TW201510649A - Photosensitive resin composition, resin cured product thereof and color filter - Google Patents

Abstract

A photosensitive resin composition is provided, which is a blue photosensitive resin composition including a pigment, a dispersing agent, and a developing resin, wherein the pigment includes a phthalocyanine pigment and a quinacridone pigment.

Description

Photosensitive resin composition, resin cured product, and color filter

The present invention relates to a photosensitive resin composition, a cured resin thereof, and a color filter.

The color filter generally forms a pixel portion including three colors of red (R), green (G), and blue (B), and is arranged on a thin plate which is arranged in an arrangement called "Bayer pattern". structure. Thereby color separation is performed spatially. In the case of a display device, light of such a color is emitted to the outside, and if it is an imaging element, incident light of such a color is accurately reached to the sensor.

In particular, recent solid-state imaging devices intended to be continuously developed by technology development are precision semiconductor articles incorporating a plurality of fine members. For example, the image sensor includes: a plurality of pixels that convert incident light into an electrical signal, and a complementary metal oxide semiconductor (CMOS) sensor that selectively reads out each pixel, further passes A charge coupled device (CCD) that charges a signal charge read from each pixel in the substrate. In order to obtain light information appropriately and with high sensitivity by the sensor, adjustment of the hue of the pixels of the color filter is highly required. Therefore, there are proposals such as In the example of the following method, the coloring materials forming the pixel portion are mixed by a specific formulation (see Patent Document 1 to Patent Document 3).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-181384

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-216952

[Patent Document 3] Japanese Patent No. 4576890

There are not many proposals for the improvement of the hue of the blue (B) color filter pixel portion. On the other hand, the required hue is not necessarily the same. There is a portion that changes according to the user's preference. Moreover, it also differs depending on the information processing using the internal sensor or circuit. Among them, there is a possibility that a brightly transmissive colored material is not displayed in a wavelength region (about 500 nm or more) that transmits blue, but a colored material whose transmittance is gradually decreased toward the long wavelength side. In particular, when considering the color separation property close to the human eye, a colored material showing continuous absorption with such a green region can be useful.

Therefore, an object of the present invention is to provide a photosensitive resin composition having a slope of a specific spectral distribution in a slope of 500 nm in a blue spectral distribution curve of a cured film, a cured resin thereof, and a color filter produced using the same. Light film. Further, an object of the invention is to provide a photosensitive resin composition which suppresses or prevents a film surface roughness when a cured film is formed, a cured resin thereof, and a color filter produced using the same. Light film.

The subject matter can be solved by the means described below.

[1] A photosensitive resin composition which is a blue photosensitive resin composition containing a pigment, a dispersant, and a developing resin, and the pigment comprises an indigo pigment and a quinacridone pigment.

[2] The photosensitive resin composition according to [1], which further contains a polymerizable compound.

[3] The photosensitive resin composition according to [1], wherein the spectral characteristics of the coating film satisfy all of the following (1) to (4), and (1) the transmittance at a wavelength of 450 nm is 75%. The above (2) transmittance at a wavelength of 475 nm is 75% or less, (3) transmittance at a wavelength of 525 nm is 20% or more, and (4) transmittance at a wavelength of 600 nm is 5% or less.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the polymer compound to be the developing resin has a polymerizable group in a molecule.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the polymer compound to be the developing resin has a weight average molecular weight of 23,000 or less.

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the pigment is contained in an amount of 30% by mass or more and 80% by mass or less of all solid components.

[7] The photosensitive resin composition according to any one of [1] to [6] wherein The quinacridone pigment is contained in an amount of from 1 part by mass to 60 parts by mass per 100 parts by mass of the indigo pigment.

The photosensitive resin composition according to any one of the above aspects, wherein the dispersing agent is contained in an amount of from 1 part by mass to 80 parts by mass per 100 parts by mass of the pigment.

The photosensitive resin composition according to any one of the above aspects, wherein the developing resin is contained in an amount of from 1 part by mass to 30 parts by mass per 100 parts by mass of the pigment.

[10] The photosensitive resin composition according to any one of [1] to [9] wherein the indigo pigment is C.I.P.B. 15:6.

[11] The photosensitive resin composition according to any one of [1] to [9] wherein the quinacridone pigment is C.I.P.R.209 or C.I.P.R.122.

[12] The photosensitive resin composition according to any one of [1] to [11] further comprising a dioxazine pigment as the pigment.

[13] The photosensitive resin composition according to [12], wherein the dioxazine pigment is C.I.P.V.23.

[14] The photosensitive resin composition according to any one of [1] to [13] which is a color filter.

[15] A resin cured product obtained by applying the photosensitive resin composition according to any one of [1] to [14].

[16] A color filter comprising the cured product of the resin according to [15].

In the blue spectral distribution curve of the cured film of the present invention, the slope of the vicinity of 500 nm shows a more oblique specific spectral distribution. Further, the photosensitive resin composition of the present invention can suppress or prevent film surface roughness when a cured film is formed, as needed. Further, the blue resin cured product and the pixel portion of the color filter formed using the photosensitive resin composition have a peculiar hue, and are particularly suitable for use in a solid-state imaging device.

The above and other features and advantages of the present invention will become more apparent from the description and the accompanying drawings.

10‧‧‧ Solid-state imaging components

11‧‧‧Upper flattening film

12‧‧‧ Lower flattening film

15‧‧‧Microlens

20‧‧‧Color filters

20B, 20G, 20R‧‧‧Color Filters

G‧‧‧ Width of the picture department

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a part of a solid-state imaging device according to a preferred embodiment of the present invention.

2 is a graph showing the spectral distribution of the cured film of the photosensitive resin composition prepared in the examples and the comparative examples.

The photosensitive resin composition for a color filter of the present invention has peculiar spectral characteristics and can be suitably used in a solid-state imaging device. Further, it is possible to suppress or prevent the surface roughness of the pixel portion which is generated depending on the situation, and to provide a high-quality color filter. The photosensitive resin composition of the present invention will be described in detail based on preferred embodiments thereof. First, a solid-state imaging device of a suitable application form will be described.

[Solid photographic element]

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial cross-sectional view showing a solid-state imaging device according to a preferred embodiment of the present invention. Only the upper side (light incident side) of the lower planarizing film 12 of the solid-state imaging element 10 is illustrated in FIG. The circuit or the light receiving element or the like is included on the lower side, but the illustration is omitted. The solid-state imaging device 10 of the present embodiment includes a light receiving element (photodiode) (not shown) provided on a substrate (not shown), a color filter 20, an upper planarizing film 11, and Microlens 15 and the like. The upper flattening film 11 and the lower planarizing film 12 are not necessarily provided. In addition, in FIG. 1, in order to make each part clear, a part of exaggeration is shown, regardless of the ratio of thickness or width of each.

The color filter 20 includes color filter pixel portions 20R, 20G, and 20B of red (R), green (G), and blue (B). In the present specification, as described above, the constituent elements of the respective colors of the color filter are referred to as "pixel portions", and the region (g in the figure) divided by the pixel portion is referred to as "pixel". There is a difference.

As described above, the color filter 20 includes a plurality of green pixel portions 20G, a green pixel portion 20R, and a green pixel portion 20B which are two-dimensionally arranged. In the present embodiment, there is no black matrix therebetween. Each of the colored pixel unit 20R, the colored pixel unit 20G, and the colored pixel unit 20B is formed at a position above the light receiving element. The green pixel portion 20G is formed in a Bayer pattern (a checkerboard pattern), and the blue pixel portion 20B and the red pixel portion 20R are formed between the respective green pixel portions 20G. In addition, in FIG. 1, in order to demonstrate that the color filter 20 contains the pixel parts of three colors, each coloring pixel part 20R, the coloring pixel part 20G, and the coloring pixel part 20B are arranged in one row, and it shows.

The planarizing film 11 is formed to cover the upper surface of the color filter 20, and planarizes the surface of the color filter. The microlens 15 is provided with a convex surface The condensing lens is disposed above the planarizing film 11 and above the light receiving element. In other words, the microlens, the color filter pixel portion, and the light-receiving element are arranged in series along the incident direction of the light, and the light from the outside is efficiently guided to the respective light-receiving elements. Further, the light receiving element and the microlens are not described in detail, but a light receiving element and a microlens which are generally used in such products can be suitably used.

In the present invention, the width g of the pixel portion is not particularly limited, and in order to remarkably exhibit the effect, it is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less. There is nothing special about the lower limit value, and it is actually 100 nm or more. The rectangular pixel of the Bayer pattern is preferably 5 μm □ or less, more preferably 3 μm □ or less, still more preferably 2 μm □ or less, and particularly preferably 1 μm □ or less in plan view. There is nothing special about the lower limit value, and it is actually 100 nm □ or more. Further, in order to make the effect of the preferred embodiment of the present invention remarkable, it is preferable that the respective pixel portions are adjacent to each other. In addition, "□(sq)" means the length of one side of a square.

[Spectral characteristics]

According to the blue photosensitive resin composition of the preferred embodiment of the present invention, the spectral characteristics are obtained in the cured film: moderate absorption in the rising region of the spectral distribution, and absorption in the peak transmission region is sufficiently suppressed. In other words, it can be said that the spectral characteristics are such that sufficient transmission is exhibited in a region of about 500 nm or more, and the spectral distribution curve is inclined at around 500 nm. The numerical representation of the spectral distribution is as follows. A more specific spectral distribution curve is shown in accompanying Figure 1. Expressed as the target value.

(1) The transmittance at a wavelength of 450 nm is 75% or more

(2) The transmittance at a wavelength of 475 nm is 75% or less

(3) The transmittance at a wavelength of 525 nm is 20% or more

(4) The transmittance at a wavelength of 600 nm is 5% or less

By exhibiting such a spectral characteristic, there is a possibility of causing a color separation of a slightly wider incident light, for example, a new design that contributes to a solid-state imaging element having performance close to the human eye. Further, unless otherwise specified, the measurement method of the spectral characteristics can be carried out by using the conditions measured in the examples described later.

[Resin hardened material (color filter)]

In each of the pixel portions of the color filter of the preferred embodiment of the present invention, it is preferred to cure the photosensitive resin composition described below. The photosensitive resin composition of this embodiment contains a pigment (a), a dispersing agent (b), and a developing resin (c). Further, it may further contain a polymerizable compound (d), a polymerization initiator (e), and the like.

(a) pigment

In the present invention, as the pigment to be a colorant, an indigo pigment and a quinacridone pigment are used. Dioxazine pigments can also be further used.

The indigo pigment is preferably a blue colorant, preferably a coloring agent which becomes a base in a blue photosensitive resin composition. Examples of the indigo pigments include Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Blue 16, Pigment Blue 75, and Pigment Blue 15. Among them, Pigment Blue 15:6 (C.I.P.B. 15:6) is preferred.

Examples of the quinacridone pigments include Pigment Violet 19, Pigment Violet 42, Pigment Red 122, and Pigment Red 192, Pigment Red 202, Pigment Red 207, Pigment Red 209, and the like. Among them, Pigment Red 122 (C.I.P.R. 122) or Pigment Red 209 (C.I.P.R. 209) is preferred.

Examples of the dioxazine pigment include Pigment Violet 23 and Pigment Violet 37. Among them, Pigment Violet 23 (C.I.P.V. 23) is preferred.

The average primary particle diameter of the pigment is actually 10 nm or more. The upper limit is preferably 1 μm or less, more preferably 500 nm or less, still more preferably 200 nm or less, still more preferably 100 nm or less, and particularly preferably 50 nm or less from the viewpoint of obtaining a better contrast. Further, as an index indicating the monodispersity of the particles, in the present invention, the ratio (Mv/Mn) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used unless otherwise specified. The monodispersity (i.e., Mv/Mn) of the pigment fine particles (primary particles) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.5. Further, in the present invention, the average primary particle diameter and the monodispersity of the particles are obtained from the images observed by the transmission electron microscope to obtain an equivalent circle diameter, and the evaluation values of 500 are used.

The preparation method of the pigment particles may be carried out by a usual method, for example, by grinding and pulverization, and may be prepared by precipitation (precipitation method) using a good solvent and a poor solvent. Regarding the former (destruction method), the pigment particles can be refined by a general method using a bead mill or the like. For example, refer to the description in "Mechanical Crushing" in the Journal of the Japan Society of Imaging Studies, Vol. 45, No. 5 (2006), pages 12 to 21. The latter (additional layer method) is also called "reprecipitation method", and the like, for example, Japanese Patent Laid-Open No. 2011-026452, Japanese Patent Laid-Open No. 2011-012214, Japanese Patent Laid-Open No. 2011-001501 Japanese Laid-Open Patent Publication No. 2010-235895, Japanese Patent Laid-Open No. 2010-2091, and Japanese Patent Laid-Open No. 2010-209160.

The concentration of the coloring agent (pigment) contained in the photosensitive resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and further more than all the solid components of the photosensitive resin composition. The best is 30% by mass or more. The upper limit is not particularly limited, but is preferably 80% by mass or less, and more preferably 60% by mass or less.

With respect to the relationship between the indigo pigment and the quinacridone pigment, it is preferred to contain 1 part by mass or more of the quinacridone pigment, more preferably 5 parts by mass based on 100 parts by mass of the indigo pigment. Further, it is more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more. The upper limit is preferably 60 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 30 parts by mass or less. It is contained in an amount of 25 parts by mass or less.

With respect to the relationship between the indigo pigment and the dioxazine pigment, it is preferred to contain 0 parts by mass or more of the dioxazine pigment, more preferably 5 parts by mass, based on 100 parts by mass of the indigo pigment. The above is more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more. The upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 40 parts by mass or less, and still more. It is preferable to contain 30 parts by mass or less, and particularly preferably 20 parts by mass or less.

The colored composition of the present invention may be suitably added with a known inorganic pigment, and Coloring agents such as machine pigments and dyes.

Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. An oxide, a composite oxide of the metal, a black pigment such as carbon black or titanium black.

Examples of the organic pigment include CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, and CI Pigment Yellow 109. , CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180 , CI Pigment Yellow 185, CI Pigment Yellow 199; CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 71; CI Pigment Red 81, CI Pigment Red 105, CI Pigment Red 122, CI Pigment Red 149 , CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 242 , CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270; CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32, CI Pigment Violet 39; CI Pigment Blue 1, CI Pigment Blue 2 , CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:3 , C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 66; C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58; C.I. Pigment Brown 25, C.I. Pigment Brown 28; C.I. Pigment Black 1 and the like.

In addition, the inclusion of the same pigment as exemplified above refers to a pigment which is different from those selected herein.

For the known dyes, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, and JP-A No. Japanese Patent No. 2, 592, 207, U.S. Patent No. 4, 480, 850, U.S. Patent No. 5, 568, 850, U.S. Patent No. 5, 567, 950, U.S. Patent No. 5, 505, 950, U.S. Patent No. 5,567, 920, Japanese Patent Laid-Open No. Hei 5- 333 207, Japanese Patent Laid-Open No. Hei 6-35183, Japan The dye disclosed in Japanese Laid-Open Patent Publication No. Hei 6-51115, and the like. As the chemical structure, a pyrazole azo type, a pyrromethene type, an anilino azo type, a triphenylmethane type, an anthraquinone type, a benzylidene type, an oxaphthalocyanine type, a pyrazolotriazole azo can be used. A dye such as a pyridone azo system, a cyanine system, a phenothiazine system, or a pyrrolopyrazole azomethine system. Further, a dye multimer can also be used as the dye. The dye polymer is a compound described in JP-A-2011-213925 and JP-A-2013-041097.

(b) Dispersant

. Polymer dispersant

Examples of the dispersing agent include polymer dispersing agents (for example, polyamidoamine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, Modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate), and polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, pigment derivative Things and so on.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure.

The polymer dispersant acts on the surface of the pigment to prevent re-agglomeration. Therefore, a terminal modified polymer having a tack-increasing site on the surface of the pigment, a graft polymer, and a block polymer are preferable. On the other hand, the pigment derivative has an effect of promoting adsorption of the polymer dispersant by modifying the surface of the pigment.

Specific examples of the pigment dispersant which can be used in the present embodiment include "Disperbyk-101 (polyamide amine phosphate), Disperbyk-107 (carboxylate), Disperbyk manufactured by BYK Chemie Co., Ltd.). -110 (copolymer containing acid group), Disperbyk-130 (polyamide), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-170 (polymer) Copolymer)", "BYK-P104, BYK-P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001", "EFKA4047, EFKA4050, EFKA4010, EFKA4165 (polyurethane) manufactured by EFKA) EFKA4330, EFKA4340 (block copolymer), EFKA4400, EFKA4402 (modified polyacrylate), EFKA5010 (polyester decylamine), EFKA5765 (high molecular weight polycarboxylate), EFKA6220 (fatty acid polyester), EFKA6745 (Indigo derivative), EFKA6750 (azo pigment derivative), taste "Ajisper PB821, Ajisper PB822" manufactured by Seiki Chemical Co., Ltd., "FLOWLEN TG-710 (urethane oligomer)", "Polyflow No. 50E, Polyflow No. 300 (acrylic acid) manufactured by Kyoeisha Chemical Co., Ltd." "Copolymer"), "DISPARLON KS-860, DISPARLON 873SN, DISPARLON 874, DISPARLON #2150 (aliphatic polycarboxylic acid), DISPARLON #7004 (polyether ester), DISPARLON DA-703-50, manufactured by Nanben Chemical Co., Ltd. DISPARLON DA-705, DISPARLON DA-725", DEMOL RN, DEMOL N (DEMOL condensate), DEMOL MS, DEMOL C, DEMOL SN-B (aromatic sulfonate fumarin polycondensate) )", "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, EMULGEN 930, EMULGEN 935, EMULGEN 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearylamine acetate) Ester)", "Solsperse 5000 (indigo derivative), Solsperse 22000 (azo pigment derivative), Solsperse 13240 (polyester amine), Solsperse 3000, Solsperse 17000, Solsperse 20000, manufactured by Lubrizol. Solsperse 27000 (polymer with functional part at the end) Solsperse 24000, Solsperse 28000, Solsperse 32000, Solsperse 38500 (grafted polymer), "Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene single hard) manufactured by Nikko Chemical Co., Ltd. Fatty acid ester) and so on.

. Phosphate dispersant

As the dispersing agent, a phosphate compound represented by the following formula (P1) is also preferably used.

(wherein, R ^P1 represents a polyester residue having a number average molecular weight of 500 to 10,000, and y represents 1 to 2)

The phosphate represented by the formula (P1) can be obtained by phosphating a polyester residue having a hydroxyl group at one terminal. The polyester residue having a hydroxyl group at a single terminal can be obtained by subjecting a monool as a starter to ring-opening addition of ε-caprolactone or the like. For details, for example, paragraphs [0023] to [0040] of Japanese Patent Laid-Open Publication No. 2007-231106 can be referred to.

Further, as the dispersing agent, a phosphate compound represented by the following formula (P2) is also preferable.

In the formula (P2), R ^P2 and R ^P3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a carbon atom number; 6 to 20 hydrocarbon groups.

m and 1 each independently represent an integer of 1 or more and 200 or less, preferably an integer of 2 or more and 20 or less, and more preferably an integer of 6 or more and 20 or less.

These dispersing agents may be used singly or in combination of two or more. In the present embodiment, it is particularly preferred to use a pigment derivative in combination with a polymer dispersant.

The concentration of the dispersing agent is preferably from 1 part by mass to 80 parts by mass, more preferably from 5 parts by mass to 70 parts by mass, even more preferably from 10 parts by mass to 60 parts by mass, per 100 parts by mass of the pigment. .

The dispersant is preferably 5% by mass or more, and more preferably 10% by mass or more based on all the solid components of the photosensitive resin composition. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.

When the amount of the dispersant is within the above range, the viscosity stability of the photosensitive resin composition is good, and the adhesion of the exposure pattern to the substrate can be maintained, which is preferable.

In the present specification, the term "solid content (solid content)" means a component which does not volatilize or disappear without evaporation when subjected to a drying treatment at 100 °C. Typically, it refers to a component other than a solvent or a dispersion medium.

(c) developing resin

In the photosensitive resin composition of the present invention, it is preferred to use a polymer compound having a polymerizable group as a developing resin.

. a site containing a polymerizable group

The repeating unit having a polymerizable group (the portion containing a polymerizable group) preferably has an acrylic group structure. The acryl-based structure which is a base of the site containing a polymerizable group preferably has a (meth) acrylonitrile group, and more preferably has a (meth) propylene fluorenyl group (CH ₂ = C(R) COO. -) or (meth) propylene decylamino group (CH ₂ = C(R)CONR ^N -). Here, R is a hydrogen atom or a methyl group. R ^{N is} as defined later, and among them, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferred.

Examples of the polymerizable group include an ethylenically unsaturated bond group (such as a vinyl group or an allyl group), an epoxy group, an oxetanyl group, and an isocyanate group.

The ratio of the polymerizable group is preferably 5 or more, more preferably 10 or more in the molecule (total amount is 100) in terms of the molar copolymerization ratio. The upper limit is preferably 50 or less, more preferably 40 or less. By setting it as such a range, the fall of a film surface roughness and developability mentioned later can be achieved more effectively.

. Part without polymerizable group

As a repeating unit having no polymerizable group (a site containing no polymerizable group), any structure can be applied, and a compound represented by the following formula (ED) (hereinafter sometimes referred to as "ether dimer" is preferable. A repeating unit obtained by polymerizing a monomer component.

In the formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ is not particularly limited, and examples thereof include a linear or branched alkyl group (preferably, the carbon number is 1). ~12, more preferably 1~6, especially preferred 1~3); aryl (preferably carbon number 6~22, more preferably 6~14); cyclohexyl, tert-butyl An alicyclic group such as a cyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group or a 2-methyl-2-adamantyl group (preferably having a carbon number of 3 to 12, More preferably, it is 3~6); an alkyl group substituted by an alkoxy group (preferably, the carbon number is 2 to 12, more preferably 2 to 6, and particularly preferably 2 to 3); An aryl-substituted alkyl group (preferably having a carbon number of 7 to 23, more preferably 7 to 15). Among these, in particular, substitution of a grade 1 or a grade 2 carbon which is difficult to be removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group or the like is preferable from the viewpoint of heat resistance.

As a specific example of the ether dimer, an ether dimer described in the paragraph [0565] of the corresponding Japanese Patent Application Laid-Open No. 2012/235099 (Japanese Patent Application Publication No. 2012/235099) Specific examples of this are incorporated in the specification of the present application.

A specific example of the ether dimer is preferably dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(Asia Methyl)]bis-2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxybis(Asia Methyl)] bis-2-acrylate.

Examples of the repeating unit obtained by polymerizing the ether dimer include the following structures. Me is a methyl group. * is a binding key.

[Chemical 4]

The repeating unit (the portion not containing a polymerizable group) which does not have a polymerizable group is preferably a repeating unit obtained by polymerizing a polymerizable monomer component having two or more and six or less hydroxyl groups. Specifically, a repeating unit obtained by polymerizing a polymerizable monomer component having the following formula (AE) is preferred.

In the formula, R ¹ and R ⁴ each independently represent a hydrogen atom, a substituted alkyl group having 1 to 5 carbon atoms, R ² represents an alkylene group having 1 to 4 carbon atoms, and R ³ represents a carbon number of An alkyl group having 1 to 40 or a single bond, and n is an integer of 2 or more and 6 or less.

The monomer represented by the formula (AE) may, for example, be a monoester of a polyhydric alcohol having an ethylenically unsaturated double bond, and is preferably a glycerol mono(meth)acrylate.

In the above formula (AE), as another form, the carbon number of the alkylene group of R ² is preferably 2 to 3. Further, the carbon number of the alkyl group of R ³ is from 1 to 20, more preferably from 1 to 10. It is preferred that the alkylene group of R ³ contains a benzene ring. Examples of the alkylene group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl(iso)propyl group.

In the present invention, as the developing resin, it is also preferred to use the following formula A polymer compound obtained by copolymerizing a compound represented by (A1).

R ^A1 represents a hydrogen atom or a methyl group. n represents an integer from 1 to 15. When n is 2 or more, a plurality of R ^A2 may be the same or different. m represents an integer from 0 to 5.

R ^A2 represents an alkylene group having 2 or 3 carbon atoms, and when n is 2 or more, a plurality of R ^A2 may be the same or different.

R ^A3 represents an alkyl group having an aromatic ring (benzene ring) and having 1 to 20 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, fluorenyl and the like can be mentioned. Examples of the alkyl group containing an aromatic ring (benzene ring) include 1-phenylethyl group, 1-phenylpropyl group, 1-phenylbutyl group, 1-phenylpentyl group, and 1-phenylhexyl group. -Phenylheptyl, 1-phenyloctyl, 1-phenylindenyl, 1-phenylindenyl, benzyl, 2-phenyl(iso)propyl, and the like. Preferred among these are benzyl and 2-phenyl (iso)propyl groups.

Examples of the compound represented by the formula (A1) include an oxirane (EO) modified (meth) acrylate of phenol, an EO of p-cumylphenol or a propylene oxide (PO) modified (meth)acrylic acid. EO modified (meth) acrylate of ester and indophenol, PO modified (meth) acrylate of nonylphenol, and the like.

A compound represented by the formula (A1) is used as a copolymerization component of a developing resin In the case of the copolymerization ratio, the molar ratio is preferably 5 or more, more preferably 10 or more in the molecule (total amount is 100). The upper limit is preferably 30 or less, more preferably 20 or less.

In the production of the developing resin, for example, a method using a known radical polymerization method can be applied. The polymerization conditions for the temperature at which the resin is produced by the radical polymerization method, the type and amount of the radical initiator, the kind of the solvent, and the like can be easily set by those skilled in the art, and the conditions can be experimentally determined.

The ratio of the polymerizable group-non-containing portion is preferably 10 or more, more preferably 20 or more in the molecule (total amount is 100) in terms of the molar copolymerization ratio. The upper limit is preferably 80 or less, more preferably 70 or less. By setting it as such a range, the solubility in a solvent can be more effectively achieved.

. Alkali soluble structure

In the developing resin, it is preferred to have an alkali-soluble structure in consideration of alkali solubility. Examples of the base which promotes alkali solubility (hereinafter also referred to as "acid group") include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, (meth)acrylic acid is particularly preferred.

A monomer which can impart an acid group after the polymerization can also be used. In this case, for example, it is preferred to incorporate a repeating unit having a hydroxyl group or an epoxy group, an isocyanate group into the resin, and convert the groups into an acid group. Examples of the monomer which imparts an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a monomer having an epoxy group such as glycidyl (meth)acrylate, ( A monomer having an isocyanate group such as methyl 2-isocyanate ethyl methacrylate or the like.

Further, when a monomer capable of imparting an acid group after polymerization is introduced as a monomer component into an acid group, a treatment for imparting an acid group after polymerization is required according to a general method.

The ratio of the alkali-soluble structure portion is preferably 10 or more, more preferably 20 or more in the molecule (total amount is 100) in terms of the molar copolymerization ratio. The upper limit is preferably 50 or less, more preferably 40 or less. By setting it as such a range, alkali developability can be improved and the formation of a rectangular pattern can be more effectively achieved.

In the production of the developing resin, for example, a method using a known radical polymerization method can be applied. The polymerization conditions for the temperature at which the resin is produced by the radical polymerization method, the type and amount of the radical initiator, the kind of the solvent, and the like can be easily set by those skilled in the art, and the conditions can be experimentally determined.

. Developing resin parameters

The developing resin is preferably 1% by mass or more, and more preferably 5% by mass or more in the photosensitive resin composition. The predetermined upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 14% by mass or less.

The developing resin component is preferably 10% by mass or more, and more preferably 20% by mass or more based on all the solid components. The regulation of the upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.

It is preferable to contain 1 mass part or more of the developing resin with respect to 100 parts by mass of the pigment, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. The upper limit is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and particularly preferably 20 parts by mass or less.

When the developing resin is in the above range, it is difficult to cause film shrinkage when it is cured to form a colored layer, and a coloring layer having excellent pattern formability and little surface roughness can be formed.

The acid value of the developing resin is preferably from 10 mgKOH/g to 200 mgKOH/g, more preferably from 20 mgKOH/g to 150 mgKOH/g. By setting it as this range, it becomes possible to reduce the residue of the unexposed part after image development.

The weight average molecular weight of the developing resin is preferably 23,000 or less, more preferably 21,000 or less, and particularly preferably 20,000 or less. The regulation of the lower limit is preferably 3,000 or more, and particularly preferably 5,000 or more.

In the present invention, the "molecular weight" means a weight average molecular weight (Mw) unless otherwise specified. The measurement can be carried out by means of gel permeation chromatography (GPC) using polystyrene-converted values. The column or the carrier may be appropriately selected in consideration of solubility and the like.

The molecular weight is measured by using HLC-8220 (manufactured by Tosoh Corporation) and using TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) as a column, unless otherwise specified. A 10 mmol/L lithium bromide NMP (N-methylpyrrolidone) solution was obtained as a dissolving solution, and the column temperature was 40 ° C.

In the present invention, it is preferred to use the polymer compound having a polymerizable group in the developing resin. It is the reason as described below. The inventors of the present application have been able to ascertain the following phenomenon: When a phthalocyanine pigment and a quinacridone pigment are used together as a material constituting one pixel portion, the film surface of the cured film is rough. This phenomenon is considered to be due to the fact that any of the indigo pigment and the quinacridone pigment has a high planarity. The material coexists in the film and is associated with each other between the indigo pigments or the quinacridone pigments by, for example, constant temperature and humidity, resulting in a rough surface. On the other hand, according to a preferred embodiment of the present invention, it can be solved as a developing resin by using a polymerizable group in the molecule, and preferably having a weight average molecular weight of 23,000 or less. This phenomenon can be explained as an effect by the fact that the developing resin has a polymerizable group in the molecule, and thus a crosslinked structure is formed in the film to suppress the movement of the pigments. Further, it is considered that if the weight average molecular weight is lowered, it is uniformly distributed in the film, so that it functions more effectively.

(d) Polymeric compounds

The polymerizable compound is preferably a monomer having an ethylenically unsaturated double bond. The monomer having an ethylenically unsaturated double bond (hereinafter sometimes referred to as "polyfunctional monomer") can be used without particular limitation. The polyfunctional monomer may be used alone or in combination of two or more. The polyfunctional monomer is preferably a (meth) acrylate monomer. As the specific compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can be suitably used in the present embodiment.

The polyfunctional monomer is preferably one having the following reactive group RA in the molecule.

(Reactive group RA: vinyl group, (meth) acrylonitrile group, or (meth) propylene oxime group)

Further, the radical polymerizable monomer represented by any one of the following formulas (MO-1) to (MO-7) can be suitably used. In addition, in the formula, T is an oxygen group In the case of an alkyl group, the terminal on the carbon atom side is bonded to R.

In the formula, R is a group having a hydroxyl group or a vinyl group at the terminal. Among them, one or more vinyl groups are contained in the molecule, and the vinyl group is preferably two or more, and more preferably three or more. R is preferably a substituent of any of the following R1 to R5. T is a linking group, and is preferably a linking group of any one of the following T1 to T5 or a combination thereof. Z is a linking group, preferably Z1 described below. Z ² is a linking group, and is preferably the following formula Z2. In addition, the orientation of T1~T5 may also be opposite to the formula.

[化8]

In the formula, n is an integer, preferably 0 to 14, respectively, more preferably 0 to 5, and particularly preferably 1 to 3. m is 1~8, preferably 1~5, and especially 1~3. The plurality of R, T and Z present in one molecule may be the same or different. In the case where T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. It is preferred that at least two of R are a polymerizable group, and more preferably three are a polymerizable group. Z ^{3 is} preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. Among them, particularly preferred is 2,2-propanediyl.

As a specific example of the radical polymerizable monomer, the compound described in Paragraph No. 0248 to Paragraph No. 0251 of JP-A-2007-269779 can be suitably used in the present embodiment.

Among them, a polymerizable monomer or the like is preferably dipentaerythritol triacrylate (commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercial product is KAYARAD D-320; Nippon Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercial product) KAYARAD DPHA; Nippon Chemical Pharmaceutical Co., Ltd. (manufactured by the company), and the structure of (meth)acryloyl sulfhydryl-based ethylene glycol, propylene glycol residues, or diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by East Asia Synthetic Company). These oligomer types can also be used.

Particularly, the polyfunctional monomer is at least one selected from the group consisting of a compound represented by the following formula (i) and a compound represented by the formula (ii).

In the formula, E represents -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ )O)-, respectively, preferably -((CH ₂ ) _y CH ₂ O)-.

y represents an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

X represents a hydrogen atom, an acryloyl group, a methacryl fluorenyl group, or a carboxyl group, respectively.

In the formula (i), the total of the acrylonitrile group and the methacrylic acid group is preferably 3 or 4, more preferably 4.

m represents an integer of 0 to 10, preferably an integer of 1 to 5. The total of each m is an integer of 1 to 40, preferably an integer of 4 to 20.

In the formula (ii), the total of the acrylonitrile group and the methacrylic acid group is preferably 5 or 6, more preferably 6.

n represents an integer of 0 to 10, preferably an integer of 1 to 5. The total of n is an integer of 1 to 60, preferably an integer of 4 to 30.

The polyfunctional monomer may also have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, in the case where the ethylenic compound is a mixture as described above, it is preferred to have an unreacted carboxyl group, and the ethylenic compound can be used as it is, and if necessary, the hydroxyl group and the non-aromatic carboxyl group of the above-mentioned ethylenic compound can be used. The acid anhydride reacts to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkyl group. Hexahydrophthalic anhydride, succinic anhydride, maleic anhydride.

The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and it is preferred to react an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to have an acid group. A functional monomer, particularly preferably in the ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercially available product, for example, the polyacid-modified acrylate oligomer manufactured by Toagosei Co., Ltd. may, for example, be M-305, M-510, M-520 or the like of the ARONIX series.

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH/g to 40 mgKOH/g, and particularly preferably 5 mgKOH/g to 30 mgKOH/g.

Regarding the polyfunctional monomers, the details of the structure, the use alone or in combination, the amount of addition, and the like can be arbitrarily set depending on the final performance design of the composition. In the present embodiment, the number of functional groups is different and/or the polymerizable group is different. A method of adjusting both sensitivity and strength (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound) is also effective. Further, in view of adjusting the developability of the composition and obtaining excellent pattern forming ability, it is preferred to use a polyfunctional monomer having three or more functional groups and eight or less functional groups and different ethylene oxide chain lengths. Further, the selection and use of the polyfunctional monomer are important for the compatibility and dispersibility with other components (for example, a polymerization initiator, a colorant (pigment), a resin, etc.) contained in the composition. For example, the compatibility may be improved by using a low-purity compound or a combination of two or more. Further, a specific structure can be selected from the viewpoint of improving the adhesion to a hard surface such as a substrate.

The concentration (mixing ratio) of the polymerizable compound is preferably 1% by mass or more, and preferably 5% by mass or more, based on all solid components in the photosensitive resin composition. The upper limit is not particularly limited, but is preferably 50% by mass or less, and more preferably 40% by mass or less.

(e) polymerization initiator

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polyfunctional monomer, and may be appropriately selected from known polymerization initiators, for example, preferably having an active energy ray. Sensitive. It may be an active agent which generates a certain action with a photo-excited sensitizer to form a living radical, and may also be an initiator which initiates cationic polymerization depending on the kind of the monomer. The polymerization initiator preferably contains at least one component having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm, more preferably 330 nm to 500 nm.

As the polymerization initiator, for example, a halogenated hydrocarbon derivative (for example, a mercaptophosphine compound such as a triazine skeleton or a oxadiazole skeleton, a mercaptophosphine oxide, a quinone compound such as a hexaarylbiimidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, or an aromatic compound A sulfonium salt, a ketone oxime ether, an aminoacetophenone compound, hydroxyacetophenone or the like.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in J. Lin et al., "Bull. Chem. Soc. Japan", 42, 2924 (1969), and a British patent. The compound described in the specification of Japanese Patent No. 1388492, the compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the "Journal of Organic Chemistry (J. Org) by FC Schaefer et al. a compound described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in Japanese Laid-Open Patent Publication No. Hei 5-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

Examples of the compound described in the specification of the above-mentioned U.S. Patent No. 4,212,976 include a compound having an oxadiazole skeleton, Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent Publication No. Sho 57-1819, and Japanese Patent No. A compound or the like described in the specification of the Japanese Patent No. 36-15455 and the specification of the Japanese Patent No. 3615455.

As the polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, the start of the aminoacetophenone group described in Japanese Laid-Open Patent Publication No. Hei 10-291969 can also be used. A sulfhydryl phosphine oxide-based initiator as described in Japanese Patent No. 42258899.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names; all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names; all manufactured by BASF Corporation) which are commercially available can be used. The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched with a long-wavelength light source such as 365 nm or 405 nm. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name; both manufactured by BASF Corporation) which is a commercially available product can be used.

More preferably, the polymerization initiator is a lanthanide compound. As a specific example of the oxime-based compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and JP-A-2006-342166 can be used. Compound.

Examples of the ruthenium compound such as an anthracene derivative which is suitably used as a polymerization initiator in the present embodiment include 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyiminobutane. Alkan-2-one, 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1- Phenylpropan-1-one, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Specifically, the oxime polymerization initiator is preferably a compound represented by the following formula. Further, it may be an anthracene compound in which the N-O bond of ruthenium is (E), or may be (Z) The quinone compound of the body may also be a mixture of the (E) body and the (Z) body.

The hydrazine compound to be a polymerization initiator is preferably represented by the following formula (OX), and more preferably represented by the formula (OX-1).

. A ¹

A ^{1 is} preferably -AC or an alkyl group of the formula (OX-1). The alkyl group preferably has a carbon number of from 1 to 12, more preferably from 1 to 6. The alkyl group may have a substituent O which will be described later. Further, the substituent O may be substituted by interposing the linking group L described later.

. R

R represents a monovalent substituent, preferably a monovalent non-metal atomic group. The monovalent non-metal atomic group may, for example, be an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or an aryl group (preferably a carbon number). 6~14, more preferably 6~10), sulfhydryl (preferably, carbon number is 2~12, more preferably 2~6, especially good is 2~3), aryl sulfhydryl (more Preferably, the carbon number is 7 to 15, more preferably 7 to 11), the alkoxycarbonyl group (preferably, the carbon number is 2 to 12, more preferably 2 to 6, and particularly preferably 2 to 3). , an aryloxycarbonyl group (preferably having a carbon number of 7 to 15, more preferably 7 to 11), a heterocyclic group (preferably having a carbon number of 2 to 12, more preferably 2 to 6) , alkylthiocarbonyl (preferably having a carbon number of 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3), or an arylthiocarbonyl group (preferably having a carbon number of 7 to 3) 15, better is 7~11) and so on. Further, these groups may have one or more substituents. Further, the aforementioned substituent may be further substituted with another substituent O. The substituent O may, for example, be a halogen atom or an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3) or an aryl group (preferably having a carbon number of 6). ~14, more preferably 6~10). The substituent O may also be via any linking group L (alkylene group having a carbon number of 1 to 6, O, S, CO, NR ^N or a combination thereof; R ^N is a hydrogen atom or a carbon number of 1 to 6) The alkyl group is substituted.

. B

B represents a monovalent substituent, and represents an alkyl group (preferably having a carbon number of 1 to 12), an aryl group (preferably having a carbon number of 6 to 14, more preferably a carbon number of 6 to 10), Heterocyclic group (preferably having a carbon number of 2 to 18, more preferably a carbon number of 2 to 12). These groups may also be bonded via the linking group L. Further, these groups may have one or more substituents O. The substituent O may be substituted via any linking group L. Specific examples of B may be as follows. * indicates the bonding position, and can also be bonded at different positions. Moreover, the groups may further link the substituent O. Specific examples thereof include a benzamidine group, a phenylthio group, and a phenoxy group.

. A

A is a single bond or a linking group. A preferred example of the linking group is the linking group L or an extended aryl group (preferably having a carbon number of 6 to 14, more preferably a carbon number of 6 to 10) or a heterocyclic linkage. The group (preferably an aromatic heterocyclic linking group) (preferably having a carbon number of 2 to 18, more preferably a carbon number of 2 to 12).

. C

C represents SAr or COAr.

. Ar

Ar is an aryl group or a heteroaryl group (aromatic heterocyclic group). The aryl group preferably has a carbon number of 6 to 14, more preferably a carbon number of 6 to 10, more preferably a phenyl group or a naphthyl group. The heteroaryl group is preferably a carbon number of 2 to 18, more preferably a carbon number of 2 to 12, and preferably a carbazolyl group having a substituent such as an alkyl group at the N position.

The oxime initiator can be referred to the formula (OX-1) and the formula (OX-2) after paragraph 0513 of the Japanese Patent Laid-Open Publication No. 2012-208494 (corresponding to [0632] of the specification of the U.S. Patent Application Publication No. 2012/235099). Or a description of the compound represented by the formula (OX-3), which is incorporated into the specification of the present application.

Specific examples (PIox-1) to specific examples (PIox-13) of the ruthenium compound which are suitably used are shown below, but the present invention is not limited to these specific examples.

[化12]

The ruthenium compound has a function as a thermal polymerization initiator which decomposes due to heat, initiates polymerization, and promotes polymerization. In the present invention, as a reason for bringing about a good result, it is considered that since the radical generation efficiency is good, even a small amount of addition is considered. Photopolymerization can also be carried out well.

The ruthenium compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a high absorbance at 365 nm and 455 nm.

From the viewpoint of self-sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. A known method can be used for the molar absorption coefficient of the compound. Specifically, for example, it is preferably an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent. The measurement was carried out at a concentration of 0.01 g/L.

As the ruthenium compound, commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (all manufactured by BASF Corporation) can be suitably used.

The polymerization initiator may be used in combination of two or more kinds as needed. The concentration of the polymerization initiator in the photosensitive resin composition (the total concentration in the case of two or more kinds) is preferably 0.1% by mass to 20% based on the total solid content of the photosensitive resin composition. The range of the mass % is more preferably in the range of 0.5% by mass to 10% by mass, particularly preferably in the range of 1% by mass to 8% by mass. If it is in this range, good sensitivity and pattern formation property are obtained.

It is also possible to contain a sensitizer for the purpose of improving the radical generating efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength. As the sensitizer which can be used in the present embodiment, it is preferred that the sensitizer is sensitized by an electron-moving mechanism or an energy-moving mechanism with respect to the polymerization initiator.

The sensitizer is, for example, a compound described in Paragraph No. 0101 to Paragraph No. 0154 of JP-A-2008-32803.

In the case of blending, the concentration of the sensitizer in the composition is preferably 0.1% by mass to 20% in terms of solid content, from the viewpoint of light absorption efficiency in the deep portion and initiation of decomposition efficiency. %, more preferably 0.5% by mass to 15% by mass.

The sensitizer may be used alone or in combination of two or more.

(f) Pigment derivatives

It is also preferred that the photosensitive resin composition contains a pigment derivative. The pigment derivative is preferably represented by the following formula Q1 or formula Q2.

In the formula, Q represents an organic dye residue. X ^Q1 represents a hydrogen atom, a carboxyl group, or a sulfonic acid group. R ^Q1 and R ^Q2 each independently represent an alkyl group which may have a substituent (preferably, the carbon number is from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3). i, j, and n each independently represent an integer of 1 to 4. Z ^Q1 represents a hydroxyl group, an alkoxy group or a substituent represented by the following formula Q3. X ^Q2 represents a single bond, SO ₂ , CO, or CH ₂ .

[Chemistry 14]

R ^Q1 , R ^Q2 , n, X ^{Q2 are} synonymous with the formula Q1.

Examples of the organic dye residue Q include a diketopyrrolopyrrole dye, an azo dye such as azo, disazo, or polyazo, an indigo dye, a diaminodifluorene, a pyrimidine, a yellow ketone, and an anthracene. Indigo, indanthrone, dermatoglycan, scutellarin, etc., dioxazine pigment, purple ketone pigment, anthraquinone pigment, thioindigonin, isoindoline pigment, isoindolinone pigment Each residue of the quinacridone dye, the Shilin pigment, and the metal complex dye.

(g) other

The photosensitive resin composition may contain other components. Examples of other components include a solvent, a surfactant, a UV absorber, a polymerization inhibitor, and a adhesion promoter.

. Solvent

The photosensitive resin composition can be generally used by using a solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the photosensitive resin composition, and is particularly preferably selected in consideration of solubility, coating property, and safety of the ultraviolet absorber and the binder resin. Further, in the preparation of the photosensitive resin composition, it is preferred to contain at least two kinds of solvents.

As the solvent, examples of the ester include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, B) Methyl oxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (for example: methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, 3) -methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-oxypropionic acid alkyl Esters (for example: methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropene) Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2-methylpropanoate and Ethyl 2-oxo-2-methylpropanoate (e.g., methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvate Ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutyrate, and the like, and ethers such as Suitable for enumerating two Alcohol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include xylene and the like.

The concentration of the solvent in the photosensitive resin composition is preferably such that the concentration of all solid components of the composition is from 5% by mass to 80% by mass, more preferably from 5% by mass to 60% by weight of the coating property. The mass% is particularly preferably 10% by mass to 50% by mass.

. Surfactant

From the viewpoint of further improving the coatability, various surfactants may be added to the composition. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used. The amount of the surfactant to be added is preferably 0.001% by mass to 2% by mass, and more preferably 0.005% by mass to 1% by mass based on the total mass of the composition.

. Polymerization inhibitor

In order to prevent unnecessary thermal polymerization of the polyfunctional monomer during or during the manufacture of the composition, it is desirable to add a small amount of a polymerization inhibitor. The polymerization inhibitor may, for example, hydroquinone, p-methoxyphenol, o-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrous Phenylhydroxylamine trivalent sulfonium salt and the like. In addition, the photosensitive resin composition may contain a co-sensitizer for the purpose of further improving the sensitivity of the sensitizing dye or the initiator to the active radiation or suppressing the polymerization inhibition of the polyfunctional monomer by oxygen. Further, in order to improve the physical properties of the hardened film, a known additive such as a diluent, a plasticizer or a lipid-sensitive agent may be added as needed. The amount of addition in the case of using a polymerization inhibitor is preferably in the range of 0.001% by mass to 0.015% by mass, and more preferably 0.03% by mass to 0.09% by mass in all the solid components in the colored photosensitive resin composition. %.

. Adhesion promoter

The amount of addition in the case of using the adhesion promoter is preferably a coloring feeling The solid content of all the solid components in the photosensitive resin composition is in the range of 0.1% by mass to 5% by mass, and more preferably 0.2% by mass to 3% by mass.

. UV absorber

The photosensitive resin composition may also contain an ultraviolet absorber. As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based or triazine-based ultraviolet absorber can be used. In the case where the ultraviolet absorber is contained, the concentration of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass based on the mass of all the solid components. the following.

Further, in the present specification, with respect to the expression of the compound (for example, when attached to the compound and the end thereof), the following meaning is used: in addition to the compound, the salt thereof and the ion thereof are contained. In addition, it is a meaning that a derivative in which a part of a substituent or the like is changed is introduced within a range that exhibits a desired effect.

In the present specification, the substituent which is unsubstituted or unsubstituted (the same applies to the linking group) is a meaning which may have any substituent in the group. The unsubstituted, unsubstituted compound is also synonymous with it. Preferred substituents include the following substituents T.

The substituent T can be exemplified below.

An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl (preferably an alkenyl group having 2 to 20 carbon atoms, such as a vinyl group, an allyl group, an oleyl group, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as an ethynyl group, a butadiynyl group, a phenylethynyl group, etc.) or a cycloalkyl group (preferably a cycloalkane having 3 to 20 carbon atoms). a group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group or the like, an aryl group (preferably an aryl group having 6 to 26 carbon atoms, such as a phenyl group, a 1-naphthyl group, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms), preferably, preferably. a 5-membered or 6-membered heterocyclic group having at least one oxygen atom, a sulfur atom, or a nitrogen atom, such as tetrahydropyran, tetrahydrofuran, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), alkoxy (preferably an alkoxy group having 1 to 20 carbon atoms, for example a methoxy group, an ethoxy group, an isopropoxy group, a benzyloxy group or the like), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, such as a phenoxy group, a 1-naphthyloxy group, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethyl a hexyloxycarbonyl group or the like, an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 6 to 26 carbon atoms, such as a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 3-methylphenoxy group) a carbonyl group, a 4-methoxyphenoxycarbonyl group or the like, an amine group (preferably an amine group having 0 to 20 carbon atoms, and an alkylamino group, an arylamine group such as an amine group, N, N) - dimethylamino group, N,N-diethylamino group, N-ethylamino group, anilino group, etc.), amine sulfonyl group (preferably sulfonyl group having 0 to 20 carbon atoms) , for example, N,N-dimethylamine sulfonyl, N-phenylamine sulfonyl, etc.), fluorenyl (preferably a fluorenyl group having 1 to 20 carbon atoms, such as ethyl acetonitrile or propyl hydrazine) Base, butyl sulfhydryl, etc., aryl fluorenyl (preferably aryl fluorenyl group having 7 to 23 carbon atoms, such as benzamidine group, etc.), decyloxy group (preferably having 1 to 1 carbon atom) 20 anthraceneoxy group, such as an ethoxylated group, etc., an aryl fluorenyloxy group (preferably an aryl fluorenyloxy group having 7 to 23 carbon atoms, such as a benzyl methoxy group, etc.), an amine formazan a base (preferably an amine carbenyl group having 1 to 20 carbon atoms, such as N,N-dimethylaminecarbamyl, N-phenylaminecarbamyl, etc.), a mercaptoamine group (preferably Is a mercaptoamine group having 1 to 20 carbon atoms, such as an ethylamino group, a benzhydrylamino group, etc., an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms) , for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio (preferably an arylthio group having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylsulfide a group, a 3-methylphenylthio group, a 4-methoxyphenylthio group or the like), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonium) a group, an ethylsulfonyl group, an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 22 carbon atoms, such as a phenylsulfonyl group), an alkylalkyl group (preferably Is an alkylalkyl group having 1 to 20 carbon atoms, such as monomethyl decyl, dimethyl decyl, trimethyl decyl, triethyl decyl, etc., aryl An alkyl group (preferably an arylalkylalkyl group having 6 to 42 carbon atoms, such as a triphenylsulfanyl group), a phosphoric acid group (preferably a phosphoric acid group having 0 to 20 carbon atoms, such as -OP) (=O)(R ^P ) ₂ ), phosphinium group (preferably a phosphinium group having 0 to 20 carbon atoms, such as -P(=O)(R ^P ) ₂ ), phosphinyl group (more Preferred are phosphinyl groups having 0 to 20 carbon atoms, such as -P(R ^P ) ₂ ), (meth)acrylinyl, (meth)acryloxy, hydroxy, cyano, halogen ( For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like).

Further, each of the groups exemplified in the substituents T may be further substituted with the substituent T.

When the compound, the substituent, the linking group and the like contain an alkyl group, an alkylene group, an alkenyl group, an alkenyl group, an alkynyl group, an alkynyl group or the like, the ring group may be a chain shape and may be straight. The chain may also be branched and may be substituted or unsubstituted as described above.

Each of the substituents defined in the present specification may be substituted by inserting the following linking group L within the range in which the effects of the present invention are exerted. For example, an alkyl group, an alkylene group, an alkenyl group, an extended alkenyl group or the like may be further inserted into the structure to form the following hetero-linking group.

The linking group L is preferably a hydrocarbon linking group (alkylene group having a carbon number of 1 to 10 (more preferably, the carbon number is 1 to 6, more preferably 1 to 3), and the carbon number is 2 to 10. An alkenyl group (more preferably a carbon number of 2 to 6, more preferably 2 to 4) and an alkynyl group having a carbon number of 2 to 10 (more preferably a carbon number of 2 to 6, further preferably) 2~4), an extended aryl group having a carbon number of 6 to 22 (more preferably a carbon number of 6 to 10), a hetero-linking group [carbonyl (-CO-), thiocarbonyl (-CS-), Ether group (-O-), thioether group (-S-), imido group (-NR ^N -), imine linkage (R ^N -N=C<, -N=C(R ^N )-) ], or a combination of these. Further, when a ring is formed by condensation, the hydrocarbon linking group may be appropriately bonded to form a double bond or a triple bond. The ring formed is preferably a 5-membered ring or a 6-membered ring. The 5-membered ring is preferably a 5-membered ring containing nitrogen. Examples of the compound to be the ring include pyrrole, imidazole, pyrazole, oxazole, indole, benzimidazole, pyrrolidine, and imidazole. , pyrazolidine, porphyrin, carbazole, or derivatives thereof. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. Further, when an aryl group, a heterocyclic group or the like is contained, these may be a monocyclic ring or a condensed ring, and may be substituted or unsubstituted as well.

R ^N is a hydrogen atom or a substituent. The substituent is preferably an alkyl group (preferably having a carbon number of from 1 to 24, more preferably from 1 to 12, still more preferably from 1 to 6, particularly preferably from 1 to 3), alkenyl (compared Preferably, the carbon number is 2 to 24, more preferably 2 to 12, still more preferably 2 to 6, particularly preferably 2 to 3), alkynyl (preferably having a carbon number of 2 to 24, More preferably, it is 2~12, further preferably 2~6, especially 2~3), aralkyl (preferably, the carbon number is 7~22, more preferably 7~14, especially Preferably, it is 7-10), aryl (preferably, the carbon number is 6 to 22, more preferably 6 to 14, and particularly preferably 6 to 10).

R ^P is a hydrogen atom, a hydroxyl group, or a substituent. The substituent is preferably an alkyl group (preferably having a carbon number of from 1 to 24, more preferably from 1 to 12, still more preferably from 1 to 6, particularly preferably from 1 to 3), alkenyl (compared Preferably, the carbon number is 2 to 24, more preferably 2 to 12, still more preferably 2 to 6, particularly preferably 2 to 3), alkynyl (preferably having a carbon number of 2 to 24, More preferably, it is 2~12, further preferably 2~6, especially 2~3), aralkyl (preferably, the carbon number is 7~22, more preferably 7~14, especially Preferably, it is 7-10), an aryl group (preferably, the carbon number is 6 to 22, more preferably 6 to 14, particularly preferably 6 to 10), and an alkoxy group (preferably, the carbon number is 1~24, more preferably 1~12, further preferably 1~6, especially 1~3), alkenyloxy (preferably carbon number is 2~24, more preferably 2 ~12, further preferably 2~6, especially 2~3), alkynyloxy (preferably, the carbon number is 2~24, more preferably 2~12, further preferably 2 ~6, particularly preferred is 2~3), aralkyloxy (preferably carbon number is 7~22, more preferably 7~14, especially good is 7~10), aryloxy (comparative The preferred carbon number is 6 to 22, more preferably 6 to 14, and particularly preferably 6 to 10).

In the present specification, the number of atoms constituting the linking group is preferably from 1 to 36, more preferably from 1 to 24, still more preferably from 1 to 12, and particularly preferably from 1 to 6. The number of linking atoms of the linking group is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more. The "number of connected atoms" refers to a path connecting the predetermined structural portions and the minimum number of atoms participating in the connection. For example, in the case of -CH ₂ -C(=O)-O-, the number of atoms constituting the linking group is 6, and the number of linking atoms is 3.

Specifically, the combination of the linking groups can be exemplified below. Oxycarbonyl (-OCO-), carbonate (-OCOO-), decyl (-CONH-), urethane (-NHCOO-), ureido (-NHCONH-), (poly) Alkyloxy (-(Lr-O)x-), carbonyl (poly)oxyalkylene (-CO-(O-Lr)x-, carbonyl (poly)alkyloxy (-CO-( Lr-O)x-), carbonyloxy (poly)alkyloxy (-COO-(Lr-O)x-), (poly)alkyleneimine (-(Lr-NR ^N )x -), alkyl (poly) imidoalkylene (-Lr-(NR ^{N -} Lr) x-), carbonyl (poly) imidoalkyl (-CO-(NR ^{N -} Lr) x-) , carbonyl (poly) alkyl imino group (-CO-(Lr-NR ^N )x-), (poly) ester group (-(CO-O-Lr)x-, -(O-CO-Lr) X-, -(O-Lr-CO)x-, -(Lr-CO-O)x-, -(Lr-O-CO)x-), (poly)decylamine (-(CO-NR ^N -Lr)x-, -(NR ^N -CO-Lr)x-, -(NR ^N -Lr-CO)x-, -(Lr-CO-NR ^N )x-, -(Lr-NR ^N -CO X-), etc. x is an integer of 1 or more, preferably 1 to 500, more preferably 1 to 100.

Lr is preferably an alkyl group, an alkenyl group or an alkynyl group. The carbon number of Lr is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3. A plurality of Lr or R ^N , R ^P , x, and the like need not be the same. The orientation of the linking group is not limited by the above description, and it can be understood that it is appropriately oriented according to a predetermined chemical formula.

(Preparation of photosensitive resin composition)

The preparation aspect of the photosensitive resin composition is not particularly limited, and for example, it can be prepared by mixing necessary components and various additives which are used in combination as needed.

(hardened film and its manufacturing method)

The cured film obtained by curing the composition has high color purity, and has a high light absorption coefficient in a thin layer, and is excellent in fastness (especially heat resistance and light resistance). Due to such an advantage, it is preferably used in the formation of a colored pixel of a solid color imaging element or a color filter for a liquid crystal display device.

The method for producing a cured film includes a step of applying a photosensitive resin composition to a substrate, and a step of exposing the photosensitive resin composition. Specifically, when a cured film is formed on an arbitrary substrate or a substrate, a photosensitive resin composition may be applied or a substrate or the like may be immersed in a photosensitive resin composition to form a photosensitive resin composition layer to be hardened. . Further, in the case of forming a patterned cured film, it can be applied to a substrate by an inkjet recording method, and a known printing method such as printing or lithography can be applied, from the viewpoint that a high-definition pattern can be formed. It is preferable to form a photosensitive resin composition layer on a substrate, which is described later, and to expose the unexposed portion of the photosensitive resin composition layer after being exposed to a pattern.

The film thickness of the resin cured film is, for example, preferably 0.2 μm or more, more preferably 0.3 μm or more, and particularly preferably 0.5 μm or more. The upper limit is preferably 2 μm or less, more preferably 1.55 μm or less, and particularly preferably 1 μm or less.

In the present specification, the thickness of the film is a value measured by a contact film thickness measuring device (Dektak 150; manufactured by Bruker) unless otherwise specified. Among them, the sampling is an average of the values of 5 points.

Color filter and its manufacturing method:

In one example of the method for producing a color filter, the step of applying a photosensitive resin composition to a substrate, and patterning the photosensitive resin composition A step of. Specifically, the method of forming a photosensitive resin composition layer by applying the photosensitive resin composition described above to a support (hereinafter also referred to as "photosensitive resin composition layer forming step"), and interposing a mask pair The photosensitive resin composition layer is subjected to pattern exposure (hereinafter also referred to as "exposure step"), and the exposed photosensitive resin composition layer is developed to form a colored pattern (hereinafter also referred to as "colored pixel" The step (hereinafter also referred to as "development step").

. Exposure step

In a preferred embodiment of the production method of the present invention, the photosensitive resin composition is irradiated with an exposure energy, and the exposed portion is developed to form a pattern of a cured resin. In the present embodiment, a photosensitive resin composition layer is formed on a support or the like before the exposure. The support can be used, for example, for a photographic element (light receiving element) provided with a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) on a substrate (for example, a ruthenium substrate). A substrate for a solid-state imaging element. The colored pattern may be formed on the imaging element forming surface side (surface) of the solid-state imaging element substrate, or may be formed on the unformed surface side (back surface) of the imaging element. A light shielding film may be provided between each of the imaging elements in the solid-state imaging element substrate or the back surface of the solid-state imaging element substrate. Further, in order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or flatten the surface of the substrate, it is also possible to provide an undercoat layer on the support as needed.

As a method of applying a photosensitive resin composition to a support, slit coating, inkjet method, spin coating, cast coating, roll coating, screen printing, etc. can be applied. Various coating methods. The drying (prebaking) of the photosensitive resin composition layer applied on the support can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds by a hot plate, an oven or the like.

In the exposure step, the photosensitive resin composition layer is subjected to pattern exposure by using a mask having a predetermined mask pattern, for example, using an exposure device such as a stepping machine. The irradiation of the exposure energy is preferably performed by irradiating an active energy ray selected from the group consisting of g-rays, h-rays, i-rays, KrF rays (excimer laser rays), and ArF rays (excimer laser rays). The exposure energy is preferably illuminance 5000W / m ² or more, more preferably is 7000W / m ² or more, and particularly preferably is 8000W / m ² or more. As the predetermined upper limit, it is preferably 18000W / m ² or less, more preferably ² or less is 15000W / m, particularly preferred is 10000W / m ² or less. By setting the irradiation energy in this range, a good resolution of the pattern can be obtained.

The exposure apparatus or the like may be a suitable exposure apparatus, and for example, a reduced projection exposure apparatus can be used. In the projection exposure apparatus, for example, an active energy ray emitted from a specific light source is incident on a projection lens via a condenser lens. In the present projection optical system, a mask having a predetermined pattern is placed before or after the condensing lens, and the active energy ray of the predetermined pattern reaches the projection lens. In this case, it is preferable that the numerical aperture of the condenser lens side (NA _1), the numerical aperture (NA ₂₎ of the projection lens side is appropriately set conditions such as the desired range. The active energy ray passing through the reduction projection optical system is emitted from the opposite side and irradiated to the exposure substrate (work). When the active energy ray is irradiated, the photosensitive resin composition layer on the substrate is exposed, preferably in a negative type (exposure hardenability), and the exposed portion is hardened. The numerical aperture (NA ₃ ) on the exit side of the projection lens is also preferably set to a desired range.

. Development step

Then, by performing development such as an alkali development treatment, the photosensitive resin composition layer in the unexposed portion of the light in the exposure step is eluted into the alkaline aqueous solution, and only the portion where the light is hardened remains. As the developer, an organic alkaline developer which does not cause damage to the photographic element or circuit of the substrate is preferable. The development temperature is usually 20 ° C to 30 ° C, and the development time is, for example, 20 seconds to 90 seconds. In order to further remove the residue, in recent years, there have been cases in which 120 seconds to 180 seconds have been carried out. Further, in order to further improve the residue removal property, there are cases in which the following steps are repeated several times: the developer is removed every 60 seconds, and the developer is further supplied again.

The alkaline aqueous solution is preferably an alkaline aqueous solution prepared by dissolving a basic compound so that the concentration thereof is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethyl. Ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7 - undecene or the like (of which an organic base is preferred).

Further, in the case where an alkaline aqueous solution is used as the developing solution, the cleaning treatment is generally performed by water after development.

. Post baking

Secondly, it is preferred to carry out heat treatment (post-baking) after drying. It is preferable to form a coloring pattern of a plurality of colors, and the steps can be sequentially performed in accordance with each color to produce a hardened film. Thereby, a color filter is obtained. Post-baking is a heat treatment for performing complete development of hardening. From the viewpoint of suppressing damage of the organic photoelectric conversion portion, the heating temperature is preferably 240 ° C or lower, more preferably 220 ° C or lower, still more preferably 200 ° C or lower, and particularly preferably 190 ° C or lower. There is no particular limitation on the lower limit. However, in consideration of efficient and effective treatment, it is preferred to carry out a heat hardening treatment at 50 ° C or higher, more preferably at 100 ° C or higher.

This post-baking treatment can use a heating plate, a convection oven (hot air circulation dryer), a high-frequency heating machine or the like to heat the coating film after development, in a continuous or batch manner. To proceed.

The color filter of the color filter may be cured by ultraviolet (UV) irradiation to be changed to the post-baking by heating. At this time, it is preferable that the UV hardener is hardened by a wavelength more than a single wavelength of an exposure wavelength of 365 nm (that is, an exposure wavelength of an initiator to be added for a usual lithography step using i-ray exposure). The UV hardener may, for example, be Ciba Irgacure 2959 (trade name). As the specific wavelength of the UV irradiation light, a material which hardens at 340 nm or less is preferable. There is no particular limitation on the lower limit of the wavelength, and it is generally 220 nm or more. Further, the exposure amount of the UV irradiation is preferably 100 mJ to 5000 mJ, preferably 300 mJ to 4000 mJ, and more preferably 800 mJ to 3500 mJ. In order to perform the low temperature hardening more efficiently, it is preferred to carry out the UV hardening step after the lithography step. The exposure light source is preferably an ozone-free mercury lamp.

It is preferred to carry out post-baking of the photosensitive resin composition in a low oxygen concentration environment. The oxygen concentration is preferably 19% or less (volume basis) or less, more preferably 15% (volume basis) or less, still more preferably 10% (volume basis) or less, and still more preferably 7% (volume basis). The following is particularly preferable as 3% (volume basis) or less. There is nothing special about the lower limit, but it is actually 10 ppm (volume basis) or more.

. Application form

The color filter of the preferred embodiment of the present invention can be used in a liquid crystal display device, a solid-state imaging device or an organic EL device, and is particularly suitable for solid-state imaging applications. The solid-state imaging device according to the preferred embodiment of the present invention has been described based on Fig. 1, and examples thereof include the following configurations. a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode including a polysilicon or the like on the support, and the photodiode and the photodiode The transfer electrode has a light-shielding film containing tungsten or the like which is opened only to the light-receiving portion of the photodiode, and includes a light-shielding film formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. An element protective film such as tantalum nitride has a color filter for a solid-state imaging element on the element protective film. In addition, it may be configured on the element protective layer and under the color filter (on the side close to the support) to have a concentrating mechanism (for example, a microlens or the like; the same below) or on the color filter. It has a configuration of a collecting mechanism and the like.

[Examples]

Hereinafter, the present invention will be further specifically described by way of examples, but The invention is not limited thereto and will be explained. In addition, "parts" and "%" are quality standards unless otherwise specified.

(Example 1)

<Preparation of Dispersion P1 Using (A1) Indigo Blue Pigment>

11.8 parts of CI Pigment Blue 15:6, 1.2 parts of the following pigment derivative, 5.2 parts of Solsperse 20000 (100% solid content) as a dispersing agent, and 81.8 parts of propylene glycol methyl ether acetate (PGMEA) as a solvent After the mixture was uniformly stirred and mixed, zirconia particles having a diameter of 0.5 mm were used, and a bead mill (high pressure disperser NANO-3000-10 (manufactured by Japan BEE Co., Ltd.) equipped with a pressure reducing mechanism) was used. The pigment dispersion P1 was prepared by dispersion in an hour.

<Preparation of dispersion (P2) using (A2) quinacridone-based magenta pigment>

11.8 parts of C.I. Pigment Red 209, 1.2 parts of the following pigment derivative 2, and 5.2 parts of Solsperse 20000 (solid content: 100%) as a dispersing agent were included. A mixture of 81.8 parts of the PGMEA of the solvent was uniformly stirred and mixed, and then zirconia particles having a diameter of 0.5 mm were used, and a bead mill (a high-pressure disperser NANO-3000-10 with a pressure-reducing mechanism (manufactured by Japan BEE Co., Ltd.) was used. )) was dispersed for 5 hours to prepare a pigment dispersion P2.

<Preparation of Dispersion P3 Using Other Pigments>

A mixture comprising 11.8 parts of CI Pigment Violet 23, 1.2 parts of the following pigment derivative 3, 5.2 parts of Solsperse 20000 (solid content: 100%) as a dispersing agent, and 81.8 parts of PGMEA as a solvent were uniformly stirred and mixed, and then used. The zirconia particles having a diameter of 0.5 mm were dispersed by a bead mill (a high-pressure disperser NANO-3000-10 (manufactured by Japan BEE Co., Ltd.) equipped with a pressure reducing mechanism) for 5 hours to prepare a pigment dispersion liquid P3.

[Chemistry 17] Pigment Derivative 3

<Preparation of Blue Coloring Photosensitive Composition>

46.8 parts of the dispersion liquid P1, 7.5 parts of the dispersion liquid P2, 3.0 parts of the dispersion liquid P3, and 5.5 parts of the following resin A (40% PGMEA solution) as a developing resin, A-DPH-12E (Xinzhongcun Chemical Industry Co., Ltd.) Manufactured) 3.6 parts, IRGACURE OXE 01 (1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzamide)], manufactured by BASF Japan Co., Ltd.) 1.7 parts 0.01 parts of p-methoxyphenol, 0.4 parts of 1.0% PGMEA solution of Megafac F781 (manufactured by Dianesei Co., Ltd.), and 27.7 parts of PGMEA. These were mixed and stirred, and then passed through the pore diameter. A 0.45 μm nylon filter (manufactured by Nippon Pall Co., Ltd.) was filtered to prepare a colored composition.

Resin A: Utilizing the Toyo-Phosphate modified "P-Phenylphenol Ethylene Oxide" The following synthesis of acrylate (ARONIX M110) and karenz MOI Five-way polymer

570 parts of cyclohexanone was added to the reaction vessel, and while the container was filled with nitrogen gas, the mixture was heated to 80 ° C, and 23.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, and benzyl methacrylate were added dropwise at the same temperature for 1 hour. 35.0 parts of ester, 22.0 parts of p-cumylphenol ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 48.0 parts of glycerin monomethacrylate, 2,2'-azodiiso The mixture was reacted with a mixture of 3.0 parts of butyronitrile. After completion of the dropwise addition, the reaction was further carried out at 80 ° C for 3 hours, and then 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and further reacted at 80 ° C for 1 hour to obtain a reaction. Transparent resin copolymer solution. Next, to 336 parts of the obtained transparent resin copolymer solution, 33.0 parts of 2-methylpropenylethyl isocyanate (karenz MOI), 0.4 part of dibutyltin dodecanoate, and cyclohexanone were added dropwise at 70 ° C for 3 hours. A photosensitive transparent resin solution was obtained by a mixture of 130.0 parts. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled, and the film was dried by heating at 180 ° C for 20 minutes, and the nonvolatile content was measured, and the nonvolatile content was 20 in the photosensitive transparent resin solution previously synthesized. A photosensitive resin solution was prepared by adding cyclohexanone in a mass % manner. The obtained resin A had a weight average molecular weight Mw of 21,000 and a double bond equivalent of 470.

In addition, the "double bond equivalent" is a value which is a measure of the amount of the ethylenic double bond contained in the resin. The weight (unit: g/mol) of the resin per 1 mol of the ethylenic double bond, and the smaller the value of the double bond equivalent, the higher the concentration of the ethylenic double bond in the resin. The double bond equivalent can be determined by the amount of each monomer in the synthesis.

[Chemistry 19]

The following composition was evaluated about the obtained composition.

<Evaluation of spectral characteristics>

The composition was applied onto a 7.5 cm × 7.5 cm glass substrate so as to have a coating film having a thickness of 0.8 μm by a spin coater, and then heated and dried at 100 ° C for 2 minutes using a hot plate. Then, heating was performed at 200 ° C for 5 minutes, and the coating film was cured to form a colored layer.

The obtained coloring layer forming substrate was subjected to spectroscopic measurement by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.), and transmittances at wavelengths of 450 nm, 475 nm, 525 nm, and 600 nm were evaluated. The measurement temperature was 25 °C. Five samples were measured for each sample, and the average value was used.

This determination is made as follows.

The first point of the determination point can be distinguished by whether it is within the range of the target upper limit value and the lower limit value of the transmittance of each wavelength. From this, it is judged whether C or B or more. C It becomes practically inappropriate.

The second point of the determination point can be distinguished by the degree of inclination of the region where the transmittance is lowered. Regarding B or more, it is determined by how much the T475 (transmittance at a wavelength of 475 nm) and T525 (transmittance at a wavelength of 525 nm) are quantified with respect to the upper limit value and the lower limit value. Specifically, it is determined using a value defined by the following formula.

△T=(T475-75)+(20-T525)...Formula A

AA: △T≦15%

A: 15% < △ T ≦ 20%

B: 20% < △ T

<Notes on the table>

Test No.: Starting with c as a comparative example

Pigment A: Indigo blue pigment

Pigment B: quinacridone magenta pigment

Txxx: transmittance at wavelength xxx nm

[Chemistry 20]

The blending amount of each of the examples was set in the same manner as in the test 101 in the total amount of the pigment, and the ratio of the pigment A, the pigment B, and the other pigments was also in agreement with the test 101. Among them, the test c103 and the test c104 became the blending ratio (parts by mass) in the table ( ) in the pigment concentration.

Dispersant 1: Solsperse 20000

Dispersant 2: Phosphate dispersant

<Synthesis method>

The reaction vessel was equipped with a condenser, a nitrogen gas inlet tube, and a stirrer in a three-neck round bottom flask, and charged with 18.6 g of dodecyl alcohol (manufactured by Nacalai Tesque Co., Ltd.) and 57.1 g of ε-caprolactone monomer (and pure light). 0.04 g of tetrabutyl titanate (manufactured by Tokyo Chemical Industry Co., Ltd.), the inside of the reaction vessel was replaced with nitrogen, and then heated and stirred at 120 ° C for 3 hours. The disappearance of the lactone monomer was confirmed by ¹ H-NMR. After cooling the reaction solution to room temperature, it was mixed with 8.45 g of polyphosphoric acid in an amount of 116% in terms of orthophosphoric acid, and the temperature was gradually raised, and the mixture was heated and stirred at 80 ° C for 6 hours to obtain a number average molecular weight of R ³ of 760. A phosphate ester dispersant 2 having a ratio of y=1 to y=2 of 100:12. The obtained phosphate ester dispersant had an acid value of 166.

Dispersant 3: The following structure

According to the results, it is understood that the photosensitive resin composition of the present invention exhibits a characteristic spectral characteristic in which the slope of the spectral distribution curve near 500 nm is more moderate with respect to the cured film. Further, in FIG. 2, the relationship between a part of the embodiment and the comparative example and the design target is shown as a graph.

(Example 2)

Next, in order to confirm the influence of the ratio of the pigment, the ratio was changed to carry out the same experiment. The results are shown in Table 2.

<Notes on the table>

Synonymous with Table 1

(Example 3)

Next, in order to confirm the influence of the developing resin, the same experiment was carried out by changing the kind of the resin. In the present example, the test for roughening the film surface was added, and the improvement effect was evaluated. The results are shown in Table 3.

<Film roughness evaluation>

Then, using a high-acceleration life tester (EHS-221 manufactured by ESPEC), the colored layer-forming substrate was subjected to a high-temperature and high-humidity test for 100 hours under the conditions of a temperature of 85 ° C and a humidity of 85%.

For the glass substrate after the high-temperature and high-humidity test, an condensed foreign matter was visually evaluated under the condition of 200-fold reflection using an optical microscope (MX-50 manufactured by Olympus Co., Ltd.). Five samples were measured for each sample, and the average value was used. Express the results below In the table.

- Evaluation criteria -

AA: Completely free of condensed foreign matter.

A: A very small amount of condensed foreign matter (five or more and less than 25 in five fields of view) is generated.

B: A small amount of condensed foreign matter (25 or more, less than 100 in 5 fields of view) was generated.

C: A large amount of aggregated foreign matter (100 or more in five fields of view) was generated.

Resin 1: the resin A

Resin 2

<Synthesis method>

In the monomer dropping container, it is prepared to add dimethyl-2,2'-[oxybi (sub. Base]] bis-2-acrylate 13 g, benzyl methacrylate 63 g, methyl methacrylate 15 g, methacrylic acid 38 g, peroxy-2-ethylhexanoic acid tert-butyl ester 2 g, diethylene glycol II A solution of 32 g of methyl ether was prepared by adding a solution of 6 g of n-dodecyl mercaptan and 20 g of diethylene glycol dimethyl ether to a container for dropping a chain transfer agent. 188 g of diethylene glycol dimethyl ether was added to the reaction container, and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C by heating. After confirming that the temperature was stable, the addition of the monomer dropping container and the chain transfer agent dropping container was started, and the dropwise addition of the monomer and the chain transfer agent was terminated in 140 minutes while maintaining the temperature at 90 °C. 60 minutes after the completion of the dropwise addition, the temperature was further raised to raise the temperature of the reaction vessel to 110 ° C, and maintained at 110 ° C for 180 minutes in this state. Thereafter, the inside of the reaction vessel was replaced by air. Next, 41 g of glycidyl methacrylate, 0.2 g of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.4 g of triethylamine were added to the reaction vessel at 110 ° C. The reaction was allowed to proceed for 9 hours. After completion of the reaction, 27 parts of diethylene glycol dimethyl ether was added, and the mixture was cooled at room temperature to obtain a resin 2. The average molecular weight of the resin 2 was 12,000. The double bond equivalent is 440.

Resin 3

<Synthesis method>

370 g of cyclohexanone was added to the reaction vessel, and while the vessel was purged with nitrogen, the mixture was heated to 80 ° C, and 20.0 g of methacrylic acid, 10.0 g of methyl methacrylate, and 55.0 g of n-butyl methacrylate were added at the same temperature. After reacting 15.0 g of 2-hydroxyethyl methacrylate and 4.0 g of 2,2'-azobisisobutyronitrile, the reaction was carried out at 80 ° C for 3 hours. Thereafter, 1.0 g of azobisisobutyronitrile was dissolved in 50 g of cyclohexanone, and the reaction was further continued at 80 ° C for 1 hour. After cooling to room temperature, it is made of non-volatile components. Resin 3 was obtained by adding cyclohexanone in a manner of 20% by mass. The weight average molecular weight of the resin 3 was 40,000.

<Notes on the table>

*( ) is the test number in Table 1.

Others are synonymous with Table 1.

According to the results, it is understood that in the photosensitive resin composition of the present invention, by selecting an appropriate value, the resin to be blended therein can suppress or prevent the occurrence of a film surface roughness.

The invention will be described based on this embodiment, but we do not limit our invention in any of the details of the description, unless otherwise specified, and should not contradict the invention shown in the accompanying claims. The spirit and scope are interpreted extensively.

The present application claims priority to Japanese Patent Application No. 2013-182286, filed on Jan. 3,,,,,,,,,,,,, This manual.

Claims (16)

A photosensitive resin composition which is a blue photosensitive resin composition containing a pigment, a dispersant, and a developing resin, and the pigment comprises an indigo pigment and a quinacridone pigment. The photosensitive resin composition as described in claim 1, further comprising a polymerizable compound. The photosensitive resin composition according to the first aspect of the invention, wherein the spectral characteristics of the coating film satisfy all of the following (1) to (4), and (1) the transmittance at a wavelength of 450 nm is 75% or more, (2) The transmittance at a wavelength of 475 nm is 75% or less, (3) the transmittance at a wavelength of 525 nm is 20% or more, and the transmittance at (4) a wavelength of 600 nm is 5% or less. The photosensitive resin composition as described in claim 1, wherein the polymer compound to be the developing resin has a polymerizable group in the molecule. The photosensitive resin composition according to the first aspect of the invention, wherein the polymer compound to be the developing resin has a weight average molecular weight of 23,000 or less. The photosensitive resin composition according to the first aspect of the invention, wherein the pigment is contained in an amount of 30% by mass or more and 80% by mass or less of all solid components. The photosensitive resin composition according to the first aspect of the invention, wherein the quinacridone pigment is contained in an amount of from 1 part by mass to 60 parts by mass per 100 parts by mass of the indigo pigment. The photosensitive resin composition according to the first aspect of the invention, wherein the dispersant is contained in an amount of from 1 part by mass to 80 parts by mass per 100 parts by mass of the pigment. The photosensitive resin composition according to the first aspect of the invention, wherein the developing resin is contained in an amount of from 1 part by mass to 30 parts by mass per 100 parts by mass of the pigment. The photosensitive resin composition according to claim 1, wherein the indigo pigment is C.I.P.B. 15:6. The photosensitive resin composition according to claim 1, wherein the quinacridone pigment is C.I.P.R.209 or C.I.P.R.122. The photosensitive resin composition as described in claim 1, further comprising a dioxazine pigment as the pigment. The photosensitive resin composition according to claim 12, wherein the dioxazine pigment is C.I.P.V.23. The photosensitive resin composition as described in any one of Claims 1 to 13, which is a color filter. A cured resin composition obtained by curing a photosensitive resin composition according to any one of claims 1 to 14. A color filter comprising the cured product of a resin as described in claim 15 of the patent application.