KR20110117010A - 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 coloring agent, (B-1) Binder resin represented by general formula (I), and having a structural unit represented by (B-2) general formula (II), and a structural unit which has an acidic group Colored photosensitive composition containing resin, (C) polymeric compound, (D) oxime system photoinitiator, and (E) solvent, and content ratio of (B-1) :( B-2) is 3: 7-7: 3. Resin composition. In formula (I), R <^3> represents a (m + n) valent organic coupling group, and R <^4> , R <^5> represents a single bond or a bivalent organic coupling group. A <^2> represents monovalent organic group containing adsorptive groups, such as an organic pigment | dye structure and an acidic group. m represents 1-8, n represents 2-9, and m + n satisfies 3-10. P ² represents a polymer skeleton. In formula (II), R <^11> -R <^15> represents 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

Colored photosensitive resin composition, pattern formation method, manufacturing method of color filter, color filter and display device provided with the same {COLORED PHOTOSENSITIVE RESIN COMPOSITION, PATTERN FORMING METHOD, METHOD OF PRODUCING COLOR FILTER, COLOR FILTER, AND DISPLAY DEVICE HAVING THE SAME}

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

In recent years, the development of liquid crystal display devices has been developed from the use of personal computers and monitors with relatively small screens, to television applications requiring large screens and high image quality.

Television applications require higher image quality, i.e., contrast and color purity, as compared to conventional monitor applications. In order to improve contrast, the particle size of the coloring agent (organic pigment etc.) used for the coloring photosensitive resin composition used for formation of a color filter is calculated | required more. Moreover, as a content rate of the coloring agent (organic pigment) which occupies in solid content of the said coloring photosensitive resin composition, in order to improve color purity, a higher thing is calculated | required.

In response to the above demands, there is a need for a pigment dispersion composition having a finer particle diameter and higher dispersibility. In order to improve the dispersibility of the pigment, for example, the pigment surface is modified on the surface of the phthalocyanine pigment with a derivative compound thereof, and the pigment is used by using a dispersing agent such as a low molecular weight resin having a polar functional group which is easily adsorbed on the modified surface. The pigment dispersion composition containing a pigment, a surface modifier, and a dispersing agent is obtained, aiming at the dispersibility and dispersion stability of this. In addition, alkali-soluble resin, a polymeric compound, a photoinitiator, and other components are further contained in the obtained pigment dispersion composition, and it is set as the photosensitive composition, and the color filter is obtained by the photolithographic method etc. using this.

When the pigment becomes finer and the content of the pigment increases, there is a problem that the line width sensitivity is lowered (the line width becomes thinner) when the image pattern is formed by the photolithography method. In TV applications, it is particularly desired to provide a color filter at a low cost. However, a problem centering on the above-described development process has caused a necessity to increase the exposure amount in the exposure process, that is, to increase the exposure time. This lowered the yield and worsened the productivity, so improvement was required.

In order to solve the said problem, many attempts are made to improve line width sensitivity by the improvement of the photoinitiator used for the photosensitive resin composition for color filters. For example, the photopolymerizable composition (for example, refer patent document 1) using the triazine-type compound of a specific structure, and the benzophenone type, acetophenone type, and thioxanthone type compound are used, or 1 or 2 or more are mixed and used. Photoresist for a color filter (for example, refer patent document 2) etc. are disclosed.

Moreover, as another proposal, the average double bond equivalent in the organic compound which adds the binder resin and polymeric compound in a coloring photosensitive resin composition is prescribed | regulated, and the pure taper shape is formed by baking by specifying the molecular weight of binder resin. The technique is disclosed (refer patent document 3).

Moreover, although it is not the coloring photosensitive resin composition for exposure by an ultraviolet light laser, using the binder resin containing an allyl group is proposed to prepare the coloring resin composition with high sensitivity and a wide development latitude (for example, patent document 4, See 5.). Moreover, using the N-phenylmaleimide copolymer as binder resin is proposed to provide the radiation sensitive composition for blue color filters with favorable color reproduction (for example, refer patent document 6). However, in these techniques, productivity in the exposure process and image development process by an ultraviolet-ray laser fell, and sufficient productivity was not able to be ensured and therefore the price of a color filter could not be reduced.

In order to improve the productivity of an exposure process and a developing process, exposure with a laser beam and pattern shaping are proposed (for example, refer patent document 7). Unlike mercury lamps that are normally used, lasers are expected to have a high straightness, a high output, a narrow focus, and a mask for pattern formation in the exposure process. However, even with the above prior art, the surface of the pixel in the developing step, the line width sensitivity of the pattern were not sufficient, or the like, did not satisfy the characteristics required for the colored photosensitive resin composition. Moreover, in order to reduce the cost as a total of a color filter, it is proposed not to use a large photomask as an exposure apparatus. (For example, refer patent document 8, 9.). However, no specific materials have been proposed, and there has been a demand for proposals for materials suitable for their devices.

In particular, in the blue colored photosensitive resin composition, due to the binder resin, a binder resin that is originally transparent to the visible light after the post-baking develops color, and there is a problem that the luminance is lowered when this is used for the coloring pattern of the color filter. Even in one case, a binder resin without coloring has been desired.

In addition, the blue colorant has a high absorption of 355 nm or 365 nm, and there is a problem that photocuring does not sufficiently proceed to the deep portion of the colored layer during exposure by an ultraviolet laser, and wrinkles occur after postbaking, and thus, the ultraviolet laser The blue coloring photosensitive resin composition with favorable hardening sensitivity which fully hardens | cures by the deep part was craving.

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

The present invention has a high sensitivity to line width, excellent linearity and heat resistance of the formed colored pattern, and is capable of forming a colored pattern in which color development or wrinkles are suppressed even after postbaking, and is suitably used for ultraviolet light laser exposure. Let it be a subject to provide a resin composition.

Moreover, the new subject of this invention is the pattern formation method in which the coloring pattern which is excellent in the shape and brightness which are made using the coloring photosensitive resin composition of this invention is formed, and the manufacturing method of a color filter, Furthermore, the coloring pattern with good pattern shape and brightness is The present invention provides a color filter having a color filter and a display device having the color filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors found out solving the said subject by the following method.

<1> At least (A) colorant, (B-1) The structural unit and acid represented by the following general formula (I), and having a acidic group in a molecule | numerator, and (B-2) the following general formula (II) Binder resin containing the structural unit which has group, (C) polymeric compound, (D) oxime system photoinitiator, and (E) solvent, The said (B-1) binder resin and (B-2) binder resin The coloring photosensitive resin composition whose content ratio by the mass reference | standard is 3: 7-7: 3.

In general formula (I), R <^3> represents a (m + n) valent organic coupling group, R <^4> and R <^5> respectively independently represents a single bond or a bivalent organic coupling group. A ² is an organic pigment structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, And monovalent organic groups comprising at least one substructure selected from hydroxyl groups. n pieces of A ² and R ⁴ may be the same or different. m represents 1-8, n represents 2-9, and m + n satisfies 3-10. P ² represents a polymer skeleton. m pieces of P ² and R ⁵ may be the same or different.

In 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 of <1> whose said (D) oxime system photoinitiator is a ketooxime system photoinitiator represented by following General formula (III).

In 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 0-5. When two or more X exists, some X may respectively independently represent a monovalent substituent, and may be same or different.

<3> The colored photosensitive resin composition as described in <1> or <2>, which is for ultraviolet light laser exposure.

<4> The colored layer formation process of providing the colored photosensitive resin composition in any one of <1>-<3> on a board | substrate, and forming a colored layer, and exposure by the pattern-shaped ultraviolet light laser with respect to the said colored layer. And a developing step of removing the uncured portion of the colored layer by development to form a pattern by curing the exposed portion.

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

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

<7> The manufacturing method of the color filter characterized by including the process of forming a coloring pattern on a board | substrate by the pattern formation method in any one of <4>-<6>.

<8> The color filter manufactured by the manufacturing method as described in <7>.

<9> The display apparatus characterized by including the color filter as described in <8>.

(Effects of the Invention)

According to the present invention, coloring is used suitably for ultraviolet light laser exposure, which has a high line width sensitivity, is excellent in linearity and heat resistance of the formed coloring pattern, and can form a coloring pattern in which color development and wrinkles are suppressed even after postbaking. The photosensitive resin composition can be provided.

Moreover, the pattern formation method which forms the coloring pattern excellent in shape and brightness | luminance by using the coloring photosensitive resin composition of the said invention, and the manufacturing method of a color filter, The color filter which has a coloring pattern with a good pattern shape and brightness, The said color A display device provided with a filter can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail.

<< coloring photosensitive resin composition >>

The colored photosensitive resin composition of this invention is represented by at least (A) coloring agent and (B-1) following General formula (I), and has a binder resin which has an acidic group in a molecule [Hereinafter, it is suitably called (B-1) binder resin. ], (B-2) Binder resin containing the structural unit represented by the following general formula (II), and the structural unit which has an acidic group [Hereinafter, it is suitably called (B-2) binder resin], (C) Polymerizable It contains a compound, (D) oxime system photoinitiator, and (E) solvent, The content ratio by the mass reference of the said (B-1) binder resin and (B-2) binder resin is 3: 7-7: 3. It is characterized by that.

Hereinafter, each structural component of the coloring photosensitive resin composition of this invention is demonstrated in detail.

<(A) Colorant>

The coloring photosensitive resin composition of this invention contains at least 1 sort (s) of (A) coloring agents.

It is preferable that content of the (A) coloring agent in the coloring photosensitive resin composition of this invention is 15 mass%-60 mass% in mass fraction with respect to solid content of a coloring photosensitive resin composition. (A) When content of a coloring agent is less than 15 mass%, in order to set it as desired hue, the film thickness must be set thick and it may become difficult to develop or the tact time may increase. On the other hand, when content of the (A) coloring agent exceeds 60 mass%, developing time becomes long, and also a profile shape may become inverse edge shape and may be unpreferable.

The "solid content" of the coloring photosensitive resin composition in this invention means the heating remainder which weighed 1g of coloring photosensitive resin compositions to the container made from aluminum, and dried at 160 degreeC for 60 minutes, and in the coloring photosensitive resin composition of this invention ( E) It contains all the components of the coloring photosensitive resin composition except a solvent.

20 mass%-50 mass% are more preferable with respect to the total solid of a coloring photosensitive resin composition, and, as for content of the (A) coloring agent in the coloring photosensitive resin composition of this invention, 25 mass%-40 mass% are more preferable.

(A) As a coloring agent, dye and a pigment can be selected suitably and used. From a viewpoint of heat resistance etc., a pigment is more preferable.

The pigment used as the colorant (A) may be either an inorganic pigment or an organic pigment, but from the viewpoint of high transmittance, the use of a small particle size is preferred. It is preferable that the average of a primary particle diameter is 0.01 micrometer-0.1 micrometer, More preferably, it is the range of 0.01 micrometer-0.05 micrometer.

In the coloring photosensitive resin composition of this invention, even if the pigment size is small by using the polymer dispersing agent mentioned later, since pigment dispersibility and dispersion stability become favorable, the coloring pixel excellent in color purity can be formed even if it is thin. .

Moreover, in this invention, the ratio of the pigment whose primary particle diameter is less than 0.02 micrometer among the pigments contained in a coloring photosensitive resin composition is less than 10% of the whole quantity of the said pigment, and also whose primary particle diameter exceeds 0.08 micrometer. It is preferred that the proportion of the pigment is less than 5% of the total amount of the pigment.

Heat resistance is good because the ratio of the pigment whose primary particle diameter is less than 0.02 micrometer is less than 10%, the chromaticity change can be prevented, and since the ratio of the pigment whose primary particle diameter exceeds 0.08 micrometer is less than 5%, contrast is improved. It is good and the aging stability of a coloring photosensitive resin composition is good, and a foreign material failure can be prevented.

As for the ratio of the pigment whose primary particle diameter is less than 0.02 micrometer, it is more preferable that it is less than 5% from a viewpoint of heat resistance and chromaticity change prevention.

It is preferable that the ratio of the pigment whose primary particle diameter exceeds 0.08 micrometer is less than 3% from a viewpoint of improving contrast.

The primary particle diameter of the pigment can be measured using a TEM (transmission electron microscope). That is, particle size distribution can be investigated by image-analyzing a TEM photograph. For example, a particle size distribution can be grasped | ascertained by measuring the total particle number in the observation sample at 3-100,000 times, and the particle number of the pigment exceeding 0.02 micrometer and exceeding 0.08 micrometer. More specifically, the pigment powder was observed at 3 to 100,000 times by a transmission electron microscope, and photographs were taken. The long diameters of the 1000 primary particles were measured to determine the proportion of primary particles smaller than 0.02 µm and larger than 0.08 µm. To calculate. This operation | movement is performed about three places in total by changing the site | part of pigment powder, and averages a result.

Examples of the inorganic pigment that can be used as the colorant include metal compounds such as metal oxides and metal complex salts, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like. The oxide of the metal, the complex oxide of the said metal, etc. are mentioned.

As said organic pigment, for example

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 , 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36 , 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139 , 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 ,

C. I. Pigment Green 7, 10, 36, 37, 58

CI substituents of CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Thing 80,

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

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

Among these, the following can be mentioned as a pigment which can be used preferably. However, in this invention, it 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 can be used individually or in various combinations in order to raise color purity. The specific example of a combination is 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 of them, a disazo pigment, an isoindolin pigment, a quinophthalone A mixture of yellow pigments such as pigments, or at least one of anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments, perylene pigments, anthraquinone pigments, condensation dise pigments, and diketopyrrolopyrrole pigments Mixture of red pigments, such as these, can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, CI pigment red 242 as a condensation disdis type red pigment. Examples of the diketopyrrolopyrrole pigment include CI Pigment Red 254. From the point of color reproducibility, a mixture of CI Pigment Red 254 and CI Pigment Yellow 139 or CI Pigment Red 177 is preferable.

In addition, the mass ratio (red pigment: other pigment) of the red pigment and the other pigment is preferably 100: 5 to 100: 80. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and color purity may not be improved. In addition, the color development ability may be lowered above 100: 81. Especially as said mass ratio, the range of 100: 10-100: 65 is optimal. In addition, in the case of the combination of red pigments, it can adjust to chromaticity.

As the pigment for the green layer (G), a halogenated phthalocyanine pigment alone or a mixture of this and a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment may be used. 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.

As for the mass ratio of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable from a viewpoint of obtaining sufficient color purity and suppressing the shift | deviation from NTSC target color. As mass ratio, the range of 100: 30-100: 120 is especially preferable.

As the pigment for the blue layer (B), a phthalocyanine-based pigment may be used alone, or a mixture of this 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. As for mass ratio of a blue pigment and a purple pigment, 100: 0-100: 50 are preferable, More preferably, it is 100: 5-100: 30.

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

In this invention, it is especially preferable to use the organic pigment as a coloring agent, and to use what coat | covered the pigment with a high molecular compound in the pigment refinement | miniaturization process or a dispersion process. By coating the pigment with a high molecular compound, the formation of secondary aggregates is also suppressed even in the finer pigment, and the coating pigment having improved dispersibility, which can be dispersed in the state of the primary particles, and the dispersion in which the dispersed primary particles are stably maintained. It is more preferable to use the coating pigment which is excellent in stability.

The coating pigment, which is a preferred form of the present invention, is a pigment coated with a polymer compound, but in the coating, a strong coating layer of the polymer compound is formed by a strong electrostatic action with the polymer compound on the new interface of the pigment having high surface activity resulting from micronization. Since it forms, it is thought that the coating pigment which has higher dispersion stability is obtained. That is, in this invention, even if the pigment after coating process wash | cleans with the organic solvent which melt | dissolves a high molecular compound, the coated high molecular compound is hardly liberated.

In the coating pigment as used in the present invention, pigment particles such as an organic pigment are coated with a polymer compound having a polar group such as a heterocyclic ring on the side chain, and the polymer compound has a higher dispersion by firmly covering part or all of the pigment particle surface. The effect of stability is achieved, and it is different from the thing which a general polymer dispersing agent adsorb | sucks to a pigment. This coating state can be confirmed by measuring the free amount (free ratio) of a high molecular compound by washing | cleaning with the organic solvent shown below. In other words, most of the polymer compounds formed by adsorption are free or removed by washing with an organic solvent, specifically, 65% or more. However, in the case of the surface-coated pigments as in the present invention, the glass ratio is very small and 30% or less. to be.

The said free amount (free ratio) washes and computes the pigment after a coating process with 1-methoxy-2-propanol. That is, 10 g of the pigment was added to 100 ml of 1-methoxy-2-propanol, shaken for 3 hours at room temperature using a shaker, and thereafter, the pigment was precipitated for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant portion was The mass is determined by the drying method. The ratio (%) is computed from the ratio of the mass of this solid content and the mass of the high molecular compound used for the coating | covering process of a pigment.

The said glass amount (glass ratio) with respect to pigments, such as a commercial item, can be measured by the following method. That is, after dissolving the whole pigment with the solvent which melt | dissolves a pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, a sulfuric acid, etc.), it isolate | separates with the organic solvent using the difference of solubility in a high molecular compound and a pigment, Mass of the polymer compound used in the coating treatment of &quot; Separately, the free amount of the high molecular compound obtained by washing the pigment with 1-methoxy-2-propanol is divided by this "mass of the high molecular compound used for coating treatment of pigment" to obtain the percentage of free ratio.

The smaller the glass ratio, the stronger the coating with the pigment, the better the dispersibility and the dispersion stability. The preferable range of free ratio is 30% or less, More preferably, it is 20% or less, Most preferably, it is 15% or less. Ideally 0%.

It is preferable to perform coating | coating process simultaneously with the refinement | miniaturization process of a pigment, Specifically, (i) A pigment, (ii) Water-soluble inorganic salt, (i) A small amount of water-soluble organic solvent which does not melt | dissolve substantially (ii), and (Iii) adding a high molecular compound and mechanically kneading with a kneader or the like to obtain a mixture (called a salt milling step); a step of adding the mixture into water and stirring with a high speed mixer or the like to form a slurry; and It carries out through the process of filtering, washing with water, and drying a slurry as needed.

The salt milling described above will be described in more detail. First, a small amount of the water-soluble organic solvent is added to the mixture of (i) the organic pigment and (ii) the water-soluble inorganic salt as a humectant, kneaded vigorously with a kneader or the like, and the mixture is poured into water, and a high speed mixer. The mixture is stirred in the form of slurry to form a slurry. Subsequently, this slurry is filtered, washed with water and dried as needed to obtain a finely pigmented pigment. In addition, when disperse | distributing and using an oily varnish, it is also possible to disperse | distribute the process pigment (called a filtration cake) before drying, removing water by the method generally called flashing, and removing oily varnish. In addition, when disperse | distributing to an aqueous varnish, a process pigment does not need to be dried, and a filter cake can be disperse | distributed as it is to a varnish.

The use of at least part of a soluble resin (v) in combination with the (v) organic solvent as the (v) polymer compound at the time of salt milling results in a finer, less cohesive aggregate of the pigment at the time of drying.

In addition, all (i) high molecular compounds may be added at the beginning of a salt milling process, and may be added separately. It is also possible to add in a dispersion process.

The polymer compound used for coating the pigment may be any one as long as it has an adsorbent group on the pigment. In particular, the high molecular compound which has a heterocycle in a side chain is preferable. The (B-1) binder resin mentioned later in this invention is also preferable as a high molecular compound used for coating | covering of a pigment.

Examples of the high molecular compound that can be used for coating the pigment include paragraphs [0029] to [0030] of JP-A-2008-83089 and paragraphs [0044] to [0047] of JP-A-2009-62457 ] Can be used.

In the case of using the coated pigment described above, it is more preferable to disperse the pigment using at least one kind of dispersant and to use it as a pigment dispersion composition. By containing this dispersing agent, the dispersibility of a pigment can be improved further.

As a dispersing agent, a well-known pigment dispersing agent and surfactant can be selected suitably, for example.

Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 [manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.], (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Kagaku Kogyo Co., Ltd.) and W001 (manufactured by Yusho Corporation); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl 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 Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Chiba Specialty Chemical Co., Ltd.), Disperse Ade 6, Disperse Ade 8, Disperse Ade 15 Polymer dispersants such as Disperse Aid 9100 (all manufactured by Sanofko Corp.);

Various solvent dispersants (manufactured by Nihon Lubrizol Co., Ltd.) such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) And Isonet S-20 [Sanyo Kasei Co., Ltd. product], 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 Chemie Co., Ltd.). In addition, the oligomer or polymer which has a polar group in a molecular terminal or a side chain, such as an acryl-type copolymer, is mentioned.

As content in the pigment dispersion composition of a dispersing agent, 1-100 mass% is preferable with respect to the above-mentioned pigment mass, and 3-70 mass% is more preferable.

A pigment derivative is one of the high molecular compounds used for coating of a pigment, and is added to a pigment dispersion composition as needed. By adsorbing a pigment derivative having affinity to the dispersant or a polar group introduced thereon onto the surface of the pigment, and using this as the adsorption point of the dispersant, the pigment can be dispersed into the photosensitive resin composition as fine particles and the reaggregation can be prevented. It is effective for forming a color filter having high contrast and excellent transparency.

A pigment derivative is a compound which made an organic pigment a mother skeleton specifically, and introduce | transduced an acidic group, a basic group, and an aromatic group into a side chain as a substituent. Specifically as an organic pigment, a quinacridone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoindolin type pigment, an isoindolinone pigment, a quinoline pigment, a diketopyrrolopyrrole pigment, and benzimida A jolon pigment etc. are mentioned. Light yellow aromatic polycyclic compounds, such as naphthalene series, anthraquinone series, triazine series, and quinoline series, which are not generally called dyes, are also included in the organic pigment. As a pigment derivative, Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Unexamined-Japanese-Patent No. 8-295810, Japanese Patent Laid-Open No. 11-199796, Japanese Patent Laid-Open No. 2005-234478, Japanese Patent Laid-Open No. 2003-240938, Japanese Patent Laid-Open No. 2001-356210, etc. can be used. .

As content in the pigment dispersion composition of a pigment derivative, 1 mass%-30 mass% are preferable with respect to the mass of a pigment, and 3 mass%-20 mass% are more preferable. When the content is in the above range, the dispersion can be satisfactorily performed while the viscosity is kept low, and the dispersion stability after dispersion can be improved, and the transmittance is high and excellent color characteristics can be obtained. It can comprise with high contrast.

The method of dispersion can be performed by pre-dispersing a pigment and a dispersing agent previously, and disperse | distributing previously with a homogenizer etc. using the bead disperser etc. which used zirconia beads etc.

In this invention, when using dye as a (A) coloring agent, the coloring photosensitive resin composition melt | dissolved uniformly is obtained.

(A) There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used for the color filter use can be used. For example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent Registration 2592207, U.S. Patent No. 4,808,501, U.S. Patent 5,667,920, U.S. Patent 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-open No. 6-51115 Japanese Patent Laid-Open No. 6-194828, Japanese Patent Laid-Open No. 8-211599, Japanese Patent Laid-Open No. 4-249549, Japanese Patent Laid-Open No. 10-123316, Japanese Patent Laid-Open No. 11-302283 Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215, Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open No. 8-62416, Japanese Patent Laid-Open No. 2002-14220, Japanese Patent Laid-Open No. 2002-14221, Japanese Patent Laid-Open No. 2002-14222, Japanese Patent Laid-Open 2002-14223, Japanese Patent Laid-Open No. 8-302224, Japanese Patent Laid-Open It is a pigment | dye as described in Unexamined-Japanese-Patent No. 8-73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531.

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine and pyrrolo. Dyestuffs, such as a pyrazole azomethine type, a xanthene type, a phthalocyanine type, a benzopyran type, an indigo type, can be used.

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

The (B-1) binder resin used for this invention is represented by the following general formula (I), and is a high molecular compound which has an acidic group in a molecule | numerator.

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

In said general formula (I), R <^3> represents a (m + n) valent organic coupling group, R <^4> and R <^5> respectively independently represents a single bond or a bivalent organic coupling group. A ² is an organic pigment structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, And monovalent organic groups containing at least one partial structure selected from hydroxyl groups. n pieces of A ² and R ⁴ may be the same or different. m represents 1-8, n represents 2-9, and m + n satisfies 3-10. P ² represents a polymer skeleton. m pieces of P ² and R ⁵ may be the same or different.

In the general formula (I), A ² represents an organic pigment structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, and alkoxy. The monovalent organic group containing at least 1 sort (s) of partial structure chosen from a silyl group, an epoxy group, an isocyanate group, and a hydroxyl group is shown. n pieces of A ² may be the same or different.

That is, A ² has a structure having adsorption capacity for pigments such as an organic dye structure and a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, and 4 carbon atoms. The monovalent organic group containing at least 1 sort (s) of functional group which has adsorption capacity with respect to a pigment like the above hydrocarbon group, an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group is shown.

In addition, below, the partial structure (the said structure and functional group) which has the adsorption ability with respect to this pigment is demonstrated generically as a "adsorption site" suitably.

The adsorption sites are good if it contains at least one member in one of A ^2, may contain two or more kinds.

In the present invention, the "monovalent organic group containing at least one adsorption site" includes the adsorption site described above, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, and 0 to 100 oxygen atoms. Or a monovalent organic group formed by combining an organic linking group formed of 1 to 400 hydrogen atoms and 0 to 40 sulfur atoms. When the adsorption site itself can constitute a monovalent organic group, the adsorption site may be the monovalent organic group represented by A ² .

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

As said "organic pigment structure", for example, a phthalocyanine system, an insoluble azo system, an azo lake system, an anthraquinone system, a quinacridone system, a dioxazine system, a diketopyrrolopyrrole system, an anthrapyridine system, an anthrone system, an indanthrone Preferred examples of the pigment structure of the system, flavanetron, perinone, perylene, and thioindigo include a pigment structure of phthalocyanine, azolake, anthraquinone, dioxazine and diketopyrrolopyrrole. More preferably, the pigment structure of a phthalocyanine series, anthraquinone series, and diketopyrrolopyrrole series is especially preferable.

Moreover, as said "heterocyclic structure", for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, Thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindoli Paddy, benzimazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone are preferred examples. , Pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindolin, iso Indolinone, benzimazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carr Sol, acridine, acridine money, anthraquinone is more preferable.

The "organic dye structure" or the "heterocyclic structure" may further have a substituent, and as said substituent, C6-C20 alkyl groups, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, etc. are mentioned, for example. C1-C20 alkoxy groups, such as acyloxy, methoxy, and ethoxy groups having 1 to 6 carbon atoms such as 16 aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamide groups, N-sulfonylamide groups, and acetoxy groups And carbonate ester groups such as alkoxycarbonyl groups having 2 to 7 carbon atoms, cyano groups and t-butyl carbonates such as halogen atoms such as chlorine and bromine, methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group. Here, these substituents may be couple | bonded with the organic pigment | dye structure or heterocycle through the coupling group which the following structural unit or the said structural unit combines.

As said "acidic group", a carboxylic acid group, a sulfonic acid group, a monosulfate ester group, a phosphoric acid group, a monophosphate ester group, a boric acid group is mentioned as a preferable example, for example, a carboxylic acid group, a sulfonic acid group, a monosulfate ester 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 especially preferable.

Moreover, as said "group which has a basic nitrogen atom", for example, an amino group (-NH ₂ ), a substituted amino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are respectively Independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), an amidinyl group represented by the following formula (a2), and the like. Preferred examples can be given.

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

In formula (a2), R <^13> and R <^14> respectively independently represents a C1-C20 alkyl group, a C6 or more aryl group, and a C7 or more aralkyl group.

Among these, 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, and a benzyl group. Guanidyl group represented by said formula (a1) (In formula (a1), R <^11> and R <^12> represents a C1-C10 alkyl group, a phenyl group, and a benzyl group each independently.), As said Formula (a2). More preferred are amidinyl groups (wherein R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a benzyl group) in the formula (a2).

In particular, 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 and a benzyl group. Guanidyl group represented by said formula (a1) (In formula (a1), R <^11> and R <^12> represents a C1-C5 alkyl group, a phenyl group, and a benzyl group each independently.), And with said Formula (a2). The amidinyl group (In formula (a2), R <^13> and R <^14> represents a C1-C5 alkyl group, a phenyl group, and a benzyl group each independently.) Etc. are used preferably.

As said "urea group", for example, -NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or carbon number). And arylene groups of 7 or more.) Are preferred examples, and -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, or carbon atoms). And aralkyl groups of 7 or more.) Are more preferable, and -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 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) is particularly preferable. Do.

As said "urethane group", for example, -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , -OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. Preferred examples thereof include -NHCOOR ¹⁸ and -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferably, -NHCOOR ¹⁸ , -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ are each independently) And an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms), and the like.

As said "group which has coordinating oxygen atom", an acetylacetonate group, a crown ether, etc. are mentioned, for example.

As said "C4 or more hydrocarbon group", a C4 or more alkyl group, a C6 or more aryl group, a C7 or more aralkyl group, etc. are mentioned as a preferable example, A C4-C20 alkyl group, a C6-C20 aryl group, Aralkyl groups having 7 to 20 carbon atoms and the like are more preferable, and an alkyl group having 4 to 15 carbon atoms (for example, an octyl group and a dodecyl group), an aryl group having 6 to 15 carbon atoms (for example, a phenyl group and a naphthyl group), and a carbon number Aralkyl groups (for example, benzyl group etc.) of 7-15 are especially preferable.

As said "alkoxy silyl group", a trimethoxy silyl group, a triethoxy silyl group, etc. are mentioned, for example.

Examples of the organic linking group in the case where the adsorption site combines with the organic linking group include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 The organic linking group formed from -20 sulfur atoms is preferable, and this organic linking group may be unsubstituted, or may have a substituent further.

As a specific example of this organic coupling group, group which the following structural unit or the said structural unit combines is comprised.

When the organic linking group has a substituent, the substituent includes, for example, 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, a hydroxyl group, an amino group, a carboxy group and a sulfonamide group. C1-C6 alkoxy groups, such as C1-C6 acyloxy groups, such as a N-sulfonylamide group and an acetoxy group, a methoxy group, an ethoxy group, halogen atoms, such as chlorine and a bromine, methoxycarbonyl group, Carbonic ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, such as a oxycarbonyl group and a cyclohexyloxycarbonyl group, etc. are mentioned.

In the above, the A ² is a monovalent organic group containing at least one moiety 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.

As said A <^2>, it is more preferable that it is a monovalent organic group represented by following General formula (4).

Wherein the general formula (4), B ¹ is a group having a group, a urea group, a urethane group, x satellite oxygen atoms having the adsorption sites (that is an organic dye structure, a heterocyclic structure, an acidic group, a basic nitrogen atom, having 4 And the above-mentioned hydrocarbon group, alkoxysilyl group, epoxy group, isocyanate group, and a site selected from hydroxyl group). R ²⁴ represents a single bond or a (a + 1) valence organic linking group. a represents the integer of 1-10, and a piece B <^1> may be same or different.

It may be mentioned as the adsorption sites represented by the B ¹ and the same adsorption sites constituting the A ² in the general formula (1) of the above-mentioned, as preferred examples.

Especially, the site | part selected from the organic pigment | dye structure, a heterocyclic structure, an acidic group, the group which has a basic nitrogen atom, a urea group, and a C4 or more hydrocarbon group is preferable.

R <^24> represents a single bond or a (a + 1) valent organic coupling group, and a represents 1-10. Preferably a is 1-7, More preferably, a is 1-5, Especially preferably, a is 1-3.

Examples of the (a + 1) valent organic linking group include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group which is established may be mentioned and may have a substituent even if it is unsubstituted.

As said (a + 1) valent organic coupling group, the group (you may form ring structure) comprised by the following structural unit or the said structural unit combined is mentioned as a specific example.

R ^{24 is formed from a} single bond or from 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms. Preferred (a + 1) valent organic linking groups are single bonds, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 More preferably, the (a + 1) valent organic linkage group formed from 7 to 7 sulfur atoms is a single bond, or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, Particularly preferred are (a + 1) valent organic linkage groups formed from 1 to 30 hydrogen atoms and 0 to 5 sulfur atoms.

In the above, when the (a + 1) valent organic linking group has a substituent, 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 hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group, an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, chlorine, and bromine Carbonic ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

In said general formula (I), R <^4> , R <^5> represents a single bond or a bivalent organic coupling group each independently. n R ^{4 's} may be the same or different. In addition, m pieces of R ⁵ may be the same or different.

Examples of the divalent organic linking group include groups 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. Even if it is unsubstituted, you may have a substituent further.

As a specific example of the said divalent organic coupling group, the group comprised by the following structural unit or the said structural unit is mentioned.

As R ⁴ and R ⁵ , a single bond or 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 Bivalent organic linkage groups formed from atoms are preferable, and are single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 More preferably, a divalent organic linking group formed from 7 to 7 sulfur atoms is a single bond, or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, or 1 to 30 carbon atoms. Particular preference is given to divalent organic linkages formed from hydrogen atoms and from 0 to 5 sulfur atoms.

In the above, when the divalent organic linking group has a substituent, the substituent includes, for example, 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, a hydroxyl group, an amino group, C1-C6 alkoxy groups, such as carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, C1-C6 alkoxy group, such as alkoxy group, halogen atom, such as chlorine and bromine, Carbonate ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

In said general formula (I), R <^3> represents the (m + n) valent organic coupling group. m + n satisfies 3-10.

Examples of the (m + n) valent organic linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 The group formed from 20 to 20 sulfur atoms may be mentioned, and even if it is unsubstituted, it may have a substituent further.

As a specific example of the said (m + n) valent organic coupling group, group (you may form ring structure) comprised by the following structural unit or the said structural unit is mentioned.

Examples of the (m + n) -valent organic linking group include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 sulfur atoms. Groups formed are preferred, and groups 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, groups 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 are particularly preferred. Do.

In the above, 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 hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group, an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, chlorine, and bromine Carbonic ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

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

Among the above specific examples, the most preferred (m + n) -valent organic linking group is from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

In said general formula (I), m shows 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.

In addition, in said general formula (I), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In addition, P <^2> in general formula (I) represents a polymer skeleton, and can be selected from a well-known polymer etc. according to the objective. m pieces of P ² may be the same or different.

Among polymers, polymers or copolymers of vinyl monomers, ester-based polymers, ether-based polymers, urethane-based polymers, amide-based polymers, epoxy-based polymers, silicone-based polymers, and modified or copolymers thereof may be used. , A polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer, or the like (any of random copolymers, block copolymers, and graft copolymers may be used). 1 type is preferable, At least 1 sort (s) chosen from the group which consists of a polymer or copolymer of a vinyl monomer, an ester type polymer, an ether type polymer, a urethane type polymer, and these modified | denatured products or a copolymer is more preferable, The polymer of a vinyl monomer, or Copolymers are particularly preferred.

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

It having at least one kind of acid in the polymer skeleton represented by P ² In the present invention, it is preferable.

There is no restriction | limiting in particular in the means which introduce | transduces an acidic group into a polymer skeleton, The means which introduce | transduces by the vinyl monomer which has an acidic group, the means which introduce | transduces by adding an acidic group using a crosslinkable side chain, etc. can be taken, As mentioned later, a polymer The structure into which an acidic group is introduce | transduced because a skeleton contains the structural unit derived from the vinyl monomer which has an acidic group is preferable from the point of easy control of the introduction amount of an acidic group, and the point of synthesis cost.

Here, the "acidic group" can mention similarly what was listed as an "acidic group" in description of said A <^2> , Preferably it is a carboxy group.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth) Acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and vinyl monomers having an acidic group are preferable.

Hereinafter, the preferable example of these vinyl monomers is demonstrated.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl (meth) acrylate. T-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( T-octyl acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxy (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylate 4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth 2- (2-methoxyethoxy) ethyl acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, ( 2-chloroethyl methacrylate, glycidyl (meth) acrylate, -3,4-epoxycyclohexylmethyl (meth) acrylic acid, vinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, (meth) -1-propenyl acrylate, allyl (meth) acrylate, 2-allyl oxyethyl (meth) acrylate, propargyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (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 Ether, (meth) acrylic acid (beta) -phenoxy ethoxyethyl, (meth) acrylic-acid nonylphenoxy polyethylene glycol, (meth) acrylic-acid dicyclopentenyl, (meth) acrylic-acid dicyclopentenyloxyethyl, (meth) a Trifluoroethyl acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyl (meth) acrylate Oxyethyl, (meth) acrylic acid-gamma-butyrolactone, etc. are mentioned.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

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

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

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

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

As (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth Acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide , (Meth) acryloyl morpholine, diacetone acrylamide, N-methyrol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, N -Allyl (meth) acrylamide, etc. are mentioned.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene and bromo Styrene, chloromethylstyrene, hydroxystyrene protected by a group which can be deprotected by an acidic substance (for example, t-Boc etc.), methyl vinyl benzoate, alpha-methylstyrene, etc. are mentioned.

Examples of 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 etc. are mentioned.

Examples of 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, isoprene and the like.

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

(Meth) acrylonitrile, a heterocyclic group substituted with a vinyl group (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinyl Midazole, vinyl caprolactone, etc. can also be used.

In addition to the said compound, the vinyl monomer which has functional groups, such as a urethane group, a urea group, a sulfonamide group, a phenol group, an imide group, can also be used, for example. The monomer which has such a urethane group or urea group can be suitably synthesize | combined using the addition reaction of an isocyanate group, a hydroxyl group, or an amino group, for example. Specifically, addition reaction of an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or a primary or secondary amino group-containing monomer and a monoisocyanate It can synthesize | combine suitably by addition reaction or the like.

The following describes the vinyl monomer having an acidic group is used in order to introduce an acidic group to the polymer backbone P ^2.

As an example of the vinyl monomer which has the said acidic group, the vinyl monomer which has a carboxyl group, and the vinyl monomer which has a sulfonic acid group are mentioned.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimers. Furthermore, the addition reaction product of the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and cyclic anhydrides, such as maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic anhydride, (omega)-carboxy- polycaprolactone mono ( Meth) acrylate etc. can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, a citraconic anhydride, as a precursor of a carboxyl group. In these, (meth) acrylic acid is especially preferable from a viewpoint of copolymerizability, cost, and solubility.

Moreover, 2-acrylamide-2-methylpropanesulfonic acid etc. are mentioned as a vinyl monomer which has a sulfonic acid group, Monophosphoric acid mono (2-acryloyloxyethyl ester), Monophosphoric acid (1-methyl-) as a vinyl monomer which has a phosphoric acid group 2-acryloyloxyethyl ester) etc. are mentioned.

Moreover, the vinyl monomer containing a phenolic hydroxy group, the vinyl monomer containing a sulfonamide group, etc. can also be used as a vinyl monomer which has an acidic group.

When the polymer skeleton P ² includes a structural unit derived from a vinyl monomer containing an acid group, the content in the polymer skeleton of the structural unit derived from a vinyl monomer having an acid group is preferably 3 mol% to 40 mol%, and 5 mol%. It is more preferable that it is the range of -20 mol%.

It is most preferable to satisfy all of R <^3> , R <^4> , R <^5> , P <^2> , m, and n shown below among the high molecular compounds represented by said general formula (I).

R ³ : the specific examples (1), (2), (10), (11), (16), or (17)

R ⁴ : A single bond or a combination of the following structural units or the above structural units, "1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 A divalent organic linking group (which may have a substituent group) formed from a hydrogen atom and 0 to 5 sulfur atoms ”, 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, and the like. C1-C6 acyloxy groups, such as the C6-C16 aryl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, N-sulfonylamide group, an acetoxy group, C1-C6, such as methoxy group and an ethoxy group Carbonate ester groups such as alkoxycarbonyl groups having 2 to 7 carbon atoms, such as alkoxy groups such as 6 alkoxy groups, chlorine and bromine, methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, cyano groups and t-butylcarbonate Can be.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)

In addition, in the following group, R <^12> represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : a copolymer of a vinyl monomer having a carboxyl group with another vinyl monomer; Polymers or copolymers of vinyl monomers having no acidic groups; A polymer selected from an ester polymer, an ether polymer, and a urethane polymer and a modified product thereof and may contain at least one acidic group.

m: 1 to 3

n: 3 to 6

Content of the acidic group in (B-1) binder resin in this invention is suitably determined by the acid value which (B-1) binder resin has. As an acid value of (B-1) binder resin, it is preferable that it is 30-200 (mgKOH / g), 40-160 (mgKOH / g) is more preferable, 50-120 (mgKOH / g) is especially preferable. When the acid value is less than 30 (mgKOH / g), the alkali developability of the colored photosensitive resin composition may be insufficient, and when the acid value exceeds 200 (mgKOH / g), the pigment is used when the pigment is used as the (A) colorant. There is a risk of adversely affecting the dispersibility and dispersion stability.

As molecular weight of (B-1) binder resin, 3000-100000 are preferable at a weight average molecular weight, 5000-80000 are more preferable, 7000-60000 are especially preferable. When the weight average molecular weight is in the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exhibited, and exhibit excellent performance in adsorption to the solid surface, micelle formation ability, and surfactant.

Although the exemplary compound of (B-1) binder resin by this invention is given to the following, this invention is not limited to this, As long as it is contained in general formula (I), arbitrary structures can be employ | adopted.

In the exemplary compound of the above-mentioned (B-1) binder resin, the content ratio (p ¹ : p ² ) of the structural unit having a carboxylic acid ester in the polymer skeleton and the structural unit having a carboxyl group is 95: 5 in terms of mass. It is preferable that it is the range of -80: 20.

Among these exemplary compounds, the content ratio of the structural unit having a structure represented by the above-mentioned B-1-22 and having a carboxylic acid ester in the polymer skeleton and a structural unit having a carboxyl group is 90:10 in terms of mass, molecular weight 20,000, Particularly preferred are compounds having an acid value of 82.

(B-1) binder resin represented by the said General formula (I) can be synthesize | combined with reference to the method of Unexamined-Japanese-Patent No. 2006-278118, for example.

As for content of (B-1) binder resin in the coloring photosensitive resin composition of this invention, the range of 5 mass%-70 mass% is preferable with respect to solid content of a coloring photosensitive resin composition, and the range of 10 mass%-50 mass% Is more preferable.

<(B-2) Binder resin containing the structural unit represented by general formula (II) and the structural unit which has an acidic group>

The coloring photosensitive resin composition of this invention contains the binder resin containing the structural unit represented by the following general formula (II) (B-2), and an acidic group.

[Structural Unit Represented by General Formula (II)]

In 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.

As R <^11> -R <^15> in general formula (II), a hydrogen atom, a halogen atom, a cyano group, a C1-C12 alkyl group, or a C5-C14 aryl group is respectively preferable, and a hydrogen atom and a bromine atom are especially preferable. , 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 is more preferable.

The alkyl group may have a substituent, and may be linear, branched, or cyclic as a substituent, and may include a methyl group, n-propyl group, iso-propyl group, t-butyl group and the like, and an alkyl group having 1 to 7 carbon atoms is preferable. Do. Moreover, the said aryl group may have a substituent, As a substituent, a C1-C7 alkyl group, a C5-C14 aryl group, etc. are mentioned, Preferably it is a phenyl group, a furyl group, a naphthyl group.

Among these, preferred as general formula (II) are those in which 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 general formula (II).

(B-2) It is preferable to contain 20 mol% or more and 90 mol% or less in the molecule | numerator, and, as for the structural unit represented by the said General formula (II) in binder resin, it is more preferable to contain 50 mol% or more and 80 mol% or less. It is more preferable to contain 60 mol% or more and 80 mol% or less. When the total amount of each structural unit in the binder resin is in the above range, the development latitude becomes good, the film decreases during the development after exposure is reduced, and the surface smoothness of the obtained cured film becomes good.

[Structural Unit Having Acidic Group]

In addition, (B-2) binder resin has a structural unit which has an acidic group in a molecule | numerator.

As a structural unit which has an acidic group, the structural unit derived from a carboxyl group-containing unsaturated monomer is mentioned. Examples of the carboxyl group-containing unsaturated monomers include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-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; Trivalent or higher unsaturated polyvalent carboxylic acid or its anhydrides; Mono [(meth) acryloyloxyalkyl] of divalent or more polyhydric carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters; and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate.

Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are trademarks of M-5300 and M-5400 (manufactured by Toagosei Co., Ltd.), respectively. It is commercially available.

The said carboxyl group-containing unsaturated monomer may be independent or may contain 2 or more types in resin.

Among these structural units having preferred acid groups are carboxylic acid, chalcogen analogue of carboxylic acid, carbohydrazonic acid [RC (= NNH ₂ ) OH], carboxylic acid [RC (= NH) OH], Sulfonic acid [RS (O) ₂ OH], sulfinic acid [RS (O) OH], sulfenic acid [RSOH], selenic acid [RSe (O) ₂ OH], selenic acid [RSe (O) OH], selenic acid [SeOH], a structural unit derived from an analog of phosphoric acid and its acid related compound, silicic acid and boric acid, and particularly preferred are structural units derived from acrylic acid, methacrylic acid, and phosphoric acid.

(B-2) It is preferable that it is 5 mol% or more and 50 mol% or less, and, as for content of the structural unit which has an acidic group in binder resin, 10 mol% or more and 30 mol% or less are more preferable. If it exists in this range, the surface smoothness and heat resistance at the time of image development will be favorable.

(B-2) In addition to each structural unit mentioned above, binder resin may contain the other structural unit. As another structural unit, the structural unit derived from the following unsaturated monomer is mentioned.

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (Meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, methoxy propylene 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;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylic Unsaturated carboxylic acid aminoalkyl esters such as acrylate and 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;

Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide, α-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 ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane;

The structural unit derived from these unsaturated monomers may contain individually or 2 types or more.

Below, exemplary compounds 1-1 to 1-8 and 2-20 of (B-2) binder resin are shown. (B-2) Binder resin is not limited to these exemplary compounds.

As the weight average molecular weight of (B-2) binder resin, it is preferable that it is the range of 10000-100000, More preferably, it is the range of 10000-50000, More preferably, it is the range of 10000-40000. If it exists in this range, developability and linearity of the pattern formed will become favorable.

As for content of (B-2) binder resin in the coloring photosensitive resin composition of this invention, the range of 10 mass%-50 mass% is preferable with respect to solid content of a coloring photosensitive resin composition, and 15 mass%-40 mass% of The range is more preferable.

Although the coloring photosensitive resin composition of this invention contains two types of binder resin of (B-1) binder resin and (B-2) binder resin as mentioned above, (B-1) binder resin and (B- 2) The content ratio based on the mass basis of binder resin needs to be 3: 7-7: 3, and it is preferable that content ratio is 4: 6-6: 4. If the content ratio is within the above range, the heat resistance of the cured film formed is satisfactory, and the effect of generating wrinkles after postbaking is effectively suppressed.

Therefore, in the range of content of each binder resin mentioned above, it is prepared so that the content ratio by the mass reference | standard of (B-1) binder resin and (B-2) binder resin may be a range of 3: 7-7: 3. do.

The colored photosensitive resin composition of this invention may also contain resin of other structures other than the said (B-1) binder resin and (B-2) binder resin which are the specific components in this invention. As (B-1) binder resin and resin of a structure other than (B-2) binder resin, it is a developing solution which acts as a binder with respect to a coloring agent, and is used in the image development processing process, especially when manufacturing a color filter. It is not particularly limited as long as it has solubility with respect to the alkaline developer, but an acrylic copolymer having a carboxyl group is preferable, and in particular, a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer is desirable.

As a specific example of the resin which can be used together which has structures other than said (B-1) binder resin and (B-2) binder resin in this 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, etc. are mentioned.

Moreover, the resin containing the following epoxy ring and oxetane ring can also be used.

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

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

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

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

p-methoxystyrene / methacrylic acid / cyclohexylacrylate / glycidyl glycidyl copolymer.

<(C) polymeric compound>

The coloring photosensitive resin composition of this invention contains the (C) polymeric compound.

The polymerizable compound which can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such compound groups are widely known in the industrial field, and in the present invention, these can be used without particular limitation. These have, for example, chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. As an example of a monomer and its copolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its esters, and amides are mentioned, Preferably it is Esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds.

Moreover, the addition reaction product of unsaturated carboxylic ester or amide which has nucleophilic substituent, such as a hydroxyl group, an amino group, and a mercapto group, with monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional carboxyl Dehydration condensation products with acids and the like are also suitably used. Moreover, the addition reaction of the unsaturated carboxylic acid ester or amide which has electrophilic substituents, such as an isocyanate group and an epoxy group, and monofunctional or polyfunctional alcohol, amines, and thiols, and desorption of a halogen group, a tosyloxy group, etc. Preference is also given to substitution reaction products of unsaturated carboxylic acid esters or amides having a substituent with monofunctional or polyfunctional alcohols, amines and thiols. In addition, it is also possible to use the compound group which used unsaturated phosphonic acid, styrene, vinyl ether, etc. instead of the said unsaturated carboxylic acid as another example.

In addition, in this specification, an acrylate and a methacrylate are named generically (meth) acrylate.

As a specific example of the ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, as (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3- butanediol di (meth) Acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, trimetholpropane tri (meth) acrylate, trimetholpropane tree (( Meta) acryloyloxypropyl) ether, trimetholethane tri (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylic acid, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaery Lithitol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol triacrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol Hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, polyester (meth) acrylate oligomer, isocyanuric acid EO modified tri (meth) acrylate,

Bisphenol A di (meth) acrylate, bisphenol A di (meth) acrylate EO modified product, trimetholpropane tri (meth) acrylate, trimetholpropane tri ((meth) acryloyloxypropyl) ether, tri Methirolethane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol diacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) ) Acrylate, pentaerythritol tetraacrylate EO modified body, dipentaerythritol hexaacrylate EO modified body, etc. are mentioned as a preferable thing.

As the itaconic acid ester, ethylene glycol dietaconate, propylene glycol dietaconate, 1,3-butanediol dietaconate, 1,4-butanediol dietaconate, tetramethylene glycol dietaconate, pentaerythritol dietaconate, sorbitol tetratacoate Nate and the like. Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. 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, sorbitol tetramalate and the like.

As examples of other esters, for example, the aliphatic alcohol esters described in JP-A-51-47334, JP-A-57-196231, JP-A-59-5240, and JP-A-JP The thing which has the aromatic skeleton of 59-5241, Unexamined-Japanese-Patent No. 2-226149, the thing containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. are also used preferably.

Moreover, as an example of the amide monomer of an aliphatic polyhydric amine compound and unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis- Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like. As an example of another preferable amide monomer, what has a cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane type addition polymeric compound manufactured using the addition reaction of an isocyanate and a hydroxyl group is also preferable, As such a specific example, 2 or more isocyanate groups per molecule are described, for example in Unexamined-Japanese-Patent No. 48-41708. The vinylurethane compound etc. which contain two or more polymeric vinyl groups in 1 molecule which added the vinyl monomer containing the hydroxyl group represented by following General formula (V) to the polyisocyanate compound which have is mentioned.

General formula (Ⅴ)

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

(However, R ⁴ and R ⁵ each independently represent H or CH _3. )

Furthermore, urethane acrylates described in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 2-32293, Japanese Patent Laid-Open No. 2-16765, Japanese Patent Laid-Open No. 58-49860, Also preferred are urethane compounds having an ethylene oxide-based skeleton described in JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418. In addition, addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238 By using it, the photopolymerizable composition which is very excellent in the photosensitive speed can be obtained.

As other examples, polyester acrylates, epoxy resins and the like described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490 Polyfunctional acrylates and methacrylates, such as epoxy acrylate which made methacrylic acid react, are mentioned. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, Unexamined-Japanese-Patent No. 1-40337, Unexamined-Japanese-Patent No. 1-40336, and Unexamined-Japanese-Patent No. 2-25493 are described. Vinyl phosphonic acid type compounds etc. are mentioned. In any case, a structure containing a perfluoroalkyl group described in Japanese Patent Application Laid-open No. 61-22048 is preferably used.

Moreover, as a commercial item, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku pulp company), DPHA (made by Nihon Kayaku Co.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) is preferable.

In addition, Japan Adhesion Society Vol. 20, No. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

The preferable aspect of the (C) polymeric compound in the coloring photosensitive resin composition of this invention uses the mixture of the compound containing 5 or more and 15 or less of polymeric groups in a molecule | numerator, and the compound containing 1 or more and 4 or less polymeric groups in a molecule | numerator. It is. As a compound containing 5 or more and 15 or less of a polymeric group in a molecule | numerator, and a compound containing 1 or more and 4 or less of a polymeric group in a molecule | numerator, Preferably they are the following compounds.

As an example of the compound containing 5 or more and 15 or less polymeric groups in a molecule | numerator, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, and sorbitol hexa (meth) acrylate And U-6HA, U-15HA, UA-32P, UA-7200 (above, manufactured by Shin-Nakamura Kagaku Corporation), TO-2248, 2349, 1382 (above, manufactured by Toagosei Co., Ltd.), and the like. Furthermore, neopentyl glycol oligo (meth) acrylate, 1, 4- butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimetholpropane oligo (meth) acrylate, pentaerythritol Although compounds containing 5 or more and 15 or less (meth) acryl groups in molecules, such as oligo (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate, are mentioned, In the case of such an oligomer, it is 1000 as a molecular weight. It is preferable that it is the range of -5000.

As a compound containing 1 or more and 4 or less polymeric groups in a molecule | numerator, a trimethol propane tri (meth) acrylate, a trimethol propane PO (propylene oxide) modified tri (meth) acrylate, and a trimethol propane EO (ethylene oxide) Modified tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tetrametholmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethol Propane tetra (meth) acrylate, an ethoxylated pentaerythritol tetra (meth) acrylate, etc. are mentioned.

When using a mixture of a compound containing 5 or more and 15 or less polymerizable groups in a molecule and a compound containing 1 or more and 4 or less polymerizable groups in a molecule, a compound containing 5 or more and 15 or less polymerizable groups in a molecule and 1 polymerizable group in a molecule The ratio of the compound containing 4 or more and 4 or less is a compound containing 5 or more and 15 or less polymerizable groups in a molecule: A compound containing 1 or more and 4 or less polymerizable groups in a molecule is preferably in the range of 60:40 to 95: 5 in terms of mass. The range of 70: 30-90: 10 is more preferable.

(C) It is preferable that the sum total of content of a polymeric compound is 10 mass%-60 mass% in the total solid in the coloring photosensitive resin composition layer of this invention, It is more preferable that it is 15 mass%-50 mass%, 18 It is more preferable that they are mass%-40 mass%.

By setting it as this range, the heat resistance of the cured film obtained becomes favorable and the surface roughening after image development and the generation | occurrence | production of the wrinkle after postbaking are suppressed effectively.

In the coloring photosensitive resin composition of this invention, mass ratio "(D) photoinitiator / (C) polymeric compound" of (C) polymeric compound and (D) oxime system photoinitiator mentioned later should just be 0.1 or more and 2.0 or less, Preferably they are 0.1 or more and 1.0 or less, Especially preferably, they are 0.3 or more and 0.9 or less. By setting it in the said range, pattern formation property is favorable and it is excellent in adhesiveness with a board | substrate. Moreover, the mask thickness after exposure and image development is enough, and pattern peeling is suppressed.

<(D) Oxime photoinitiator>

As a (D) oxime system photoinitiator in this invention, if it is a compound which has an oxime ester structure and starts and promotes superposition | polymerization of the said (C) polymeric compound, a conventionally well-known thing can be used without a restriction | limiting, An oxime ester compound, And And ketooxime compounds. Specifically, the ketooxime system photoinitiator represented by the following general formula (III), the oxime system photoinitiator represented by the following general formula (D-1) described in Unexamined-Japanese-Patent 2005-220097, and Unexamined-Japanese-Patent The oxime system photoinitiator etc. as described in 2006-516246 are mentioned, The ketooxime system photoinitiator represented by following General formula (III) is preferable from a viewpoint of hardening sensitivity and the coloring inhibition after postbaking.

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

In 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 0-5. In the case where a plurality of X's are present, a plurality of X's each independently represents a monovalent substituent.

As a monovalent substituent represented by said R, it is preferable that it is a monovalent nonmetallic atom group shown below.

As the monovalent nonmetallic atom group represented by R, 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, Arylsulfinyl group which may have a substituent, Alkylsulfonyl group which may have a substituent, Arylsulfonyl group which may have a substituent, Acyl group which may have a substituent, Alkoxycarbonyl group which may have a substituent, Aryloxy which may have a substituent Carbonyl group, phosphinoyl group which may have substituent, heterocyclic group which may have substituent, alkylthiocarbonyl group which may have substituent, arylthiocarbonyl group which may have substituent, dialkylaminocarbonyl group which may have substituent, and substituent Preferred dialkylaminothiocarbonyl groups may be mentioned.

As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2- Naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluoro A phenacyl group, 3-trifluoromethyl phenacyl group, 3-nitro phenacyl group, etc. are mentioned.

As an aryl group which may have a substituent, a C6-C30 aryl group is preferable, For example, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1- Pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , m-, and p-cumenyl group, mesityl group, pentarenyl group, vinaphthrenyl group, ternaphtanyl group, quarter naphthrenyl group, heptarenyl group, biphenylenyl group, indaseyl group, fluoranthenyl group, ace Naphthylenyl group, aceanthrylenyl group, phenenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, Pyrenyl group, clinsenyl group, naphthacenyl group, playadenyl group, pisenyl group, perylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hex 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.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, For example, a vinyl group, an allyl group, a styryl group, etc. are mentioned.

As an alkynyl group which may have a substituent, a C2-C10 alkynyl group is preferable, for example, an ethynyl group, a propynyl group, a propargyl group, etc. are mentioned.

As an alkyl sulfinyl group which may have a substituent, a C1-C20 alkyl sulfinyl group is preferable, For example, methyl sulfinyl group, ethyl sulfinyl group, propyl sulfinyl group, isopropyl sulfinyl group, butyl sulfinyl group, hexyl sulfinyl group, cyclo Hexyl sulfinyl group, octyl sulfinyl group, 2-ethylhexyl sulfinyl group, decanoyl sulfinyl group, dodecanoyl sulfinyl group, octadecanoyl sulfinyl group, cyanomethyl sulfinyl group, methoxymethyl sulfinyl group, etc. are mentioned.

As an aryl sulfinyl group which may have a substituent, a C6-C30 aryl sulfinyl group is preferable, For example, a phenyl sulfinyl group, 1-naphthyl sulfinyl group, 2-naphthyl sulfinyl group, 2-chlorophenyl sulfinyl group, 2 -Methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulphi Neyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulphi And a silyl group.

As the alkylsulfonyl group which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms is preferable, and for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclo Hexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, perfluoroalkylsulfonyl group Etc. can be mentioned.

As an arylsulfonyl group which may have a substituent, a C6-C30 arylsulfonyl group is preferable, For example, a phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2 -Methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfo Neyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminophenylsulfo And a silyl group.

As an acyl group which may have a substituent, a C2-C20 acyl group is preferable, For example, an acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2 -Naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2- Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-sia A nobenzoyl group, 4-methoxy benzoyl group, etc. are mentioned.

As an alkoxycarbonyl group which may have a substituent, a C2-C20 alkoxycarbonyl group is preferable, For example, a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, Octadecyloxycarbonyl group, a trifluoromethyloxycarbonyl group, etc. are mentioned.

Examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyl Oxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3- Trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc. are mentioned. .

As the phosphinoyl group which may have a substituent, a phosphinoyl group having 2 to 50 carbon atoms is preferable, and for example, dimethyl phosphinoyl group, diethyl phosphinoyl group, dipropyl phosphinoyl group, diphenyl phosphinoyl group, dimethoxy A phosphinoyl group, a diethoxy phosphinoyl group, a dibenzoyl phosphinoyl group, a bis (2, 4, 6- trimethylphenyl) phosphinoyl group, etc. are mentioned.

As the heterocyclic group which may have a substituent, an aromatic or aliphatic heterocycle including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is preferable. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, kuromeryl group, xanthenyl group, and phen Noxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolinyl group, isoindolinyl group, 3H-indole Aryl group, indolyl group, 1H-indazolyl group, furinyl group, 4H-quinolinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxaniryl group, quinazolinyl group, sinolinyl group , Pterridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group , Isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl , Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, kynuclidinyl group, morpholinyl group, thioxane A tril group etc. are mentioned.

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

Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethylaminophenylthiocarbonyl group, 4 -Diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-trifluoromethylphenyl A thiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, 4-methoxyphenylthiocarbonyl group, etc. are mentioned.

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

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

As said R, the acyl group which has an unsubstituted or substituted group from a point of high sensitivity is more preferable, and the acetyl group, propionyl group, benzoyl group, and toluyl group which have an unsubstituted or substituted group are specifically, preferable.

As said substituent, group represented by the following structural formula is mentioned, for example, Especially, any of (d-1), (d-4), and (d-5) is preferable.

As a divalent organic group represented by said A, C1-C12 alkylene which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent are mentioned.

As a substituent which can be introduce | transduced into these groups, For example, halogen atoms, 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, a phenoxy group, p-tolyl jade Alkoxycarbonyl groups, such as the aryloxy group, methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group, such as the time period, or acyloxy group, acetyl group, benzoyl group, such as an aryloxycarbonyl group, acetoxy group, propionyloxy group, benzoyloxy group, etc. , Aryl sulfa such as acyl groups such as isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, phenylsulfanyl group and p-tolylsulfanyl group Dialkylamino groups, such as alkylamino groups, such as a silyl group, a methylamino group, and a cyclohexylamino group, a dimethylamino group, a diethylamino group, a morpholino group, and a piperidino group, a phenylamino group, and a p-tolylamino group Alkyl groups, such as an arylamino group, a methyl group, an ethyl group, tert- butyl group, and a dodecyl group, such as an aryl group, such as a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, and phenanthryl group, etc. , Hydroxy group, carboxyl group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, A phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumyl group, a triphenyl phenacyl phosphoniumyl group, etc. are mentioned.

Among them, A is an alkylene group substituted with an unsubstituted alkylene group and an alkyl group (for example, methyl group, ethyl group, tert-butyl group and dodecyl group) from the point of increasing the sensitivity and suppressing coloring due to heating over time. Alkylene group and aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group substituted with a vinyl group (for example, vinyl group, allyl group)) Preference is given to alkylene groups substituted with).

As an aryl group represented by said Ar, a C6-C30 aryl group is preferable and may have a substituent.

Specifically, Ar is a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2 -Azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentare Nilyl group, vinaptanyl group, ternaphtanyl group, quarter naphthalenyl group, heptarenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, acenatrilenyl group, phenenyl group, fluorene Nyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, clinsenyl group, naphthacenyl group, playadenyl group, Picenyl group, perylenyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl , And the like cyclohepta hexenyl group, a pyran group Trail, Oh ballet group. Especially, a substituted or unsubstituted phenyl group is preferable at the point which raises a sensitivity and suppresses coloring by time-lapse of heating.

When the phenyl group has a substituent, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy group such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p. -Arylthiooxy groups such as aryloxy groups such as tolyloxy group, alkylthiooxy groups such as methylthiooxy group, ethylthiooxy group and tert-butylthiooxy group, phenylthiooxy group and p-tolylthiooxy group , Alkoxycarbonyl or aryloxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryl Arylsulfanyl groups such as acyl groups such as royl group, methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, phenylsulfanyl group and p-tolylsulfanyl group, methylamino group and cyclic Dialkylamino groups such as alkylamino groups such as hexylamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino groups such as phenylamino group, p-tolylamino group, ethyl group, tert-butyl group, dodecyl group, etc. Alkyl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group , Phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group, and the like.

In general formula (III), if the structure of "SAr" formed from S adjacent to said Ar is a structure shown below, it is preferable at the point of a sensitivity.

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, and a substituent An aryloxy group which may have, an alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amide group which may have a substituent on N, or a substituent A good acyloxy group, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, An arylsulfonyl group which may have a substituent, The acyl group which may have a substituent, The alkoxycarbonyl group which may have a substituent, or aryloxy carbon A carbonyl group, a carbamoyl 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, a halogen atom, etc. are mentioned. Can be.

As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, Isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2- Naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluoro A phenacyl group, 3-trifluoromethyl phenacyl group, 3-nitro phenacyl group, etc. are mentioned.

As an aryl group which may have a substituent, a C6-C30 aryl group is preferable, For example, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1- Pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , m-, and p-cumenyl groups, mesityl groups, pentarenyl groups, vinaphthrenyl groups, ternaphtanyl groups, quarternaphthalenyl groups, heptarenyl groups, biphenylenyl groups, indaseyl groups, fluoranthrenyl groups, aces Naphthylenyl group, aceanthrylenyl group, phenenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, Pyrenyl group, clinsenyl group, naphthacenyl group, playadenyl group, pisenyl group, perylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hex 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.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, For example, a vinyl group, an allyl group, a styryl group, etc. are mentioned.

As an alkynyl group which may have a substituent, a C2-C10 alkynyl group is preferable, for example, an ethynyl group, a propynyl group, a propargyl group, etc. are mentioned.

As an alkoxy group which may have a substituent, a C1-C30 alkoxy group is preferable, For example, a methoxy group, an ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- Butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyl jade A time period, N-octylaminocarbonylmethyloxy group, N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, cyanomethyloxy group, etc. are mentioned.

As an aryloxy group which may have a substituent, a C6-C30 aryloxy group is preferable, For example, a phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyl jade Period, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, 4 -Fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, etc. Can be mentioned.

As an alkylthiooxy group which may have a substituent, a C1-C30 alkylthiooxy group is preferable, For example, a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, an isopropylthiooxy group, a butylthiooxy group , Isobutylthiooxy group, sec-butylthiooxy group, tert-butylthiooxy group, pentylthiooxy group, isopentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthiooxy group, 2-ethyl Hexylthiooxy group, decylthiooxy group, dodecylthiooxy group, an octadecylthiooxy group, a benzylthiooxy group, etc. are mentioned.

As an arylthiooxy group which may have a substituent, a C6-C30 arylthiooxy group is preferable, For example, a phenylthiooxy group, 1-naphthylthiooxy group, 2-naphthylthiooxy group, 2-chlorophenyl Thiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthiooxy group, 3-sia Nophenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group, 4-methylsulfanylphenylthiooxy group, 4-phenylsulfanylphenylthiooxy group, etc. are mentioned.

As an acyloxy group which may have a substituent, a C2-C20 acyloxy group is preferable, For example, an acetyloxy group, a propanoyloxy group, butanoyloxy group, pentanoyloxy group, trifluoromethylcarbonyloxy group, benzoyl An oxy group, a 1-naphthyl carbonyloxy group, 2-naphthyl carbonyloxy group, etc. are mentioned.

As the alkylsulfanyl group which may have a substituent, an alkylsulfanyl group having 1 to 20 carbon atoms is preferable, and for example, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, cyclo Hexyl sulfanyl group, octyl sulfanyl group, 2-ethylhexyl sulfanyl group, decanoyl sulfanyl group, dodecanoyl sulfanyl group, octadecanoyl sulfanyl group, cyanomethyl sulfanyl group, methoxymethyl sulfanyl group, etc. are mentioned.

As an arylsulfanyl group which may have a substituent, a C6-C30 arylsulfanyl group is preferable, For example, a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2 -Methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfa Neyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfanyl group, 4-dimethylaminophenylsulfa And a silyl group.

As an alkyl sulfinyl group which may have a substituent, a C1-C20 alkyl sulfinyl group is preferable, For example, methyl sulfinyl group, ethyl sulfinyl group, propyl sulfinyl group, isopropyl sulfinyl group, butyl sulfinyl group, hexyl sulfinyl group, cyclo Hexyl sulfinyl group, octyl sulfinyl group, 2-ethylhexyl sulfinyl group, decanoyl sulfinyl group, dodecanoyl sulfinyl group, octadecanoyl sulfinyl group, cyanomethyl sulfinyl group, methoxymethyl sulfinyl group, etc. are mentioned.

As an aryl sulfinyl group which may have a substituent, a C6-C30 aryl sulfinyl group is preferable, For example, a phenyl sulfinyl group, 1-naphthyl sulfinyl group, 2-naphthyl sulfinyl group, 2-chlorophenyl sulfinyl group, 2 -Methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulphi Neyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulphi And a silyl group.

As the alkylsulfonyl group which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms is preferable, and for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclo Hexyl sulfonyl group, octyl sulfonyl group, 2-ethylhexyl sulfonyl group, decanoyl sulfonyl group, dodecanoyl sulfonyl group, octadecanoyl sulfonyl group, cyanomethylsulfonyl group, methoxymethyl sulfonyl group, etc. are mentioned.

As an arylsulfonyl group which may have a substituent, a C6-C30 arylsulfonyl group is preferable, For example, a phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2 -Methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfo Neyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminophenylsulfo And a silyl group.

As an acyl group which may have a substituent, a C2-C20 acyl group is preferable, For example, an acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2 -Naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2- Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-sia A nobenzoyl group, 4-methoxy benzoyl group, etc. are mentioned.

As an alkoxycarbonyl group or an aryloxycarbonyl group which may have a substituent, a C2-C20 alkoxycarbonyl group or an aryloxycarbonyl group is preferable, For example, a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, Octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenyl Sulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylfe 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.

As the carbamoyl group which may have a substituent, a carbamoyl group having 1 to 30 carbon atoms is preferable, and for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-butylcarb Bamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2 -Methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarba Barmoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4- Methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-Deep And the like can be a carbamoyl group.

As a sulfamoyl group which may have a substituent, the sulfamoyl group of 0-30 total carbons is preferable, For example, a sulfamoyl group, N-alkyl sulfamoyl group, N-aryl sulfamoyl group, N, N-dialkyl sulfone Pamoyl group, N, N- diaryl sulfamoyl group, N-alkyl-N-aryl sulfamoyl group, etc. are mentioned. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propyl sulfamoyl group, N-butyl sulfamoyl group, N-hexyl sulfamoyl group, N-cyclohexyl sulfamoyl group, N- Octyl sulfamoyl group, N-2-ethylhexyl sulfamoyl group, N-decyl sulfamoyl group, N-octadecyl sulfamoyl group, N-phenyl sulfamoyl group, N-2-methylphenyl sulfamoyl group, N-2- Chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N -3-cyanophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanyl Phenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N -A diphenyl sulfamoyl group, etc. are mentioned.

Examples which may have a substituent, an amino group is an amino group of a small number of bullets preferably 0 to 50, and for example, -NH _2, N- alkylamino, N- arylamino group, N- acylamino group, N- sulfonyl amino group, N, N- Dialkylamino group, N, N- diarylamino group, N-alkyl-N-arylamino group, N, N- disulfonylamino group, etc. are mentioned. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N -Octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N- 2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3- Cyanophenylamino group, N-3-trifluoromethylphenylamino group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanyl Phenylamino group, N-4-phenylsulfanylphenylamino group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-di Tylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N -(Dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, 5-dimethyl morpholino group, a carbazole group, etc. are mentioned.

As the phosphinoyl group which may have a substituent, a phosphinoyl group having 2 to 50 carbon atoms is preferable, and for example, dimethyl phosphinoyl group, diethyl phosphinoyl group, dipropyl phosphinoyl group, diphenyl phosphinoyl group, dimethoxy A phosphinoyl group, a diethoxy phosphinoyl group, a dibenzoyl phosphinoyl group, a bis (2, 4, 6- trimethylphenyl) phosphinoyl group, etc. are mentioned.

As the heterocyclic group which may have a substituent, an aromatic or aliphatic heterocycle including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is preferable. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, kuromeryl group, xanthenyl group, and phen Noxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolinyl group, isoindolinyl group, 3H-indole Aryl group, indolyl group, 1H-indazolyl group, furinyl group, 4H-quinolinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxaniryl group, quinazolinyl group, sinolinyl group , Pterridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group , Isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl , Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, kynuclidinyl group, morpholinyl group, thioxane And tril groups.

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

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

Examples of the amide group which may have a substituent on N include N, N-dimethylamide group, N, N-diethylamide group and the like.

Moreover, the alkyl group which may have a substituent mentioned above, 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, and the aryl jade which may have a substituent are mentioned. The time period, the alkylthiooxy group which may have a substituent, the arylthiooxy group which may have a substituent, the acyloxy group which may have a substituent, the alkylsulfanyl group which may have a substituent, the arylsulfanyl group which may have a substituent, and a substituent Alkylsulfinyl group which may have, arylsulfinyl group which may have substituent, alkylsulfonyl group which may have substituent, arylsulfonyl group which may have substituent, acyl group which may have substituent, alkoxycarbonyl group which may have substituent Or an aryloxycarbonyl group, a carbamoyl group which may have a substituent, a sulfamoyl group which may have a substituent, and an amino which may have a substituent The heterocyclic group which may have a group and a substituent may be substituted by the other substituent.

Such substituents include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy such as phenoxy group and p-tolyloxy group Acyloxy groups such as alkoxycarbonyl or aryloxycarbonyl groups such as period, methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, acetoxy group, propionyloxy group and benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, Arylsulfanyl groups such as acyl groups such as acryloyl group, methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, phenylsulfanyl group and p-tolylsulfanyl group, methylamino group, Arylamino groups, such as dialkylamino groups, such as an alkylamino group, such as a cyclohexylamino group, a dimethylamino group, a diethylamino group, a morpholino group, and a piperidino group, a phenylamino group, and a p-tolylamino group Alkyl groups such as methyl, ethyl, tert-butyl, dodecyl, phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl, and aryl groups such as phenanthryl; , Formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, A trimethyl ammoniumyl group, a dimethylsulfoniumyl group, a triphenyl phenacyl phosphoniumyl group, etc. are mentioned.

Among these, X has an alkyl group which may have a substituent, an aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, and a substituent from the point of solvent solubility and the absorption efficiency improvement of a long wavelength region. An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amino group which may have a substituent, or The amide group which may have a substituent on N is preferable, and the alkyl group which may have a substituent is especially preferable.

In addition, although n in general formula (III) shows the integer of 0-5, the integer of 0-3 is preferable from a viewpoint of the ease of synthesis, and the integer of 0-2 is more preferable.

When two or more X exists in general formula (III), some X may be same or different.

The specific example of the photoinitiator represented by said general formula (III) is shown below.

The compound represented by general formula (III) used for this invention has an absorption wavelength in the wavelength range of 250 nm-500 nm. More preferably, what has an absorption wavelength in the wavelength range of 300 nm-380 nm is mentioned. In particular, it is preferable that the absorbances of 308 nm and 355 nm are high.

It is preferable that content of the (D) oxime system photoinitiator used by this invention is 3 mass% or more and 20 mass% or less with respect to the total solid of a coloring photosensitive resin composition, The range of 5 mass% or more and 15 mass% or less is preferable, The range of 10 mass% or more and 15 mass% or less is more preferable.

In addition to said (D) oxime system photoinitiator, the coloring photosensitive resin composition of this invention is another photoinitiator different from the structure of (D) oxime system photoinitiator, unless the range of this invention is impaired. D-2) called another photopolymerization initiator].

As another (D-2) photoinitiator different from the structure of (D) oxime system photoinitiator, if it is a compound which starts and accelerates superposition | polymerization of the said (C) polymeric compound, a conventionally well-known thing can be used without a restriction | limiting. Specifically, for example, a ropin type photoinitiator, 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, an azide compound And metallocene compounds, organoboric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide) compounds and the like.

(D-2) As a lophin type photoinitiator which can be used as another photoinitiator, a hexaaryl biimidazole compound is mentioned, for example. As a hexaaryl biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2- Chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 '-Tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarb Carbonylphenyl) biimidazole, 2,2'-bis (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 (2,4 , 6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-cyanophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-cyanophenyl) -4,4', 5,5'-tetrakis (4 Phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4 , 4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetrakis (4 -Phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2 , 2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-ethylphenyl)- 4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-phenylphenyl) -4,4', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole , 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole,

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

2,2'-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', 5,5'-tetraphenylbiimidazole, 2, 2'-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) -4,4 ', 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) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Bis (2-fluorophenyl) -4,4 ', 5,5'-tet And the like can be mentioned phenyl biimidazole.

Among the above, particularly preferred compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, Hodogaya Kagaku Kogyo B-CIM), 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra- (3,4-dimethoxyphenyl) biimidazole (e.g., Nihon Sibelhegina HABI1311), 2 And 2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, Kurogane Kasei).

Further, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, organoboronic acid compounds, As a specific example of a disulfonic acid compound, an onium salt compound, and an acyl phosphine (oxide) compound, Wakabayashi etc. "Bull Chem. Soc. 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication 60-239736, Japanese Patent Laid-Open No. 61-169835, Japanese Patent Laid-Open No. 61-169837, Japanese Patent Laid-Open No. 62-58241, Japanese Patent Laid-Open No. 62-212401, Japanese Patent Laid-Open 63-70243, Japanese Patent Laid-Open No. 63-298339, MP Hutt "Journal of Heterocyclic Chemistry" 1 (No3), (1970), Japanese Patent Publication No. 6-29285, US Patent No. 3,479,185, 4,311,783, 4,622,286, etc., Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. 9-188685, Japanese Patent Laid-Open No. 9-188686 Japanese Patent Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open 2002- Organic borates described in Japanese Patent Application No. 107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin &quot; Rad Tech'98. Proceeding April 19-22, 1998, Chicago &quot; Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561, Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553 Japanese Patent Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128785, Japanese Patent Laid-Open No. 7-140589, Japanese Patent Laid-Open No. 7-306527 , Japanese Patent Application Laid-Open No. 7-292014, JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Laid-Open 2000-66385 Photopolymerization disclosed in Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Publication No. 2004-534797 I can be given as specific examples.

In this invention, it is preferable that content when using (D-2) another photoinitiator together is 100 mass parts or less with respect to 100 mass parts of content of the said (D) oxime system photoinitiator. Moreover, as total amount [(D) + (D-2)] of the photoinitiator with respect to the total solid of a coloring photosensitive resin composition, the range of 5 mass%-20 mass% is preferable, The range of 5 mass%-15 mass% Is more preferable, and the range of 10 mass%-15 mass% is still more preferable.

In addition, when using the compound which does not have absorption in an exposure wavelength as (D) specific polymerization initiator or (D-2) another photoinitiator, it is preferable to use the compound which has absorption in an exposure wavelength as a sensitizer. A sensitizer is mentioned later.

<(E) solvent>

The coloring photosensitive resin composition of this invention contains the (E) solvent and can be prepared using the (E) solvent. Moreover, the pigment dispersion composition mentioned above is also prepared using (E) solvent.

As the solvent (E), esters such as ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters , Methyl lactate, ethyl lactate, methyl oxyacetic acid, ethyl oxyacetic acid, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid, and 3-oxypropionic acid 3-oxypropionic acid alkyl esters such as methyl and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate) To alkyl 2-oxypropionates such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate. Ste (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2-methylpropionic acid Methyl, 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, and 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, Ethyl acetoacetic acid, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate and the like;

Ethers, for example, 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- Propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, tri Propylene glycol methyl ether acetate and the like;

Alkoxyalkyl acetates, for example 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate , 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, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, and cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like are preferable.

You may use (E) solvent combining 2 or more types other than using independently.

The coloring photosensitive resin composition of this invention can further contain other components, such as (F) sensitizer, surfactant, a thermosetting resin, as needed.

<(F) sensitizer>

In the colored photosensitive resin composition of this invention, it is preferable to use the compound which has absorption in an exposure wavelength as a sensitizer, and to improve the start efficiency of (D) oxime system photoinitiator. By exposure of the wavelength which this sensitizer can absorb, the radical generating reaction of the (D) oxime system photoinitiator component, and the polymerization reaction of the polymeric compound by it are accelerated | stimulated.

As such a sensitizer, well-known spectroscopic sensitizing dye or dye, or dye or pigment which absorbs light and interacts with a photoinitiator is mentioned.

Spectral sensitizing dyes or dyes suitable as the sensitizer which can be used in the present invention include polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, and rhoda). Min B, Rose Bengal), Cyanines (e.g. thiacarbocyanine, oxacarbocyanine), Melocyanines (e.g. melocyanine, carbomelocyanine), Thiazines (e.g. Nine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acriflavin), phthalocyanines (e.g. phthalocyanine, metal phthalocyanine), porphyrins (e.g. tetraphenyl Porphyrins, core metal substituted porphyrins), chlorophylls (eg chlorophyll, chloropyrine, core metal substituted chlorophyll), metal complexes, anthraquinones (eg anthraquinones), squarylium (eg squarylium) ) And the like, and among them, a thiol compound described in detail below is preferable.

The thiol compound further has a function of further improving the sensitivity of the photopolymerization initiator to active radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.

Examples of the thiol compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimetholpropane tristyropropionate (TMTP), pentaerythritol tetrakistyropropionate (PETP), and the like. Each polyfunctional thiol compound, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazolin, (beta) mercaptonaphthalene, N- Monofunctional thiol compounds, such as phenyl mercaptobenzimidazole, are mentioned.

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

Content of the thiol compound in the coloring photosensitive resin composition of this invention is 0.5 mass%-10 mass% with respect to the appetizer solid content mass of the photosensitive resin composition from a viewpoint of the improvement of the curing rate by the balance of polymerization growth rate and chain transfer. A range is preferable and the range of 0.5 mass%-5 mass% is more preferable.

<Other additives>

The coloring photosensitive resin composition of this invention may contain the other additive as needed in addition to (A) component-(E) component which is an essential component, and (F) component which is a preferable combined component. Hereinafter, arbitrary additives are demonstrated.

(Surfactants)

The coloring photosensitive resin composition of this invention can contain surfactant.

When the pigment concentration is increased, the thixotropy of the coating liquid is generally increased, so that the film thickness variation after the formation of the colored photosensitive resin composition layer (color layer coating film) is easily generated by applying or transferring the colored photosensitive resin composition onto the substrate. Moreover, especially in the formation of the coloring photosensitive resin composition layer (color layer coating film) by the slit coating method, it is important to level the coating liquid for coloring photosensitive resin composition layer formation to dry, and to form the coating film of uniform thickness. For this reason, it is preferable to contain an appropriate surfactant in the said colored photosensitive resin composition. As said surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a preferable thing.

As surfactant for improving applicability | paintability, a nonionic surfactant, a fluorine-type surfactant, a silicon type surfactant, etc. are added.

As nonionic surfactant, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, polyoxypropylene alkyl ether And nonionic surfactants such as polyoxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters are preferable.

Specifically, Polyoxy alkylene glycol, 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 octylphenyl ether, polyoxyethylene polythiylated ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polytyrylated ether and polyoxyethylene nonylphenyl ether; And nonionic surfactants such as polyoxyalkylenedialkyl esters such as polyoxyethylenedilaurate and polyoxyethylene distearate, sorbitan fatty acid esters, and polyoxyalkylene sorbitan fatty acid esters.

These specific examples are Adeka Pluronic series, Adecanol series, Tetronic series (above, made by ADEKA Co., Ltd.), Emulgen series, Leodol series [Above Kao Co., Ltd. product] , Eleminol series, noni pole series, octapole series, dodekapol series, new pole series [above, Sanyo Kasei Co., Ltd.], pioneer series [product made in Takemoto Yushi], Nissan Biion series [Nihon Yushi ( Note) etc.]. These commercially available can be used suitably. Preferable HLB value is 8-20, More preferably, it is 10-17.

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

As a specific commercial item, for example, Mega Pack F142D, F172, F173, F176, F177, F183, F780, F781, F782, F784, F552, F554, F30, F30, F R8, F R8 [ The above is DIC Corporation], fluoride FC-135, copper FC-170C, copper FC-430, copper FC-431 [above, Sumitomo Industries Co., Ltd.], sufflon S-112, copper S- 113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC- 106 (above, manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (above, manufactured by JEMCO Corporation), and the like.

As a silicon type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428 , DC-57, DC-190 [above, made by Toray Dow Corning Silicon Co., Ltd.], TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 [more, GE Toshiba Silicone Co., Ltd.] etc. are mentioned.

Among them, preferred surfactants for the present invention are Megapack F780, F781, F782, F784, F552, and F554 (above, manufactured by DIC Corporation).

These surfactant is 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 exceeds 5 parts by mass, streaks and surface roughness in coating drying tend to occur, and smoothness tends to deteriorate.

(Thermosetting resin)

The coloring photosensitive resin composition of this invention can contain thermosetting resins, such as an epoxy resin and an oxetane resin, as needed.

Examples of the epoxy resins include bisphenol A, cresol novolac, biphenyl, and alicyclic epoxy compounds.

For example, as bisphenol A, Efototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. (Above, made by Toto Kasei), Denacol EX-1101, EX-1102, EX-1103 (above, made by Nagase Kasei), Fraxel GL-61, GL-62, G101, G102 (above, made by Daicel Kagaku) ), And the like. In addition, similar bisphenol F type and bisphenol S type are mentioned to these. In addition, epoxy acrylates, such as Ebecryl 3700, 3701, 600 (above, made from Daicel ECB), can also be used.

As the cresol novolac type, Efototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, made by Toto Kasei), Denacol EM-125, etc. (made by Nagase Kasei), As biphenyl type, 3,5,3 ', 5'- tetramethyl-4,4' diglycidyl biphenyl etc. are mentioned.

Examples of the alicyclic epoxy compound include ceoxide 2021, 2081, 2083, 2085, eporide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above, manufactured by Daicel Kagaku), Santoto ST- 3000, ST-4000, ST-5080, ST-5100, etc. (above, Toto Kasei) etc. are mentioned. In addition, glycidyl ester etc. which modified | denatured the skeleton of the epoto YH-434, YH-434L which are amine epoxy resins, and the bisphenol-A epoxy resin with dimer acid can also be used.

Among these epoxy resins, Preferably novolak-type epoxy compounds and alicyclic epoxy compounds are preferable, It is especially preferable that epoxy equivalent is 180-250. As such a material, Epiclon N-660, N-670, N-680, N-690, YDCN-704L (above, DIC Corporation make), and EHPE3150 (made by Daicel Kagaku) are mentioned.

As oxetane resin, aron oxetane OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ, PNOX (above, Toagosei) can be used.

In addition, an oxetane resin can be used individually or in mixture with an acrylic copolymer, an epoxy resin, and a maleimide resin. In particular, when used in combination with an epoxy resin, the reactivity to heat generated by ultraviolet light laser exposure is high, and is preferable from the viewpoint of adhesion with the substrate.

As content in the coloring photosensitive resin composition of the epoxy resin and oxetane resin which concerns on this invention, 0.5-15 mass% is preferable with respect to the total solid of a coloring photosensitive resin composition, and 1-10 mass% is the solubility with respect to alkali. It is preferable from a viewpoint of compatibility of adhesiveness with a board | substrate.

(Organic carboxylic acid)

When promoting alkali solubility of an uncured part and further improving developability of a coloring photosensitive resin composition, addition of organic carboxylic acid, Preferably low molecular weight organic carboxylic acid with a molecular weight of 1000 or less can be performed. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azeline acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic 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, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Other carboxylic acids such as phenylacetic acid, phenoxyacetic acid, methoxyphenoxyacetic acid, hydratroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, cinnamildeacetic acid, coumalic acid and umbelic acid Can be mentioned.

(Silane coupling agent)

A silane coupling agent can be used for the coloring photosensitive resin composition of this invention from a viewpoint of the adhesive improvement with a further board | substrate.

As a silane coupling agent, what has an alkoxy silyl group as a hydrolyzable group which can chemically couple | bond an inorganic material is preferable. Moreover, it is preferable to have a group which shows affinity by interaction or bond formation with organic resin, and it is preferable to have a (meth) acryloyl group, a phenyl group, a mercapto group, glycidyl group, and oxetanyl group as such a group. Especially, what has a (meth) acryloyl group or glycidyl group is preferable.

That is, it is preferable that it is a compound which has an alkoxy silyl group, a (meth) acryloyl group, or an epoxy group as a silane coupling agent used for this invention, Specifically, the (meth) acryloyl- trimethoxysilane compound of the following structure, And glycidyl-trimethoxysilane compounds.

As addition amount at the time of using a silane coupling agent, it is preferable that it is the range of 0.2 mass%-5.0 mass% in the total solid in the colored photosensitive resin composition used for this invention, and 0.5 mass%-3.0 mass% are more preferable.

(No Polymerization)

In this invention, it is preferable to add a small amount of thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of a polymeric compound during manufacture or storage of a coloring photosensitive resin composition.

Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3 -Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine first cerium salt, phenoxazine, phenothiazine Etc. can be mentioned.

As for the addition amount of a thermal-polymerization inhibitor, 0.01 mass%-5 mass% are preferable with respect to colored photosensitive resin composition.

Moreover, in order to prevent the inhibition of polymerization by oxygen, you may add higher fatty acid derivatives, such as behenic acid and behenic acid amide, and may make it localize on the surface of the photosensitive layer in the process of drying after application | coating. As for the addition amount of a higher fatty acid derivative, 0.5 mass%-10 mass% of a coloring photosensitive resin composition are preferable.

(Plasticizer)

In addition, in this invention, in order to improve the physical property of a coloring photosensitive resin composition, you may add an inorganic filler, a plasticizer, etc.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine, and the like (C) polymerization. It can be added in the amount of 10 mass% or less with respect to the total mass of a sex compound and binder resin.

Although the colored photosensitive resin composition of this invention can be hardened | cured by a conventionally well-known exposure means, it hardens with high sensitivity especially by exposure of an ultraviolet light, and also shows high adhesiveness with a board | substrate. Although either the laser exposure method or the proximity exposure method may be used as exposure means of an ultraviolet light, the laser exposure method is preferable from a viewpoint of suppressing surface reticulation. The coloring photosensitive resin composition of this invention can be used suitably for formation of the coloring pattern of a color filter.

`` Pattern forming method, color filter and manufacturing method thereof ''

The coloring photosensitive resin composition and the pattern formation method of this invention are suitable for the color filter for liquid crystal display devices. Hereinafter, although the pattern formation method using the coloring photosensitive resin composition of this invention is demonstrated as a formation method of the pattern in the manufacturing method of the color filter for liquid crystal display devices, this invention is not limited to this method.

The pattern formation method of this invention provides the coloring layer formation process of providing the coloring photosensitive resin composition of this invention on a board | substrate, and forms a colored layer, exposure with the said patterned ultraviolet light laser with respect to the said colored layer, It includes an exposure process to form, and the image development process which develops a pattern by developing the colored layer in which the said latent image was formed, It is characterized by the above-mentioned. Moreover, you may provide the process (baking process) of baking the said colored layer, and the process (baking process) of baking the developed said colored layer as needed. Together these processes may be called a pattern formation process.

[Color layer formation process]

The colored layer formation process in this invention is a process of providing the coloring photosensitive resin composition of this invention on a board | substrate, and forming a colored layer.

As a board | substrate, alkali free glass, soda glass, borosilicate glass, quartz glass used for a liquid crystal display device, etc., and the thing which adhered the transparent conductive film to these, and the photoelectric conversion element board used for a solid-state image sensor etc. are mentioned, for example. Also, a plastic substrate can be used. It is preferable to form a black matrix in a lattice shape or the like using these substrates, and to form colored patterns in the empty portions of the lattice.

On these board | substrates, you may form an undercoat layer as needed for the improvement of the contact | adherence with the upper layer, the prevention of the diffusion of a substance, or the planarization of a board | substrate surface. It is preferable that a board | substrate is large (mostly 1 side or more 1m or more) at the point which achieves the effect of this invention more.

As a method of imparting the colored photosensitive resin composition of the present invention to form a colored layer on the substrate, a method of applying by various coatings such as slit coating, ink jet method, rotational coating, cast coating, roll coating, screen printing, etc. Can be applied. In the coating method, slit coating is preferable in view of precision and speed.

Moreover, the provision method which transfers the coating film previously formed on the support body by the said apply | coating method on a board | substrate can also be applied.

Regarding the transfer method, paragraphs [0023], [0036] to [0051] of JP 2006-23696A, and paragraphs [0096] to [0108] of JP 2006-47592A are prepared. The method can be suitably used also in the present invention.

In order to obtain sufficient color reproduction region and to obtain sufficient luminance of the panel, the colored layer in the present invention is preferably formed so that the film thickness after drying is 0.5 µm to 3.0 µm, and the thickness is 1.5 µm to 2.5 µm. More preferred.

[Drying process]

After the provision of the colored photosensitive resin composition as described above is completed, a drying step of drying the solvent by vacuum drying (VCD) may be performed. Moreover, you may heat-dry (prebak) the coating film on a board | substrate, and may obtain a colored layer.

60 degreeC-140 degreeC is preferable, and, as for the prebaking temperature of a coating film, 80 degreeC-120 degreeC is more preferable. Moreover, 30 second-300 second are preferable, and, as for a prebaking time, 80 second-200 second are more preferable.

Exposure process

The exposure process in this invention is a process of exposing with a patterned ultraviolet light laser with respect to the said colored layer, hardening an exposure area | region, and forming a latent image. In the exposure area of the pattern shape in a coloring photosensitive resin composition by the exposure process of this invention, the polymerization hardening reaction of (C) polymeric compound generate | occur | produces and advances by the start species generate | occur | produced from the (D) specific polymerization initiator, and it hardens | cures a hardening area | region And a pattern consisting of an uncured region is formed.

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

As an exposure wavelength of the ultraviolet light laser used for this invention, the range of 300 nm-380 nm is preferable at the point which is excellent in sensitivity, according to the photosensitive wavelength of a coloring photosensitive resin composition, The range of 310 nm-360 nm is more preferable, In particular, the 355 nm wavelength laser exposure method is preferable.

Specifically, the third harmonic (355 nm) of Nd: YAG laser, which is a relatively low cost solid laser, and the XeCl (308 nm) and XeF (353 nm) of the excimer laser can be suitably used.

Moreover, as an exposure amount of a to-be-exposed object (pattern), the range of 1mJ / cm <2> -100mJ / cm <2> may be sufficient, and the range of 1mJ / cm <2> -50mJ / cm <2> is more preferable. It is preferable at the point of productivity of pattern formation that an exposure amount is this range.

The ultraviolet light 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.

Although there is no restriction | limiting in particular as an exposure apparatus which can be used for this invention, As what is marketed, EGIS (made by V Technology Inc.), DF2200G (made by Dainippon Screen Co., Ltd.), etc. can be used. Devices other than the above are also preferably used.

The ultraviolet light laser has good parallelism of light and can perform pattern exposure 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, since the linearity of a pattern becomes higher, the pattern exposed using a mask is preferable.

[Developing process]

The developing process in this invention is a process of developing the colored layer in which the latent image was formed by hardening in the said exposure area | region, removing an unexposed part, and forming a pattern. The exposure area | region by an ultraviolet-ray laser is hardened in pattern shape, and in the image development process, the alkali development process is performed, the unirradiated part (uncured part) in the said exposure process is eluted and removed in alkaline aqueous solution, and the photocured part is carried out. By leaving only the pattern can be formed.

As the developing solution, an organic alkali developing solution, an inorganic alkaline developing solution or a mixture thereof is used.

As an alkali chemicals used for a developing solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetra, for example. Organic alkaline compounds such as ethyl ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and the like, and the concentration of these alkaline compounds in the range of 0.001 to Alkaline aqueous solution diluted with pure water so that it may become 10 mass%, Preferably it is 0.01-1 mass% is used suitably as a developing solution. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinses) with pure water after image development.

As image development temperature, 20 degreeC-35 degreeC is preferable, and 23 degreeC-30 degreeC is more preferable. 30 second-120 second are preferable, and, as for image development time, 40 second-90 second are more preferable. Among these, the preferable combination of developing temperature and developing time is 50 second-100 second at the temperature of 25 degreeC, and 40 second-80 second is mentioned at the temperature of 30 degreeC, for example.

The shower pressure is preferably 0.01 MPa to 0.5 MPa, preferably 0.05 MPa to 0.3 MPa, and preferably 0.1 MPa to 0.3 MPa. By selecting these conditions, the shape of the pattern can be rectangular, forward tapered, or arbitrarily designed.

[Post Baking Process]

In this invention, in order to make hardening of a coloring photosensitive resin composition complete, it is preferable to provide the post-baking process which bakes the developed said colored layer. The baking method can be performed by heating a board | substrate which has a pattern after image development and rinse continuously or batch type using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater.

As baking conditions, 150 degreeC-260 degreeC is preferable, 180 degreeC-260 degreeC is more preferable, and 200 degreeC-240 degreeC is the most preferable. The baking time is preferably 10 minutes to 150 minutes, more preferably 20 minutes to 120 minutes, and most preferably 20 minutes to 90 minutes.

In addition, when forming the coloring pattern of multiple colors, such as RGB tricolor and a light shielding layer, you may repeat formation cycle of formation of a colored layer, exposure, image development, and baking by the desired number of colors, and formation and exposure of a colored layer for every color After performing the and and development, the whole color powder may be baked at the same time. Thereby, the color filter provided with the colored pixel which consists of desired color is manufactured.

`` Liquid crystal display device ''

The color filter of the present invention is preferable for the production of a liquid crystal display device, and the liquid crystal display device using the color filter produced by the pattern forming method of the present invention can display high quality images.

For the definition of the display device and the description of each display device, for example, "Electronic display device (by Akio Sasaki, High School Research Co., Ltd., 1990)", "Display device (by Ibuki Sumiaki, Sangyo Tosho) 1989 Issuance). In addition, the liquid crystal display device is described, for example, in "next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo Kogyo Co., Ltd. 1994)." There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in the said "next-generation liquid crystal display technology."

The color filter for liquid crystal display devices is especially effective among the color TFT type liquid crystal display devices. About the liquid crystal display device of a color | collar TFT system, it describes in a "color TFT liquid crystal display (Kyoritsu Shootpan Co., Ltd. 1996 issuance). In addition, the present invention can be applied to a liquid crystal display device having an enlarged viewing angle, such as a transverse electric field driving method such as IPS, a pixel splitting method such as MVA, or an STN, TN, VA, IPS, OCS, FFS, R-OCB, or the like. Can be. These methods are described, for example, on page 43 of EL, PDP, LCD Display Technology and the Latest Trends in the Market (Published by Toray Research Center, Research and Research, 2001).

In addition to the color filter, the liquid crystal display 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. The color filter for liquid crystal display elements of this invention can be applied to the liquid crystal display device comprised from these well-known members.

About these members, for example, the market of '94 liquid crystal display peripheral materials and chemicals (Kentaro Shima, CMC 1994 issuance), and the current status and future prospects of the 2003 liquid crystal display market (the lower volume) Kichi, Fuji Chimera Souken 2003).

Backlighting is described in SID meeting Digest 1380 (2005) (A. Konno et. Al), pages 18-24 (Shima Yasuhiro), pages 25-30 (Yagi Takaaki), etc. of the December 2005 issue of the monthly display. have.

When the color filter produced by the pattern forming method of the present invention is used in a liquid crystal display device and combined with a three-wavelength tube of a conventionally known cold cathode tube, a high contrast can be realized, and red, green, and blue LED light sources (RGB) -LED) as a backlight can provide a liquid crystal display device having high luminance and high color reproducibility.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "%" and "part" are mass references | standards unless there is particular notice.

Synthesis Example 1 Synthesis of Alkali-Soluble Resin 1 [(B-2) Binder Resin] Containing an Allyl Group>

54 g of 1-methoxy-2-propanol was put into a 200 mL three-necked flask equipped with a stirring rod equipped with a stirring blade, a reflux cooling tube, and a thermometer, and heated to 70 ° C. under a nitrogen stream. 10.07 g of allyl methacrylate, 1.93 g of methacrylic acid, and 0.185 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were dissolved in 54 g of 1-methoxy-2-propanol as a plunger. It was dripped in the three neck flask over 2.5 hours using the pump. After completion of the dropwise addition, the mixture was further stirred at 70 ° C for 2 hours. After the completion of heating, the mixture was poured into 1 L of water and reprecipitated. The precipitate was filtered and dried in vacuo to give 9 g (yield 75%) of a polymer compound.

0.01 g of the polymer obtained as a weight-average molecular weight measurement sample was weighed into a 10 mL volumetric flask, and about 8 mL of tetrahydrofuran was added and dissolved at room temperature. This solution was measured using gel permeation chromatography (GPC). The weight average molecular weight of alkali-soluble resin 1 (allyl methacrylate / methacrylic acid copolymer, molar ratio = 80/20, the following structure) was 35000.

Synthesis Example 2: Binder Resin B-1-1

Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; Sakai Kagaku Kogyo Co., Ltd., 7.83 parts, and 15.57 parts of the compound (A-1) which have the following adsorption site, and also has a carbon-carbon double bond, are dissolved in 93.60 parts of dimethylformamide under nitrogen stream, Heated to 70 ° C. To this was added 0.06 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 3 hours. Further, 0.06 parts of V-65 was added and reacted at 70 ° C for 3 hours under a nitrogen stream. Then, by cooling to room temperature, a 20% solution of the reaction product of DPMP and compound A-1 was obtained.

Further, 23.4 parts of a 20% solution of the reaction product, a mixed solution of 18 parts of methyl methacrylate (MMA; monomer) and 2 parts of methacrylic acid were heated to 80 ° C. under a nitrogen stream. To this was added 0.007 parts of 2,2'-azobis (isobutyronitrile) (AIBN, manufactured by Wako Pure Chemical Industries, Ltd.), and after heating for 3 hours, 0.007 parts of AIBN was added again, at 80 ° C. under nitrogen stream. The reaction was carried out for 3 hours. Thereafter, the mixture was cooled to room temperature and diluted with acetone. After reprecipitation using a large amount of methanol, 19 parts of solids of the high molecular compound (B-1-1: polystyrene conversion weight average molecular weight 32000) of this invention shown below were obtained by vacuum-drying. In addition, in the following formula (B-1-1), the content ratio of the structural unit contained in the polymer skeleton is p ¹ : p ² = 90: 10 in terms of mass.

Example 1

(Preparation of a colored photosensitive resin composition)

(1-1.Preparation of Pigment Dispersion 1)

Pigment dispersion liquid 1 was prepared as follows. That is, the components of the composition described below were stirred and mixed at a rotational speed of 3,000 rpm for 3 hours using a homogenizer to prepare a mixed solution, and a bead disperser ultra apex mill using 0.1 mmφ zirconia beads (Kotobuki Kogyo Co., Ltd.) 8) dispersion | distribution process was performed for 8 hours.

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

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

24 parts of Disbybyk 161 big chemical company (30% solution)

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

                                                            100 copies in total

(1-2. Preparation of Photosensitive Resin Composition)

The component of the following compositions was further added to the obtained pigment dispersion liquid 1 39.2 parts, and it stirred and mixed, and prepared the 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

     (Nihon Kayaku Co., Ltd., KAYARAD DPHA) 3.9 copies

(C) Polymerizable Compound: Tetramethyrolmethane Tetraacrylate

     (Shin-Nakamura Kagaku Corporation make, NK ester A-TMMT) 0.69 parts

(D) Oxime type photoinitiator: 2.74 parts of compound A (following structure)

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

Epoxy compound: 0.60 part (made by Daicel Kagaku Co., Ltd., EHPE3150)

(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: Megapack F-554 (manufactured by DIC Corporation) 0.02 parts

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

Type and content of (B-1) binder resin, (A) coloring agent, (D) oxime system photoinitiator in adjustment of the coloring photosensitive resin composition of the said Example 1, and content ratio of (B-2) binder resin The coloring photosensitive resin composition of Examples 2-15 and Comparative Examples 1-6 was similarly prepared except having changed to the description of following Tables 1-7.

In addition, the numerical value described in (C) polymeric compound in the following table shows the functional group number of the polymeric compound used, and a "ratio" is content rate of a 5-functional or more functional polymeric compound, and a 1-4 functional polymeric compound. Indicates.

Evaluation of colored photosensitive resin composition

(Formation of pattern shape pixel)

The colored photosensitive resin composition of Examples 1-15 and Comparative Examples 1-6 obtained as mentioned above was slit-coated (Hirata) on the surface of an alkali-free glass substrate (Corning, Inc., 1737, 550 mm x 660 mm). After coating using Kiko Co., Ltd., HC-6000), prebaking was performed in a clean oven at 90 ° C. for 120 seconds to form a coating film (colored layer) having a thickness of 2.0 μm, thereby obtaining a substrate on which the coating film was formed (colored). Layer formation process).

Subsequently, a pulse of about 1 mJ / cm 2 was applied to the surface of the photosensitive resin composition layer (colored layer) using EGIS (V Technology, third harmonic of YAG laser (355 nm), pulse width 6 ns) as the laser exposure apparatus. Irradiation was performed 20 times through a photomask, and the exposure part was hardened (exposure process).

Subsequently, this substrate was subjected to 1.0% developer (CDK-1 1 part by mass) of potassium hydroxide developer CDK-1 [manufactured by Fujifilm Electronics Material Co., Ltd.] using a developing device (manufactured by Hitachi High Technologies). The solution was diluted with a mass part, 25 degreeC), it developed for 50 second by setting a shower pressure to 0.20 Mpa, wash | cleaned with pure water, and air-dried (development process). Thereafter, 30 minutes post-bake was performed in a 230 degreeC clean oven, and the blue stripe pixel array was formed on the board | substrate.

(Evaluation of Linewidth Sensitivity)

The gap (gap) of the surface of the photosensitive resin composition layer and the mask on the board | substrate with a coating film was set to 200 micrometers, and it exposed at 20mJ / cm <2> of exposure amounts using the mask which has a line and space of 20 micrometer width. In the thus-obtained exposed substrate, the above development, washing, air drying, and post-baking treatment were performed. The obtained line pattern was observed with the optical microscope, the line width was measured, and the following reference | standard evaluated.

A: 30 µm or more

B: 27 micrometers or more and less than 30 micrometers

C: 25 micrometers or more and less than 27 micrometers

D: less than 25 μm

E: A pattern is not formed. Or peeled off and cannot be evaluated.

(Evaluation of linearity)

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

Evaluation standard

A: No shaking, no cracking, straight lines.

B: There are several shakes, but the line is almost straight.

C: The line unevenness about 2 micrometers generate | occur | produces.

D: The line unevenness | corrugation generate | occur | produces about 5 micrometers.

E: A pattern is not formed. Or peeled off and cannot be evaluated.

(Evaluation of heat resistance)

The board | substrate obtained by evaluation of line width sensitivity was further baked in a 240 degreeC clean oven for 60 minutes, and color change ((DELTA) E ^* ab) before and after further baking was performed using the Otsuka Denshi Corporation spectrophotometer MCPD-2000. Measured. (DELTA) E * ab here means the color difference in L ^* a ^* b ^* color system. Color change ΔE ^* ab was evaluated based on the following criteria.

Evaluation standard

5: ΔE ^* ab is greater than or equal to 0 and less than 1.0.

4.5: ΔE ^* ab is 1.0 or greater but less than 2.0

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

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

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

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

2: ΔE ^* ab is 5.0 or more

1: There is peeling.

(Evaluation of the wrinkle)

The board | substrate obtained by evaluation of line width sensitivity was baked in 230 degreeC clean oven for 30 minutes, and the presence or absence of wrinkles of the coloring pattern before and after baking was observed with the optical microscope (magnification: 200 times), and the following references | standards evaluated.

Evaluation standard

(Circle): The generation | occurrence | production of a wrinkle is not seen.

(Triangle | delta): Wrinkles generate | occur | produce weakly.

X: Wrinkles generate strongly.

(General evaluation)

Line width sensitivity, linearity and heat resistance were evaluated based on the following criteria. The results are summarized in Table 8.

Evaluation standard

5: Very good.

4.5: Excellent.

4: No problem in normal use.

3.5: Slightly poor performance, but no problem.

3: Lowest level in normal use.

2.5: Problems slightly below the limit.

2: can not be used due to insufficient performance.

1: Level at which no evaluation can be made.

As clearly shown in Table 8, the colored photosensitive resin compositions of Examples 1-15 according to the present invention had good line width sensitivity, the obtained pattern was excellent in linearity, and the color change was small even when the colored pattern was heated, The generation | occurrence | production of the wrinkle after postbaking was also suppressed, and the favorable coloring pattern was obtained.

On the other hand, the comparative example 1 which does not contain the (B-1) binder resin in this invention, and the comparative example 2 using initiators other than (D) oxime system photoinitiator are line width sensitivity, linearity of pattern, heat resistance, and wrinkles. In Comparative Example 3 in which the content of the (B-2) binder resin is too high, the occurrence of wrinkles after the post-baking is remarkable, and in Comparative Example 3 in which the content of the (B-1) binder resin is too large, Comparative Examples 4 and (B- 2) All of the comparative example 5 which does not contain binder resin was inferior compared with an Example in any of line width sensitivity, linearity, and a wrinkle. Moreover, the comparative example 6 which used initiators other than the (D) oxime system photoinitiator, and used the sensitizer further became inferior to line width sensitivity and the linearity of a pattern.

Claims (9)

At least (A) a colorant, (B-1) a binder resin represented by the following general formula (I) and having at least one acidic group, (B-2) having a structural unit and an acidic group represented by the following general formula (II) Binder resin containing a structural unit, (C) polymeric compound, (D) oxime system photoinitiator, and (E) solvent; The coloring photosensitive resin composition whose content ratio by the mass reference of the said (B-1) binder resin and (B-2) binder resin is 3: 7-7: 3.

[In General Formula (I), R <^3> represents a (m + n) valent organic coupling group, R <^4> and R <^5> respectively independently represents a single bond or a bivalent organic coupling group. A ² is an organic pigment structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, And monovalent organic groups containing at least one substructure selected from hydroxyl groups. n pieces of A ² and R ⁴ may be the same or different. m represents 1-8, n represents 2-9, and m + n satisfies 3-10. P ² represents a polymer skeleton. m pieces of P ² and R ⁵ may be the same or different.]

[In formula (II), R <^11> -R <^15> respectively independently represents 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 of claim 1,
The said (D) oxime system photoinitiator is a ketooxime system photoinitiator represented by the following general formula (III), The coloring photosensitive resin composition characterized by the above-mentioned.

[In 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 0-5. When there are a plurality of X's, a plurality of X's may be the same or different.] The method according to claim 1 or 2,
It is for ultraviolet light laser exposure, The coloring photosensitive resin composition characterized by the above-mentioned. The colored layer formation process of providing the colored photosensitive resin composition of Claim 1 or 2 on a board | substrate, and forming a colored layer, and the exposure process which hardens an exposure area | region by performing ultraviolet light laser exposure of pattern shape to the said colored layer. And a developing step of developing and removing the unexposed part of the colored layer to form a pattern. The method of claim 4, wherein
The exposure wavelength of the said ultraviolet light laser is 300 nm-380 nm, The pattern formation method characterized by the above-mentioned. The method of claim 4, wherein
And said ultraviolet light laser is a pulse laser oscillating at a frequency of 20 Hz to 2000 Hz. It has the process of forming a coloring pattern on a board | substrate by the pattern formation method of Claim 4, The manufacturing method of the color filter characterized by the above-mentioned. The color filter manufactured by the manufacturing method of the color filter of Claim 7. A display device comprising the color filter according to claim 8.