect of the present invention.

Examples of the method of imparting the colored photosensitive resin composition of the present invention for forming a colored layer on a substrate include a method of applying by various application such as slit coating, inkjet method, spin coating, pouring, roll coating, Can be applied. In the coating method, slit coating is preferable from the viewpoints of precision and speed.

It is also possible to apply a method of transferring a coated film formed by the above coating method onto a substrate in advance on a substrate.

The transfer method is described in detail in paragraphs [0023], [0036] to [0051] of Japanese Patent Application Laid-Open No. 2006-23696 or in paragraphs [0096] to [0108] of Japanese Patent Application Laid- Method can be suitably used in the present invention.

The colored layer in the present invention is preferably formed so as to have a film thickness after drying of 0.5 to 3.0 탆 in order to obtain a sufficient color reproduction area and sufficient panel brightness, More preferable.

[Drying process]

After the application of the colored photosensitive resin composition is completed, a drying step of drying the solvent by vacuum drying (VCD) may be performed. Further, the colored layer may be obtained by heating and drying (prebaking) the coating film on the substrate.

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

[Exposure step]

The exposure process in the present invention is a process for forming a latent image by exposing the colored layer with a patterned ultraviolet laser and curing the exposed area. By the exposure process of the present invention, the polymerization curing reaction of the polymerizable compound (C) occurs and proceeds in the exposed region of the pattern shape in the colored photosensitive resin composition, (D) And a non-cured area is formed.

As the excitation medium of the laser, a crystal, a glass, a liquid, a coloring matter, a gas and the like can be used, and a laser having an oscillation wavelength in a known ultraviolet region such as a solid laser, a liquid laser, a gas laser and a semiconductor laser can be used. Among them, a solid laser and a gas laser are preferable from the viewpoints of the output of the laser and the oscillation wavelength.

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 in the range of 310 nm to 360 nm, Particularly, a 355 nm wavelength laser exposure method is preferable.

Concretely, the third harmonic (355 nm) of a Nd: YAG laser which is a relatively inexpensive solid laser with a large output, XeCl (308 nm) and XeF (353 nm) of an excimer laser can be suitably used.

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

The ultraviolet laser used in the present invention is preferably a pulse laser oscillating at a frequency of 20 Hz to 2000 Hz from the viewpoint of productivity.

The exposure apparatus usable in the present invention is not particularly limited, and examples of commercially available exposure apparatuses include EGIS (V-Technology Corporation) and DF2200G (Dainippon Screen Corporation). Devices other than those described above are also preferably used.

The ultraviolet laser has good parallelism of light, and pattern exposure can be performed without using a mask at the time of exposure, but the pattern shape is affected by the shape and profile of the output light. Therefore, exposure of the pattern using a mask is preferable because the linearity of the pattern is increased.

[Development process]

The developing step in the present invention is a step of developing the colored layer in which the latent image is formed by the curing in the exposure area to remove the unexposed portion and form a pattern. The exposed area by the ultraviolet laser is cured in a pattern shape, and in the developing process, the alkali developing process is performed to elute and remove the unirradiated area (uncured area) in the alkaline aqueous solution in the above exposure process, The pattern can be formed.

As the developer, an organic alkali developer, an inorganic alkali developer, or a mixture thereof is used.

Examples of the alkali agent for use in the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetra And organic alkaline compounds such as ethyl ammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5.4.0] -7-undecene. 10% by mass, preferably 0.01 to 1% by mass, of an alkaline aqueous solution is preferably used as the developer. When a developer comprising such an alkaline aqueous solution is used, it is generally rinsed with pure water after development.

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

The shower pressure is preferably 0.01 MPa to 0.5 MPa, preferably 0.05 MPa to 0.3 MPa, and more preferably 0.1 MPa to 0.3 MPa. By selecting these conditions, the shape of the pattern can be made rectangular or can be designed as a net taper or arbitrarily.

[Post baking process]

In the present invention, it is preferable to provide a post-baking step of baking the developed colored layer in order to complete curing of the colored photosensitive resin composition. The baking can be carried out by continuously or batchwise heating the substrate having the pattern after developing and rinsing by using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), or a high-frequency heater.

The baking condition is preferably a temperature of 150 to 260 캜, more preferably 180 to 260 캜, and most preferably 200 to 240 캜. The baking time is preferably from 10 minutes to 150 minutes, more preferably from 20 minutes to 120 minutes, most preferably from 20 minutes to 90 minutes.

Further, when forming a coloring pattern of a plurality of colors such as RGB three colors or a light-shielding layer, the cycle of formation of the coloring layer, exposure, development, and baking may be repeated for a desired number of colors, , And the baking may be performed all at once after the developing process. Thus, a color filter having colored pixels of a desired color is produced.

&Quot; Liquid crystal display device &

The color filter of the present invention is preferable for manufacturing a liquid crystal display device, and a liquid crystal display device using the color filter manufactured by the pattern forming method of the present invention can display a high-quality image.

The definition of the display device and the description of each display device are described in, for example, &quot; Electronic display device (Sasaki Akio Kogyo Co., Quot; issued &quot; The liquid crystal display device is described in, for example, &quot; Next Generation Liquid Crystal Display Technology (edited by Utsuda Tatsuo, published by Kogyo Kogyo K. 1994) &quot;. The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various liquid crystal display devices described in the &quot; next generation liquid crystal display technology &quot;.

The color filter for a liquid crystal display device is particularly effective for a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Shotpan Co., Ltd. 1996)". The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as IPS, a pixel division system such as MVA or the like, or a STN, TN, VA, IPS, OCS, FFS and R-OCB . These methods are described, for example, on page 43 of "EL, PDP, LCD DISPLAY - Latest Trends in Technology and Market - (issued by Toray Research Center Research Division, 2001)".

The liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to a color filter. The color filter for a liquid crystal display element of the present invention can be applied to a liquid crystal display apparatus constituted by these known members.

These members are described in, for example, "Market of materials and chemicals around '94 liquid crystal displays (CMC Shimada, published by CMC in 1994)", "2003 Current condition and future prospects of LCD related markets Kichi, Fuji Chimera &lt; / RTI &gt; Suken 2003).

Regarding the backlight, it is described in the SID meeting Digest 1380 (2005) (A. Konno et al), Monthly Display December 2005, pages 18-24 (Yamazaki Shimaya), 25-30 pages (Yagi Takaaki) have.

The color filter fabricated by the pattern forming method of the present invention is used in a liquid crystal display device and can realize high contrast when combined with a conventionally known three-wavelength tube of a cold cathode tube. In addition, a red, green, and blue LED light source RGB -LED) as a backlight, it is possible to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless the scope of the present invention is exceeded. Unless otherwise stated, "%" and "parts" are on a mass basis.

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

A 200-mL three-necked flask equipped with a stirring rod equipped with a stirring blade, a reflux condenser and a thermometer was charged with 54 g of 1-methoxy-2-propanol and heated to 70 캜 under a nitrogen stream. A solution of 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 in 54 g of 1-methoxy-2- was added dropwise into a three-necked flask over a period of 2.5 hours using a plunger pump. After completion of the dropwise addition, the mixture was further stirred at 70 DEG C for 2 hours. After the completion of the heating, the reaction mixture was poured into 1 L of water and refolded. The precipitate was filtered and vacuum dried to obtain 9 g (yield 75%) of a polymer compound.

Measurement of weight average molecular weight 0.01 g of the obtained polymer was weighed into a 10 mL volumetric flask, and about 8 mL of tetrahydrofuran was added and dissolved at room temperature to make the total volume to 10 mL. This solution was measured by gel permeation chromatography (GPC). The weight average molecular weight of the alkali-soluble resin 1 (allyl methacrylate / methacrylic acid copolymer, molar ratio = 80/20, the structure shown below) was 35,000.

&Lt; Synthesis Example 2: Binder Resin B-1-1 >

Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; 7.83 parts of the following structure, manufactured by Sakaikagaku Kogyo Co., Ltd., and 15.57 parts of a compound (A-1) having a carbon-carbon double bond and the following adsorption sites were dissolved in 93.60 parts of dimethylformamide, And heated to 70 ° C. To this was added 0.06 part of 2,2'-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.], and the mixture was heated for 3 hours. Further, 0.06 part of V-65 was added, and the mixture was reacted at 70 DEG C for 3 hours under a nitrogen stream. Subsequently, the solution was cooled to room temperature to obtain a 20% solution of the reaction product of DPMP and Compound A-1.

Further, a mixed solution of 23.4 parts of a 20% solution of the reaction product, 18 parts of methyl methacrylate (MMA; monomer) and 2 parts of methacrylic acid was heated to 80 占 폚 in a nitrogen stream. Then, 0.007 part of 2,2'-azobis (isobutyronitrile) (AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and after heating for 3 hours, 0.007 parts of AIBN was further added and the mixture was heated at 80 ° C And reacted for 3 hours. The mixture was then cooled to room temperature and diluted with acetone. Reprecipitated with a large amount of methanol, and then vacuum-dried to obtain 19 parts of a solid of the polymer compound (B-1-1: weight average molecular weight of 32000 in terms of polystyrene) of the present invention shown below. 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 terms of mass.

[Example 1]

(Preparation of colored photosensitive resin composition)

(1-1 Preparation of Pigment Dispersion 1)

The pigment dispersion 1 was prepared as follows. That is, the components of the composition described below were mixed and stirred for 3 hours at a rotation speed of 3,000 rpm using a homogenizer to prepare a mixed solution. Further, a mixed solution was prepared using a bead dispersing machine Ultra Apex mill using 0.1 mm phi zirconia beads ) For 8 hours.

C. I. Pigment Blue 15: 6 [(A) Colorant] 11.8 parts

C. I. Pigment Violet 23 [(A) Colorant] 1.0 part

· Disperbyk 161 made by Bigukemasa (30% solution) 24 parts

Propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) 63.2 parts

                                                            A total of 100 copies

(1-2. Preparation of Photosensitive Resin Composition)

To the resulting Pigment Dispersion 1 (39.2 parts), the following components were further added and stirred to prepare a photosensitive resin composition for blue (B).

Alkali-soluble resin 1 [(B-2) binder resin] 8.2 parts

Alkali-soluble resin (B-1-1) [(B-1) binder resin] 8.2 parts

(C) Polymerizable compound: dipentaerythritol hexaacrylate

     (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 3.9 parts

(C) Polymerizable compound: tetramethylol methane tetraacrylate

     (NK Ester A-TMMT, manufactured by Shin-Nakamura Kagaku Co., Ltd.) 0.69 part

(D) Oxime photopolymerization initiator: Compound A (the following structure) 2.74 parts

(F) sensitizer [monofunctional thiol compound SH-1 (the following structure)] 0.55 part

Epoxy compound: 0.60 part (EHPE3150, manufactured by Daicel Chemical Industries, Ltd.)

(E) Solvent: 35.9 parts of a mixed solution of propylene glycol methyl ether acetate and ethyl 3-ethoxypropionate (= 80/20 (mass ratio))

Polymerization inhibitor: 0.001 part of p-methoxyphenol

Surfactant 1: Megafack F-554 (manufactured by DIC) 0.02 part

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

The kind and content of (B-1) the binder resin, (A) the colorant, (D) the oxime-based photopolymerization initiator and (B-2) the content ratio of the binder resin in the adjustment of the colored photosensitive resin composition of Example 1 Were changed as shown in the following Tables 1 to 7, the colored photosensitive resin compositions of Examples 2 to 15 and Comparative Examples 1 to 6 were prepared.

In the following table, the numerical values described in the polymerizable compound (C) show the number of functional groups of the polymerizable compound used, and the "ratio" is the ratio of the polymerizable compound having five or more functional groups and the polymerizable compound having one to four functional groups .

- Evaluation of colored photosensitive resin composition -

(Formation of pattern shape pixel)

The colored photosensitive resin compositions of Examples 1 to 15 and Comparative Examples 1 to 6 obtained as described above were coated on a surface of a non-alkali glass substrate (Corning, 1737, 550 mm x 660 mm) with a slit coater (Coloring layer) having a thickness of 2.0 탆 was formed by baking for 120 seconds in a clean oven at 90 캜 to obtain a substrate on which a coating film was formed (coloring Layer forming process).

Subsequently, a pulse of about 1 mJ / cm 2 was applied to the surface of the photosensitive resin composition layer (colored layer) by using EGIS (V-Technology Co., Ltd., third harmonic (355 nm) The irradiation was performed 20 times through a photomask to cure the exposed portion (exposure step).

Thereafter, this substrate was immersed in a 1.0% developer (CDK-1, 1 part by mass) of a potassium hydroxide-based developer CDK-1 (manufactured by Fuji Film Electronics Matrix Co., Ltd.) (25 占 폚) at a pressure of 0.20 MPa for 50 seconds, washed with pure water and then air-dried (developing step). Thereafter, post-baking was performed in a clean oven at 230 캜 for 30 minutes to form a blue stripe-shaped pixel array on the substrate.

(Evaluation of line width sensitivity)

Using a mask having a line-and-space of 20 mu m width, the gap (gap) between the surface of the photosensitive resin composition layer on the substrate on which the coating film was formed and the mask was 200 mu m and exposure was performed at an exposure dose of 20 mJ / cm2. The thus-obtained exposed substrate was subjected to development, cleaning, air drying, and post-baking treatment. The obtained line pattern was observed with an optical microscope, and the line width was measured and evaluated according to the following criteria.

A: 30 탆 or more

B: 27 탆 or more and less than 30 탆

C: 25 탆 or more and less than 27 탆

D: less than 25 탆

E: No pattern is formed. Or peeled off and can not be evaluated.

(Evaluation of linearity)

The line pattern obtained in the evaluation of the line width sensitivity was observed with an optical microscope (200 times), and the linearity (shaking state) of the line width was evaluated based on the following criteria.

Evaluation standard

A: There is no shaking, no break, and the line is straight.

B: There are some shakes, but the lines are almost straight.

C: Line unevenness of about 2 占 퐉 is generated in a twisted state.

D: Line unevenness of 5 占 퐉 or so is generated.

E: No pattern is formed. Or peeled off and can not be evaluated.

(Evaluation of heat resistance)

The substrate obtained in the evaluation of the line width sensitivity was further baked in a 240 ° C clean oven for 60 minutes and the color change (ΔE ^* ab) before and after the additional baking was measured using a spectrophotometer MCPD-2000 manufactured by Otsuka Denshi Co., Ltd. Respectively. Here,? E * ab means a color difference in the L ^* a ^* b ^* color system. The color change? E ^* ab was evaluated based on the following criteria.

Evaluation standard

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

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

4:? E ^* ab is 2.0 or more and less than 3.0.

3.5:? E ^* ab is not less than 3.0 and less than 3.5.

3:? E ^* ab is not less than 3.5 and less than 4.0.

2.5:? E ^* ab of not less than 4.0 and less than 5.0.

2:? E ^* ab is 5.0 or more

1: There is peeling.

(Evaluation of wrinkles)

The substrate obtained in the evaluation of the line width sensitivity was baked in a clean oven at 230 캜 for 30 minutes and the presence or absence of wrinkles of the colored pattern before and after baking was observed with an optical microscope (magnification: 200 times).

Evaluation standard

○: No occurrence of wrinkles was observed.

△: Creation of wrinkles is weak.

X: Wrinkles occur strongly.

(Comprehensive evaluation)

Line width sensitivity, linearity, and heat resistance. The results are summarized in Table 8.

Evaluation standard

5: Very good.

4.5: Excellent.

4: No problem level in normal use.

3.5: A slight drop in performance, but no problem level.

3: lowest level in normal use.

2.5: There is a problem because it is slightly lower than the limit.

2: It can not be used because of insufficient performance.

1: Levels that can not be evaluated.

As clearly shown in Table 8, the colored photosensitive resin compositions of Examples 1 to 15 according to the present invention had good line width sensitivity, the obtained patterns were excellent in linearity, and the color change was small even when the coloring pattern was heated, The generation of wrinkles after the post-baking was suppressed, and a good coloring pattern was obtained.

On the other hand, Comparative Example 1, which did not contain the binder resin (B-1) in the present invention, and Comparative Example 2, which used an initiator other than the oxime-based photopolymerization initiator (D), exhibited line width sensitivity, pattern linearity, Comparative Example 3 in which the content of the binder resin is too large, the occurrence of wrinkles after the post-baking is remarkable, and the content of the binder resin in (B-1) is too large, 2) Comparative Example 5 containing no binder resin were all inferior in line width sensitivity, linearity and wrinkle, compared with the examples. Further, in Comparative Example 6 using an initiator other than the oxime-based photopolymerization initiator (D) and a sensitizer in combination, the line width sensitivity and the linearity of the pattern were inferior.

Claims (9)

(B-1) a binder resin having at least one acidic group represented by the following general formula (I), (B-2) a binder resin having a structural unit represented by the following general formula (II) A binder resin containing a structural unit, (C) a polymerizable compound, (D) an oxime-based photopolymerization initiator, and (E) a solvent; Wherein the content ratio by mass of the binder resin (B-1) and the binder resin (B-2) is 3: 7 to 7: 3.

[In the general formula (I), R ³ represents an organic linking group of (m + n), and R ⁴ and R ⁵ each independently represent a single bond or a divalent organic linking group. A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, And a hydroxyl group. The term &quot; monovalent organic group &quot; n A ² and R ⁴ may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ² represents a polymer skeleton. m P &lt; ² &gt; and R &lt; ⁵ &gt; 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 method according to claim 1,
Wherein the oxime-based photopolymerization initiator (D) is a ketoxime-based photopolymerization initiator represented by the following general formula (III).

[In the formula (III), each of R and X independently represents a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0 to 5; When there are a plurality of X's, the plurality of X's may be the same or different.] 3. The method according to claim 1 or 2,
Wherein the photosensitive resin composition is for ultraviolet laser exposure. A colored layer forming step of applying the colored photosensitive resin composition according to claim 1 or 2 on a substrate to form a colored layer; and an exposure step of curing the exposed area by subjecting the colored layer to pattern ultraviolet laser exposure And a developing step of developing and removing the unexposed portion of the colored layer to form a pattern. 5. The method of claim 4,
Wherein an exposure wavelength of said ultraviolet laser is in the range of 300 nm to 380 nm. 5. The 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 manufacturing a color filter, comprising the step of forming a colored pattern on a substrate by the pattern forming method according to claim 4. A color filter produced by the method of manufacturing a color filter according to claim 7. A display device comprising the color filter according to claim 8.