TWI720100B - Radiation-sensitive composition, film, color filter, light-shielding film and solid-state imaging element - Google Patents

Abstract

The present invention provides a radiation-sensitive composition, film, color filter, light-shielding film, and solid-state imaging element with excellent lithographic properties. The radiation-sensitive composition of the present invention includes: a resin, a colorant, a polymerizable compound, and a photopolymerization initiator; the mass ratio of the resin to the colorant, that is, resin/colorant, is 1.0 to 6.0, and the polymerizable compound contains an acid group The polymerizable compound.

Description

Radiation-sensitive composition, film, color filter, light-shielding film and solid-state imaging element

The present invention relates to a radiation-sensitive composition. In more detail, the present invention relates to a radiation-sensitive composition that can be used for the formation of a film (gray film, etc.) that can appropriately block light in the visible region. In addition, the present invention relates to a film, a color filter, a light-shielding film, and a solid-state imaging device.

For the purpose of improving the resolution of image sensors, the number of pixels has been expanded and the number of pixels has been miniaturized. On the other hand, the opening becomes smaller, which causes a decrease in sensitivity. Therefore, attempts are being made to use gray pixels (a film that moderately shields the light in the visible area) and expand the dynamic range of the image sensor.

As a radiation-sensitive composition for forming a cured film for appropriately blocking light in the visible region, for example, those described in Patent Document 1, Patent Document 2, and the like are known.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2002-71911

[Patent Document 2] Japanese Patent Laid-Open No. 2014-111734

In the case of manufacturing a cured film using a radiation-sensitive composition, it may be performed by increasing the exposure illuminance in order to shorten the exposure time at the time of pattern formation. However, as the exposure illuminance increases, it tends to be difficult to obtain a desired pattern. Therefore, in recent years, further improvement of the lithographic properties of radiation-sensitive compositions has been demanded. In particular, in the radiation-sensitive composition used in the manufacture of a cured film or the like for appropriately transmitting light in the visible region, it is often difficult to adjust the sensitivity, and further improvement in lithography is required.

Therefore, an object of the present invention is to provide a radiation-sensitive composition, film, color filter, light-shielding film, and solid-state imaging element with excellent lithography properties.

The inventors of the present invention conducted detailed studies, and as a result, found that the above-mentioned object can be achieved by the following configuration, and completed the present invention. That is, the present invention is as follows.

<1> A radiation-sensitive composition comprising: a resin, a colorant, a polymerizable compound, and a photopolymerization initiator; the mass ratio of the resin to the coloring agent, that is, the resin/colorant is 1.0 to 6.0, and the polymerizable compound includes A polymerizable compound having at least one group selected from a hydroxyl group and an acid group.

<2> The radiation-sensitive composition as described in <1>, wherein the mass ratio of resin to coloring agent, that is, resin/coloring agent, is 1.5 to 4.0.

<3> The radiation-sensitive composition according to <1> or <2>, wherein the colorant contains a pigment and contains 7 with respect to the total solid content of the radiation-sensitive composition. Mass% to 50% by mass of pigments.

<4> The radiation-sensitive composition according to <3>, wherein the pigment includes a black pigment.

<5> The radiation-sensitive composition according to any one of <1> to <4>, wherein the resin includes an alkali-soluble resin, and the alkali-soluble resin has an ethylenically unsaturated bond equivalent of 1.0 mmol/g or less.

<6> The radiation-sensitive composition according to any one of <1> to <5>, which further contains an ultraviolet absorber.

<7> The radiation-sensitive composition according to any one of <1> to <6>, wherein the photopolymerization initiator includes an α-aminoketone compound.

<8> The radiation-sensitive composition according to any one of <1> to <7>, wherein when the radiation-sensitive composition is used to form a film with a film thickness of 0.5 μm, the film's The absorbance Ab ⁵⁵⁰ of the film is 0.1 to 0.8, the standard deviation of the transmittance in the wavelength range of 400 nm to 700 nm of the film is 10% or less, and the absorbance of the film relative to the light of the wavelength of 365 nm Ab ^{365 is} compared with the film relative to the wavelength of 550 nm. The ratio of light absorbance Ab ^{550 , namely Ab 365} /Ab ^550, is 1.7 to 3.7.

<9> The radiation-sensitive composition according to any one of <1> to <8>, wherein when the radiation-sensitive composition is used to form a film with a thickness of 0.5 μm, the refractive index of light with a wavelength of 633 nm is 1.20~1.65.

<10> A film using the radiation-sensitive composition according to any one of <1> to <9>.

<11> A film in which the absorbance Ab ⁵⁵⁰ of the film relative to light with a wavelength of 550 nm is 0.1 to 0.8, and the standard deviation of the transmittance in the range of the film wavelength from 400 nm to 700 nm is 10% or less, and the film relative to the wavelength of 365 nm The ratio of the absorbance Ab ^{365 of light to the absorbance Ab 550} of the film with respect to the light having a wavelength of 550 nm, that is, Ab ³⁶⁵ /Ab ⁵⁵⁰ is 1.7 to 3.7.

<12> The film according to <10> or <11>, wherein the refractive index of the film with respect to light having a wavelength of 633 nm is 1.20 to 1.65.

<13> A color filter having a cured film using the radiation-sensitive composition according to any one of <1> to <9>.

<14> A light-shielding film having a cured film using the radiation-sensitive composition according to any one of <1> to <9>.

<15> A solid-state imaging element having a cured film using the radiation-sensitive composition according to any one of <1> to <9>.

According to the present invention, it is possible to provide a radiation-sensitive composition, film, color filter, light-shielding film, and solid-state imaging element with excellent lithographic properties.

In addition, the film of the present invention having the above-mentioned spectral characteristics has good lithography properties, and can further be made into a gray film (cured film) that does not exhibit excessive absorption at a specific wavelength, in other words, the wavelength dependence of light absorption is small. ), for example, when used as a gray pixel of a solid-state image sensor, good performance without deviation in transmittance can be achieved.

10: Coloring pixels

11: Hardened film

12: Support

A: Incident light

Fig. 1 is a diagram showing an embodiment of a color filter using the cured film of the present invention.

Fig. 2 is a diagram showing an embodiment of a color filter using the cured film of the present invention.

Fig. 3 is a diagram showing an embodiment of a color filter using the cured film of the present invention.

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

In the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) not having a substituent and includes a group (atomic group) having a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group).

In this specification, "light" refers to actinic rays or radiation. In addition, the so-called "actinic rays" or "radiation rays" refer to, for example, the bright line spectrum of mercury lamps, extreme ultraviolet light represented by excimer lasers, extreme ultraviolet light (Extreme Ultraviolet (EUV) light), X-rays, and electrons. Beam and so on.

In this specification, the term "exposure", unless otherwise specified, includes not only exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet light represented by excimer lasers, X-rays, EUV light, etc., but also exposure using electron beams, ion beams, etc. The description of the particle beam is also included in the exposure.

In this manual, the numerical range indicated by "~" refers to the range that includes the numerical values described before and after "~" as the lower limit and the upper limit.

In this specification, the "total solid content" refers to the total mass of the components after removing the solvent from all the components of the composition.

In this specification, "(meth)acrylate" means both or either of acrylate and methacrylate, and "(meth)acrylic" means both or either of acrylic acid and methacrylic acid , "(Meth)allyl" means both or either of allyl and methallyl, "(meth)acryloyl" means both of acryloyl and methacryloyl , Or either.

In this specification, the term "step" not only refers to an independent step, but even when it cannot be clearly distinguished from other steps, as long as the desired effect of the step is achieved, it is included in this term.

In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by Gel Permeation Chromatography (GPC).

<Radiation Sensing Composition>

The radiation-sensitive composition of the present invention includes: resin, colorant, polymerizable compound, and photopolymerization initiator; the mass ratio of resin to colorant, that is, resin/colorant is 1.0 to 6.0, and the polymerizable compound contains A polymerizable compound of at least one of a hydroxyl group and an acid group. Furthermore, the term “resin/colorant” refers to the mass ratio of resin to colorant (mass of resin/mass of colorant). When the radiation-sensitive composition contains two or more resins, the quality of the resin is a combination of two or more resins. meter. In addition, when the radiation-sensitive composition contains two or more coloring agents, the mass of the coloring agent is the total of two or more coloring agents.

According to the present invention, by adopting the above-mentioned configuration, a radiation-sensitive composition having excellent lithographic properties can be produced. That is, by setting the mass ratio of resin/coloring agent to 1.0-60 and using a polymerizable compound having at least one group selected from hydroxyl groups and acid groups, the dispersibility of the coloring agent in the composition can be improved. And the sensitivity can be adjusted appropriately, so that excellent lithography can be obtained.

In addition, by setting the mass ratio of the resin/coloring agent to 1.0 to 6.0 and containing the polymerizable compound having an acid group, the cleaning performance with respect to the cleaning liquid or the like is good, and the maintenance performance of the coating device is excellent. That is, since the radiation-sensitive composition of the present invention has a large resin content and contains a polymerizable compound having an acid group, it has good solubility in a cleaning solution. For example, a cleaning solution such as a solvent can be used to easily clean the adhesive on the coating. Dirt on the nozzle of the cloth device, etc.

In addition, by setting the mass ratio of the resin/coloring agent to 1.0 to 6.0 and including the polymerizable compound, the wettability to the coated substrate becomes good, and therefore the coating property can be made good. In particular, the effect is obvious on the edge of the coating, and the coating uniformity of the edge of the film is excellent.

The radiation-sensitive composition of the present invention preferably uses a coloring agent containing a black pigment. According to this aspect, it is possible to produce a radiation-sensitive composition suitable for the production of a cured film that appropriately transmits light in the visible region.

The radiation-sensitive composition of the present invention preferably uses an alkali-soluble resin having an ethylenically unsaturated bond equivalent of 1.5 mmol/g or less. To make the visible area In the case of a cured film in which light is transmitted moderately, the transmittance of i-rays (light having a wavelength of 365 nm) of the film becomes high, and therefore, sensitivity tends to increase when high-illuminance exposure is performed. In contrast, by using an alkali-soluble resin with an ethylenically unsaturated bond equivalent of 1.5 mmol/g or less as the alkali-soluble resin, the sensitivity of the radiation-sensitive composition can be appropriately adjusted, and the formation can be easily achieved even if the exposure illuminance is increased. The desired pattern. Therefore, it is easy to obtain excellent lithography properties. In particular, in the case of using a coloring agent containing a black pigment, it is easy to obtain excellent lithographic properties.

The radiation-sensitive composition of the present invention preferably uses an α-aminoketone compound as a photopolymerization initiator. In the case of manufacturing a cured film that appropriately transmits light in the visible region, the i-ray transmittance of the film becomes high, and therefore the sensitivity tends to increase when high-illuminance exposure is performed. In contrast, by using an α-aminoketone compound as a photopolymerization initiator, the sensitivity can be appropriately adjusted, and even if the exposure illuminance is increased, a desired pattern can be easily formed. Therefore, it is easy to obtain excellent lithography properties. In particular, in the case of using a coloring agent containing a black pigment, it is easy to obtain excellent lithographic properties.

The radiation-sensitive composition of the present invention is preferably used when the radiation-sensitive composition is used to form a film with a film thickness of 0.5 μm, the absorbance Ab ⁵⁵⁰ of the film with respect to light with a wavelength of 550 nm is 0.1 to 0.8, and the film has a wavelength of 400 nm. The standard deviation of the transmittance in the 700nm range is 10% or less, and the ratio ^{of the absorbance Ab 365 of the film with respect to light with a wavelength of 365 nm to the absorbance Ab 550} of the film with respect to the light with a wavelength of 550 nm ^{is Ab 365} /Ab ⁵⁵⁰ 1.7~3.7. In addition, the film is a film in a state before exposure. That is, the spectral characteristics are the spectral characteristics of the film in the state before exposure.

By using the radiation-sensitive composition having the above-mentioned characteristics, a cured film that appropriately transmits light in the visible region can be formed. That is, the film having the above characteristics has a low transmittance in the wavelength range of 400 nm to 700 nm, and a specific wavelength in the wavelength range does not have an excessive absorption peak, and the entire transmission spectrum is in a flat state in the region. Therefore, by exposing and hardening the film, it is possible to produce a good gray film that does not exhibit excessive absorption at a specific wavelength in the visible region. For example, when used as a gray pixel of a solid-state image sensor, good performance without deviation in transmittance can be achieved. Therefore, for example, when the cured film obtained by curing the film obtained by using the radiation-sensitive composition of the present invention is used in combination with the colored pixels of a color filter, it is easy to obtain good image recognition. Sex and so on. In addition, since the film of the present invention has Ab ³⁶⁵ /Ab ⁵⁵⁰ of 1.7 to 3.7, the absorbance of light with a wavelength of 365 nm is relatively high. That is, the film is also a film with a low transmittance of light having a wavelength of 365 nm. Therefore, the i-ray transmittance is moderately low, the operability during exposure is good, and the lithography is excellent.

The radiation-sensitive composition of the present invention preferably uses the radiation-sensitive composition to form a film with a thickness of 0.5 μm, and the refractive index of light with a wavelength of 633 nm is 1.20 to 1.65. By using the radiation-sensitive composition having this characteristic, it is possible to suppress the reflection of light on the surface of the film or the interface with other layers. Therefore, for example, when the cured film obtained by using the radiation-sensitive composition of the present invention is used in combination with colored pixels of a color filter, the surface of the film or other layers (such as colored pixels) can be suppressed. The reflection of light on the interface, etc., making it easy to obtain good image recognition.

Hereinafter, the radiation-sensitive composition of the present invention will be described in detail.

<<Colorant>>

The radiation-sensitive composition of the present invention contains a colorant. In addition, the colorant may be a color colorant or a black colorant. It is preferable to contain at least a black colorant. The colorant may be a pigment or a dye. Preferably it is a pigment. By using pigments, it is easy to manufacture a film with a small standard deviation of transmittance in the wavelength range of 400 nm to 700 nm. In particular, when a black pigment is used as the pigment, it is easy to manufacture a film having a standard deviation of transmittance in the above range of 10% or less.

(pigment)

As the pigment, various previously known pigments can be cited.

As a colored organic pigment, the following can be mentioned. However, the present invention is not limited to these.

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

In addition, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in the molecule of 10-14, an average of 8-12 bromine atoms, and an average of 2-5 chlorine atoms may also be used. As a specific example, the compound described in International Publication WO2015/118720 can be cited.

These organic pigments can be used alone or in combination of various organic pigments in order to improve color purity.

As the black pigment, various well-known black pigments can be used. For example, carbon black or black metal-containing inorganic pigments shown below can be cited. Examples of inorganic pigments containing ferrous metals include metal oxides containing one or two or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Materials, metal nitrides. Only one kind of these may be used, or a mixture of two or more kinds may be used. In addition, by further combining other shades of inorganic pigments with black The combination of color pigments can be adjusted so as to have the desired light-shielding properties. Examples of specific inorganic pigments that can be used in combination include zinc bloom, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitating barium sulfate and barite powder, red lead, and red iron oxide. , Chrome yellow, zinc yellow (zinc potassium chromate, zinc tetroxy chromate), ultramarine, Prussian blue (potassium ferricyanide), zircon gray ), 鐠 yellow, chrome titanium yellow, chrome green, malachite green, Victoria green, dark blue (not related to Prussian blue), vanadium zirconium blue, chrome tin red, manganese red, orange red, etc. In particular, for the purpose of expressing light-shielding properties in a wide-wavelength region from ultraviolet to infrared, not only these black pigments or inorganic pigments having other hues can be used alone, but also a plurality of pigments can be mixed and used.

The black pigment is preferably carbon black or titanium black. From the viewpoint of having light-shielding properties in a wide wavelength range from ultraviolet to infrared, titanium black is particularly preferred. The so-called titanium black refers to black particles having titanium atoms. Preferably it is low-order titanium oxide or titanium oxynitride. It is not particularly limited. As the titanium oxynitride, WO2008/123097, Japanese Patent Laid-Open No. 2009-58946, Japanese Patent Laid-Open No. 2010-14848, Japanese Patent Laid-Open No. 2010-97210, and Japan can be used as titanium oxynitride. Titanium oxynitride described in Japanese Patent Application Publication No. 2011-2274670 and the like, a mixture of titanium oxynitride and titanium carbide described in Japanese Patent Application Publication No. 2010-95716, and the like. For the purpose of improving dispersibility, suppressing cohesion, etc., the surface of the titanium black particles may be modified as necessary. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, and zirconium oxide. In addition, the water-repellent substance shown in Japanese Patent Laid-Open No. 2007-302836 can also be used. To process. Titanium black can also contain Cu, Fe, Mn, V, Ni and other composite oxides, cobalt oxide, iron oxide, carbon black and other black pigments in one or more combinations for the purpose of adjusting dispersibility and coloring properties. .

As a method of producing titanium black, there are the following methods: a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing environment (Japanese Patent Laid-Open No. 49-5432), and a method of reducing it in a reducing environment containing hydrogen A method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open) 60-65069, Japanese Patent Laid-Open No. 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610 )Wait. However, the present invention is not limited to these.

The specific surface area of titanium black is not particularly limited. The value measured by the Brunauer-Emmett-Teller (BET) method is preferably 5m ² /g or more and 150m ² /g or less, more preferably 20m ² /g or more And 120m ² /g or less.

Examples of commercially available products of titanium black include: titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), and Tilack D (trade name, manufactured by Ako Chemical Co., Ltd.), etc.

The average primary particle diameter of the black pigment is preferably 5 nm or more, more preferably 10 nm or more. From the same viewpoint, the upper limit is preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 100 nm or less. Let the average primary particle diameter of the black pigment be the value measured by the following method. And set the mixture containing black pigment It is diluted to 80 times in propylene glycol monomethyl ether acetate, and the obtained diluted solution is measured by dynamic light scattering method. Let it be the average particle diameter obtained by performing this measurement using Microtrac (trade name) UPA-EX150 manufactured by Nikkiso Corporation.

(dye)

As the dye, for example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japan Patent No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5,667,920, U.S. Patent No. 505,950, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent A pigment disclosed in Kaihei 6-51115 and Japanese Patent Laid-open No. 6-194828. If distinguished in the form of chemical structure, you can use pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonine compounds, Pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. In addition, dye multimers can also be used as dyes. Examples of the dye multimer include the compounds described in Japanese Patent Application Publication No. 2011-213925 and Japanese Patent Application Publication No. 2013-041097.

(Preferable combination of colorants)

As a preferable aspect of a coloring agent, the following (1), (2), etc. are mentioned. By using the following coloring agents, a radiation-sensitive composition suitable for the production of films, etc., which satisfies the following conditions can be obtained: when the radiation-sensitive composition of the present invention is used to form a film with a thickness of 0.5 μm ^{, The absorbance Ab 550} of the film with respect to light with a wavelength of 550 nm is 0.1 to 0.8, the standard deviation of the transmittance in the range of the film with a wavelength of 400 nm to 700 nm is 10% or less, and the absorbance of the film with respect to the light with a wavelength of 365 nm Ab ³⁶⁵ The ratio of ^{Ab 550 to} the absorbance of the film with respect to the light with a wavelength of 550 nm, ^{namely Ab 365} /Ab ^550, is 1.7 to 3.7.

(1) Use a coloring agent containing a black pigment, and contain 7 mass% to 50 mass% (preferably 10 mass% to 40 mass %, and more preferably 12 mass% relative to the total solid content of the radiation-sensitive composition ~30% by mass) of black pigments.

(2) Use a coloring agent that contains more than one black pigment and more than one color pigment, and contains 5.8% to 43.7% by mass (preferably 8.3% to 39.3% by mass relative to the total solid content of the radiation-sensitive composition Mass%, more preferably 10.0 mass% to 35.0 mass%) of the black pigment containing 1.5 mass% to 17.5% by mass (preferably 2.1 mass% to 15.7% by mass) relative to the total solid content of the radiation sensitive composition, More preferably, it is a color pigment of 2.5% by mass to 14.0% by mass).

The aspect of (1) is preferably a coloring agent containing 60% by mass or more of black pigment, and more preferably a coloring agent containing 80% by mass or more of black pigment. The black pigment is preferably carbon black and titanium black, more preferably titanium black.

The aspect of (2) is preferably a coloring agent containing 50% to 99% by mass of black pigments and 1% to 50% by mass of color pigments, more preferably 60% to 90% by mass of black A coloring agent for pigments and 10% to 40% by mass of color pigments. The black pigment is preferably carbon black and titanium black, more preferably titanium black. Color The material is preferably at least one pigment selected from the group consisting of red pigments, orange pigments and yellow pigments.

The content of the colorant is preferably 7% by mass to 50% by mass relative to the total solid content of the radiation-sensitive composition. The lower limit is preferably 7% by mass or more, more preferably 10% by mass or more, and still more preferably 12% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.

The content of the pigment of the colorant is preferably 80% by mass or more, more preferably 90% by mass or more.

In addition, the content of the pigment relative to the total solid content of the radiation-sensitive composition is preferably 7 to 50% by mass. The lower limit is preferably 10% by mass or more, more preferably 12% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less.

In addition, the content of the black pigment relative to the total solid content of the radiation-sensitive composition is preferably 7 to 50% by mass. The lower limit is preferably 10% by mass or more, more preferably 12% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.

<<Polymerizable compound>>

The radiation-sensitive composition of the present invention contains a polymerizable compound. The polymerizable compound is preferably a compound containing one or more groups having an ethylenically unsaturated bond, more preferably a compound containing two or more groups having an ethylenically unsaturated bond, and still more preferably three or more groups having an ethylenic unsaturated bond. The compound of the radical unsaturated bond. The upper limit of the group having an ethylenically unsaturated bond is, for example, preferably fifteen or less, and more preferably six or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

The polymerizable compound may be any of chemical forms such as monomers, prepolymers, ie, dimers, trimers, and oligomers, or mixtures of these, and multimers of these. Preferably it is a monomer. The molecular weight of the polymerizable compound is preferably 100 to 3000, more preferably 250 to 1500. The polymerizable compound is preferably a trifunctional to pentafunctional (meth)acrylate compound, and more preferably a trifunctional to hexafunctional (meth)acrylate compound.

The radiation-sensitive composition of the present invention preferably contains a polymerizable compound having at least one group selected from a hydroxyl group and an acid group as the polymerizable compound. By using a polymerizable compound having at least one group selected from a hydroxyl group and an acid group, even when there are many solid components other than the coloring agent in the composition, the developability is excellent, and excellent lithography can be obtained. As an acid group, a carboxyl group, a sulfo group, a phosphoric acid group, etc. are mentioned, Preferably it is a carboxyl group.

The acid value of the polymerizable compound having at least one group selected from a hydroxyl group and an acid group is preferably 10 mgKOH/g~200mgKOH/g, more preferably 15mgKOH/g~100mgKOH/g, and still more preferably 20mgKOH/g~50mgKOH/ g. If the acid value is in the above range, the effect of obtaining a uniform film with less unevenness after lithography can be obtained.

The polymerizable compound having at least one group selected from a hydroxyl group and an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably unreacted a non-aromatic carboxylic acid anhydride and an aliphatic polyhydroxy compound The polymerizable compound in which the hydroxyl group of reacts to have an acid group is particularly preferably one in which the aliphatic polyhydroxy compound in the ester is pentaerythritol and/or dipentaerythritol. As a commercially available product, for example, Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd. Wait.

The polymerizable compound having at least one group selected from a hydroxyl group and an acid group is preferably a compound represented by the following general formula (1).

General formula (1)(A) _n1 -L-(Ac) _n2

(In the general formula (1), A represents a hydroxyl group or an acid group, L is a (n1+n2) valent group containing at least a carbon atom and a hydrogen atom, and Ac represents a (meth)acryloxy group. n1 represents 1 or more Integer, n2 represents an integer greater than 1)

The acid group represented by A includes a carboxyl group, a sulfo group, a phosphoric acid group, etc., and a carboxyl group is preferred.

L represents a (n1+n2) valence group containing at least a carbon atom and a hydrogen atom. For example, as the divalent group, there can be enumerated: -CH ₂ -, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO- , -SO ₂ -and a group formed by connecting two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. L is preferably a group containing at least -CH _{2 -.} The number of carbon atoms constituting L is preferably 3-100, more preferably 6-50. Examples of the trivalent or higher group include a group obtained by removing one or more hydrogen atoms from a divalent group.

n1 is preferably 1 or 2, more preferably 1. n2 is preferably 1-6, more preferably 2-5.

The polymerizable compound having at least one group selected from a hydroxyl group and an acid group is preferably a compound represented by the following general formula (11) or (12).

In the general formula (11), R ¹ , T ¹ , and X ¹ each independently represent any of the groups shown below ^{as R 1} , T ¹ , or X ^1. n represents an integer from 0 to 14.

[化3]

In the general formula (12), Z ¹ and G ¹ each independently represent any one of the groups shown below. The meaning of W ^{1 is} the same as the group represented by ^{R 1} or X ¹ in the general formula (11). ^{Among the six W 1s} , three or more represent R ¹ , and one or more represent X ¹ . p represents an integer from 0 to 14.

Among the compounds represented by general formula (11) or general formula (12), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.

Specific examples of the polymerizable compound having at least one group selected from a hydroxyl group and an acid group include the following compounds. In addition, the chemical described in paragraph 0093 to paragraph 0096 of Japanese Patent Laid-Open No. 2009-221114 can also be used. Compound. Incorporate this content into this manual.

The radiation-sensitive composition of the present invention may further include a polymerizable compound that does not have a hydroxyl group and an acid group (hereinafter, also referred to as other polymerizable compound), and preferably includes another polymerizable compound. Other polymerizable compounds may be in any of chemical forms such as monomers, prepolymers, ie, dimers, trimers, and oligomers, or mixtures of these, and multimers of these. Preferably it is a monomer. The molecular weight of other polymerizable compounds is preferably 100-3000, more preferably 250-1500. The other polymerizable compound is preferably a trifunctional to pentafunctional (meth)acrylate compound, and more preferably a trifunctional to hexafunctional (meth)acrylate compound. As these specific compounds, reference can be made to paragraphs 0095 to 0108 of Japanese Patent Laid-Open No. 2009-288705, paragraphs 0227 of Japanese Patent Laid-Open No. 2013-29760, and paragraphs of Japanese Patent Laid-Open No. 2008-292970 The compounds described in 0254 to paragraph 0257 are incorporated into this specification.

Other polymerizable compounds are preferably dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol triacrylate Tetraol tetraacrylate (the commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (the commercially available product is KAYARAD) D -310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available product is KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.; A-DPH-12E, Shin Nakamura Chemical Industry Co., Ltd. (Manufactured by Sartomer), and compounds having a structure in which (meth)acrylic acid groups are bonded via ethylene glycol residues and propylene glycol residues (for example, SR454 and SR499 commercially available from Sartomer). These oligomer types can also be used. In addition, KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. In addition, the following compounds can also be used.

Among other polymerizable compounds, compounds having a caprolactone structure are also preferred. Polymerizable compounds having a caprolactone structure are, for example, commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

Other polymerizable compounds can also be polymerized with alkoxyl groups Compound. The polymerizable compound having an ethyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or an propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and more preferably 4-20 An ethoxylated trifunctional~hexafunctional (meth)acrylate compound.

As commercially available products of polymerizable compounds having ethylene oxide groups, for example, SR494, a tetrafunctional acrylate having four ethylene oxide groups manufactured by Sartomer Co., Ltd., and SR494 manufactured by Nippon Kayaku Co., Ltd. The hexafunctional acrylate with three pentoxy groups is DPCA-60, and the trifunctional acrylate with three isobutoxy groups is TPA-330. In addition, the following compounds can also be used.

As other polymerizable compounds, as described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765 General urethane acrylates, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418 Those with an ethylene oxide-based skeleton described in the bulletin Urethane compounds are also preferred. In addition, it is also preferable to use the structure described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238 having an amino group in the molecule or Sulfide structure addition polymerizable compounds.

As commercially available products, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Co., Ltd.), and DPHA-40H (Nippon Kayaku Co., Ltd.) Manufacturing), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

In the radiation-sensitive composition of the present invention, the content of the polymerizable compound (the total of the polymerizable compound having an acid group and the polymerizable compound not having an acid group) relative to the total solid content of the radiation-sensitive composition is preferably 10% to 70% by mass. The lower limit is, for example, more preferably 15% by mass or more, and still more preferably 20% by mass or more. The upper limit is, for example, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

In addition, the content of the polymerizable compound having an acid group is preferably 9% by mass to 50% by mass, and more preferably 12% by mass to 40% by mass relative to the total solid content of the radiation-sensitive composition.

In addition, the ratio of the polymerizable compound having an acid group in all polymerizable compounds is preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 80% by mass.

The polymerizable compound having an acid group may be only one type or two or more types. When two or more are contained, it is preferable that the total amount falls within the said range.

<<hardening accelerator>>

The radiation-sensitive composition of the present invention can also be used to promote the reaction of polymerizable compounds. Add a hardening accelerator for the purpose of lowering the hardening temperature. Examples of the curing accelerator include polyfunctional thiol compounds (polyfunctional mercapto compounds) having two or more mercapto groups in the molecule, and the like. The polyfunctional thiol compound can also be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkane thiol, and particularly preferably a compound having a structure represented by the following general formula (T1).

(In formula (T1), n represents an integer from 2 to 4, and L represents a divalent linking group to a tetravalent linking group)

In the general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbons, particularly preferably n is 2, and L is an alkylene group having 2 to 12 carbons. As a specific example of a polyfunctional thiol compound, the compound represented by the following structural formula (T2)-formula (T4) is mentioned, Especially preferably, it is a compound represented by a formula (T2). These polyfunctional thiol compounds can be used singly or in combination of multiple types.

[化9]

In addition, the hardening accelerator may also use methylol-based compounds (for example, compounds exemplified as crosslinking agents in paragraph 0246 of JP 2015-34963 A), amines, phosphonium salts, amidine salts, and amide compounds. (The above are, for example, the curing agent described in paragraph 0186 of JP 2013-41165 A), alkali generators (for example, ionic compounds described in JP 2014-55114 A), cyanate ester compounds (For example, the compound described in paragraph 0071 of Japanese Patent Laid-Open No. 2012-150180), alkoxysilane compounds (for example, the alkoxysilane having an epoxy group described in Japanese Patent Laid-Open No. 2011-253054 Compound), onium salt compound (for example, the compound exemplified as an acid generator in Paragraph 0216 of JP 2015-34963 A, the compound described in JP 2009-180949 A), and the like.

When the radiation-sensitive composition of the present invention contains a hardening accelerator, the content of the hardening accelerator is preferably 0.3% by mass to 8.9% by mass, and more preferably 0.8% by mass relative to the total solid content of the radiation-sensitive composition %~6.4% by mass.

<<Compounds with epoxy groups>>

The radiation-sensitive composition of the present invention also preferably contains a compound having an epoxy group.

The compound having an epoxy group is preferably a compound having two or more epoxy groups in one molecule. The number of epoxy groups is preferably 2 to 10 in one molecule, more preferably 2 to 5, and particularly preferably 3.

As the compound having an epoxy group, a compound having a structure in which two benzene rings are connected via a hydrocarbon group can also be used. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.

In addition, the epoxy group is preferably connected via a linking group. As the linking group, an alkylene group selected from an alkylene group, an arylene group, -O-, -NR'-(R' represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent is preferable. Is a hydrogen atom) _{and a group of at least one of -SO 2} -, -CO-, -O-, and -S-.

The epoxy equivalent of the epoxy-containing compound (= the molecular weight of the epoxy-containing compound/the number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 g/eq to 400 g/eq, and still more preferably 100g/eq~300g/eq.

The compound having an epoxy group may be a low-molecular compound (for example, the molecular weight is less than 2000, and the molecular weight is less than 1000), or a macromolecule (for example, the molecular weight is 1000 or more, in the case of a polymer, The weight average molecular weight is 1000 or more). Compounds with epoxy groups The weight average molecular weight of the substance is preferably 200 to 100,000, more preferably 500 to 50,000.

The compound having an epoxy group can also use paragraph 0034 to paragraph 0036 of JP 2013-011869, paragraph 0147 to paragraph 0156 of JP 2014-043556, and JP 2014-089408 The compound described in paragraph 0085 to paragraph 0092. These contents are incorporated into this manual.

Examples of commercially available products include "EHPE3150 (manufactured by Daicel)", "EPICLON N660 (manufactured by DIC)" and the like.

When the radiation-sensitive composition of the present invention contains a compound having an epoxy group, the content of the compound having an epoxy group relative to the total solid content of the radiation-sensitive composition is preferably 0.1% by mass to 40% by mass . The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less. The compound having an epoxy group may be one kind alone, or two or more kinds may be used in combination. When using two or more types together, it is preferable that the total amount falls within the said range.

<<Resin>>

The radiation-sensitive composition of the present invention contains a resin. The resin is formulated for the purpose of dispersing the colorant in the composition and the use of the binder, for example. In addition, the resin mainly used to disperse the colorant is also referred to as a dispersant. Among them, such use of resin is an example, and it can also be used for purposes other than such use.

The weight average molecular weight (Mw) of the resin is preferably 2,000~ 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

The ethylenically unsaturated bond equivalent of the resin is preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less. If the ethylenically unsaturated bond equivalent of the resin is 1.0 mmol/g or less, the sensitivity of the radiation-sensitive composition can be appropriately adjusted, and the handleability is excellent. Therefore, good lithography properties can be obtained. In particular, in the case of using a coloring agent containing a black pigment, a good lithography property can be obtained.

In the radiation sensitive composition of the present invention, the content of the resin is preferably 5% to 50% by mass of the total solid content of the radiation sensitive composition, more preferably 15% to 35% by mass.

In addition, the mass ratio (resin/colorant) of the resin to the coloring agent in the radiation-sensitive composition is 1.0 to 6.0, preferably 1.5 to 4.0, and more preferably 1.5 to 3.0. If the resin/colorant is 1.0 or more, the pixel linearity after lithography is good, and if it is 6.0 or less, a film having the spectral characteristics of the present invention can be formed.

The composition of the present invention may include only one type of resin, or may include two or more types. When two or more are contained, it is preferable that the total amount falls within the said range.

In the present invention, relative to the total mass of the resin, the content of the resin having an ethylenically unsaturated bond equivalent in the resin exceeding 1.0 mmol/g is preferably 70% by mass or less, more preferably 40% by mass or less, and still more preferably 10% by mass % Or less, especially preferably not contained.

(Alkali-soluble resin)

The radiation-sensitive composition of the present invention contains an alkali-soluble resin as the resin. By containing alkali-soluble resin, developability and pattern formation are improved. Furthermore, alkali Soluble resins can also be used as dispersants or binders.

The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5,000 to 100,000. In addition, the number average molecular weight (Mn) is preferably 1,000 to 20,000.

As the alkali-soluble resin, it can be appropriately selected from the following alkali-soluble resins. The alkali-soluble resin can be a linear organic polymer polymer and has a molecular weight (preferably based on acrylic copolymers and styrene copolymers). The chain molecule) has at least one group that promotes alkali solubility.

As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxy styrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred. From the viewpoint of controlling developability, acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred.

Examples of groups that promote alkali solubility (hereinafter, also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Preferably, they are soluble in organic solvents and can be weakly alkaline. As an aqueous solution developer, a (meth)acrylic group is particularly preferred. These acid groups may be only one type or two or more types.

The ethylenically unsaturated bond equivalent of the alkali-soluble resin is preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less. If the ethylenically unsaturated bond equivalent of the alkali-soluble resin is 1.0 mmol/g or less, the sensitivity of the radiation-sensitive composition can be appropriately adjusted, and even if the exposure illuminance is increased, the desired pattern is easily formed, and the operability is excellent. Therefore, good lithography properties can be obtained. Especially when using black pigment Next, good lithography can be obtained. Furthermore, in the present invention, the ethylenically unsaturated bond equivalent (double bond equivalent) is defined by the ratio of the molar number of the ethylenically unsaturated group to the mass of the resin.

For the production of alkali-soluble resin, for example, a known radical polymerization method or the like can be applied. The polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing alkali-soluble resin by radical polymerization method can be easily set by those skilled in the art and can also be tested. Decide the conditions sexually.

The alkali-soluble resin is preferably a polymer having a carboxylic acid group in the side chain, and examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partial esters. Alkali-soluble phenol resins such as maleic acid copolymers and novolak type resins, acidic cellulose derivatives having carboxyl groups in side chains, and polymers having hydroxyl groups added with acid anhydrides. In particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is preferable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds, and the like. Examples of alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate Butyl acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. Examples of vinyl compounds include styrene, α-methylstyrene, and vinyl toluene , Glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, Tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. In addition, as other monomers, the N-substituted maleimide monomer described in JP-A 10-300922 can also be cited. Examples of the N-substituted maleimide monomer include N-phenylmaleimide, N-cyclohexylmaleimide, and the like. Furthermore, these other monomers that can be copolymerized with (meth)acrylic acid may be only one type or two or more types.

Alkali-soluble resins can preferably use benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid 2-hydroxyethyl copolymer , A multi-element copolymer containing benzyl (meth)acrylate/(meth)acrylic acid/other monomers. In addition, a copolymer of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate/polystyrene described in Japanese Patent Laid-Open No. 7-140654, can also be preferably used. Macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/formaldehyde Benzyl acrylate/methacrylic acid copolymer, etc. In addition, as a commercially available product, for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can also be used.

The alkali-soluble resin also preferably contains a polymer that contains a compound represented by the following general formula (ED1) and/or a compound represented by the following general formula (ED2) (hereinafter, sometimes These compounds are also called "ether dimers") by polymerizing monomer components.

In the general formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), reference can be made to the description in Japanese Patent Laid-Open No. 2010-168539.

In the general formula (ED1), ^{the optionally substituted hydrocarbon group with 1 to 25 carbons represented by R 1} and R ² is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, Linear or branched alkyl groups such as n-butyl, isobutyl, tertiary butyl, tertiary pentyl, stearyl, lauryl, and 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, Alicyclic groups such as tertiary butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl, etc.; 1-methoxyethyl , 1-ethoxyethyl and other alkyl groups substituted by alkoxy; benzyl and other alkyl groups substituted by aryl groups. Among these hydrocarbon groups, in terms of heat resistance, substituents of primary or secondary carbon such as methyl, ethyl, cyclohexyl, and benzyl, which are difficult to be removed by acid or heat, are particularly preferred.

As a specific example of the ether dimer, for example, paragraph 0317 of JP 2013-29760 A can be referred to, and this content is incorporated into this specification. There may be only one type of ether dimer, or two or more types. Structures derived from ether dimers can also copolymerize other monomers.

Alkali-soluble resin may also contain the structural unit derived from the compound represented by following formula (X).

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may contain a benzene ring. n represents an integer of 1-15.

In the formula (X), the carbon number of the alkylene group of _{R 2 is preferably 2-3.} Moreover, _{the carbon number of the alkyl group of R 3} is 1-20, More preferably, it is 1-10, and _{the alkyl group of R 3} may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group, a 2-phenyl(iso)propyl group, and the like.

As a specific example of alkali-soluble resin, the following can be mentioned. The following structure In the formula, Me represents a methyl group.

Alkali-soluble resins can refer to paragraphs 0558 to 0571 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of the specification of U.S. Patent Application Publication No. 2012/0235099), and these contents are incorporated into In this manual.

Furthermore, the copolymer (B) described in paragraph 0029 to paragraph 063 of JP 2012-32767 A, the alkali-soluble resin used in the examples, and the paragraph of JP 2012-208474 A can also be used. 0088 to the adhesive resin described in paragraph 0098 and the adhesive resin used in the examples, the adhesive resin described in paragraph 0022 to paragraph 0032 of JP 2012-137531 A, and the adhesive used in the examples Adhesive resin, the binder resin described in paragraph 0132 to paragraph 0143 of JP 2013-024934 A, and the binder resin used in the examples, paragraph 0092 to paragraph 0098 of JP 2011-242752 A And the binder resin used in the examples, Japanese Patent Laid-Open The binder resin described in paragraph 0030 to paragraph 0072 of 2012-032770. These contents are incorporated into this manual.

The acid value of the alkali-soluble resin is preferably 30 mgKOH/g to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and still more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, further preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and particularly preferably 120 mgKOH/g or less.

The content of the alkali-soluble resin is preferably 0.1% by mass to 20% by mass relative to the total solid content of the radiation-sensitive composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is more preferably 12% by mass or less, and still more preferably 10% by mass or less. The radiation-sensitive composition of the present invention may contain only one kind of alkali-soluble resin, or two or more kinds. When two or more are contained, it is preferable that the total amount falls within the said range.

(Dispersant)

The radiation-sensitive composition of the present invention may contain a dispersant in the form of a resin. Especially in the case of using a pigment, it is preferable to include a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (alkaline resins). The dispersant preferably contains at least an acidic dispersant, more preferably only an acidic dispersant. When the dispersant contains at least an acidic dispersant, the dispersibility of the colorant is improved, and excellent developability can be obtained. Therefore, photolithography can be used to better pattern formation. In addition, the dispersant is only an acidic dispersant. For example, the content of the acidic dispersant in the total mass of the dispersant is preferably 99% by mass or more, and may be 99.9% by mass or more.

Here, the so-called acidic dispersant (acidic resin) means that the amount of acid groups is large The amount of the resin in the basic group. When the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more, and more preferably is substantial The above resin contains only acid groups. The acid group possessed by the acidic dispersant (acid resin) is preferably a carboxyl group.

In addition, the so-called basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. When the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, the basic dispersant (alkaline resin) is preferably a resin in which the amount of basic groups accounts for 50 mol% or more. The basic group possessed by the basic dispersant is preferably an amino group.

The acid value of the acidic dispersant (acid resin) is preferably 40mgKOH/g~105mgKOH/g, more preferably 50mgKOH/g~105mgKOH/g, and still more preferably 60mgKOH/g~105mgKOH/g.

The resin used as a dispersant preferably contains a repeating unit having an acid group. Since the resin contains the repeating unit with acid groups, when the pattern is formed by photolithography, the residue generated on the base of the pixel can be further reduced.

In addition, the resin used as a dispersant is also preferably a graft copolymer. Since the graft copolymer can increase the affinity with the solvent by the graft chain, it is excellent in the dispersibility of the colorant and the dispersion stability over time. In addition, the presence of graft chains in the composition can increase the affinity with polymerizable compounds, alkali-soluble resins, and the like, and therefore it is difficult to generate residues during alkali development. In addition, in the present invention, the so-called graft copolymer refers to a resin having a graft chain. In addition, the term “graft chain” means from the root of the main chain of the polymer to the end of the group branched from the main chain.

In the present invention, the graft copolymer preferably has atoms other than hydrogen atoms The number is the resin of the graft chain in the range of 40 to 10,000. In addition, the number of atoms other than hydrogen atoms in each grafted chain is preferably 40 to 10,000, more preferably 50 to 2,000, and still more preferably 60 to 500.

Examples of the main chain structure of the graft copolymer include (meth)acrylic resins, polyester resins, polyurethane resins, polyurea resins, polyamide resins, polyether resins, and the like. Among them, (meth)acrylic resin is preferred.

As the graft chain of the graft copolymer, in order to increase the interaction between the graft site and the solvent and thereby improve the dispersibility, it is preferable to have a graft chain of poly(meth)acrylic acid, polyester, or polyether, More preferably, it has a graft chain of polyester or polyether.

The graft copolymer is preferably calculated in terms of mass, relative to the total mass of the graft copolymer, and contains the repeating unit having the graft chain in the range of 2% by mass to 90% by mass, and more preferably in the range of 5% by mass to 5% by mass. The range of 30% by mass includes a repeating unit having a graft chain. If the content of the repeating unit having a graft chain is within this range, the dispersibility of the colorant will be good.

In the present invention, as a graft copolymer, a copolymer containing a repeating unit represented by any one of the following formula (1) to formula (4) can also be used. The graft copolymer can be particularly used as a dispersant for black pigments.

[化14]

In formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ , and W ^{4 are} preferably oxygen atoms.

In formula (1) to formula (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ^{5 are} preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbons, more preferably each independently a hydrogen atom or a methyl group, and particularly preferably methyl.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking is not particularly restricted based on the structure. As the ^{divalent linking group represented by Y 1} , Y ² , Y ³ , and Y ⁴ , specifically, the linking group of the following (Y-1) to (Y-21) and the like can be given as examples. In the structure shown below, A and B respectively refer to the bonding site with the left end group and the right end group in formulas (1) to (4).

[化15]

In formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples include: alkyl, hydroxyl, alkoxy, aryloxy, heteroaryloxy, alkylsulfide, arylsulfide, and heteroarylsulfide Group, and amine group, etc. Among these, particularly from the viewpoint of improving dispersibility, the ^{organic groups represented by Z 1} , Z ² , Z ³ , and Z ⁴ are preferably groups having a stereo-repulsive effect, and each independently is preferably carbon Alkyl group or alkoxy group having 5 to 24, particularly preferably each independently a branched alkyl group having 5 to 24 carbons, a cyclic alkyl group having 5 to 24 carbons, or an alkane having 5 to 24 carbons. Oxy. In addition, the alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic.

In formula (1) to formula (4), n, m, p, and q are each independently an integer of 1 to 500.

In addition, in formula (1) and formula (2), j and k each independently represent an integer of 2-8. From the viewpoint of dispersion stability and developability, j and k in formula (1) and formula (2) are preferably an integer of 4 to 6, and most preferably 5.

In the formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, multiple R ³ may be the same as or different from each other.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited based on the structure. R ^{4 is} preferably a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbons, a branched alkyl group having 3 to 20 carbons, or a cyclic alkyl group having 5 to 20 carbons. It is more preferably a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is 2 to 500, multiple X ⁵ and R ⁴ present in the graft copolymer may be the same as or different from each other.

From the viewpoint of dispersion stability and developability, the repeating unit represented by the formula (1) is more preferably a repeating unit represented by the following formula (1A).

In addition, from the viewpoint of dispersion stability and developability, the repeating unit represented by the formula (2) is more preferably a repeating unit represented by the following formula (2A).

In addition, from the viewpoint of dispersion stability and developability, the formula (3) The repeating unit represented is more preferably a repeating unit represented by the following formula (3A) or formula (3B).

In the formula ^{(1A), X 1, X} Y 1, Z 1 and n are as defined in the formula (1) is ^1, Y ^1, Z ¹ and n, respectively, preferred ranges are also the same.

In formula ^{(2A), X 2, Y} 2, Z 2 and m are as defined for the formula X (2) is ^2, Y ^2, Z ² and the same as m, the preferred range is also the same.

In formula (3A) or the formula ^{(3B), 3, Y 3} , Z 3 and same ^{p X 3, Y 3, Z} 3 and p are defined for the formula X (3) is, preferred ranges are also the same.

In addition, the graft copolymer preferably also has hydrophobic repeating units in addition to the repeating units represented by the formulas (1) to (4). among them, In the present invention, the hydrophobic repeating unit is a repeating unit that does not have an acid group (for example, a carboxyl group, a sulfo group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

The hydrophobic repeating unit is preferably a (corresponding) repeating unit derived from a compound (monomer) having a ClogP value of 1.2 or more, and more preferably a repeating unit derived from a compound having a ClogP value of 1.2 to 8.

The ClogP value is a value calculated using the program "CLOGP" available from Daylight Chemical Information System, Inc. (Daylight Chemical Information System, Inc.). This program provides the value of "calculated logP" calculated by Hansch-Leo's fragment approach (refer to the following document). The fragment method is to divide the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and sum the logP contributions allocated to the fragments to estimate the logP value of the compound. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.

AJ Leo, "Comprehensive Medicinal Chemistry" Issue 4, C. Hansch, PG Sammons, and JB Taylor and CA Caramsden (CARamsden) editor, p. 295, Pergamon Press, 1990; C. Hansch (C. Hansch) and AJ Leo (AJ Leo), "Chemistry and Biology Substituent Constants For Correlation Analysis in Chemistry and Biology", John Wiley &Sons.; AJ Leo, "Calculation of Hydrophobic Constants from Structure ( Calculating logPoct from structure)", Chemistry Review (Chemical Reviews, Chem. Rev.), No. 93, pp. 1281-1306, 1993.

logP refers to the common logarithm of the partition coefficient P (Partition Coefficient). It is the physical property value that expresses how an organic compound is distributed in the equilibrium of the two-phase system of oil (usually 1-octanol) and water as a quantitative value. , Is shown by the following formula.

logP=log(Coil/Cwater)

In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase.

If the value of logP sandwiches 0 and increases in the positive direction, it means that the oil solubility increases. If the absolute value of the negative direction increases, it means that the water solubility increases, and there is a negative correlation with the water solubility of organic compounds, as an estimate The parameters of the hydrophilic and hydrophobic properties of organic compounds are widely used.

The graft copolymer preferably has one or more repeating units selected from repeating units derived from monomers represented by the following general formula (i) to general formula (iii) as a hydrophobic repeating unit.

In the formulas (i) to (iii), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or the number of carbon atoms is 1 to 6 alkyl groups (for example, methyl, ethyl, propyl, etc.).

R ¹ , R ² , and R ^{3 are more} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. R ² and R ^{3 are} particularly preferably hydrogen atoms.

X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkene group) , Divalent aromatic group (for example, aryl group, substituted aryl group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH- ), a substituted imino group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl group (-CO-), or a combination of these groups, and the like.

L is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. The oxyethylene structure is more preferably an oxyethylene structure or an oxyethylene structure. In addition, L may also include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. The polyoxyethylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by -(OCH ₂ CH ₂ ) _n -, and n is preferably an integer of 2 or more, more preferably an integer of 2-10.

Examples of Z include aliphatic groups (for example, alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (for example, aryl groups, substituted aryl groups). Group), heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ³¹ -, where R ³¹ is Aliphatic group, aromatic group or heterocyclic group), carbonyl group (-CO-), or a combination of these groups, etc.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group further includes a ring assembly hydrocarbyl group and a cross-linked cyclic hydrocarbyl group. Examples of the ring assembly hydrocarbyl group include bicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the cross-linked cyclic hydrocarbon ring include: pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]octane Bicyclic hydrocarbon rings such as alkane ring, bicyclic [3.2.1] octane ring, etc.), tricyclic [5.2.1.0 ^3,8 ] decane (homobredane), adamantane (adamantane), tricyclic [5.2.1.0 ^{2 ,6} ]decane, tricyclic [4.3.1.1 ^2,5 ] undecane ring and other tricyclic hydrocarbon rings, tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, perhydro-1 , 4-methano-5, 8-methanophthalene ring (perhydro-1,4-methano-5, 8-methanonaphthalene ring) and other tetracyclic hydrocarbon rings. In addition, the cross-linked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, such as: perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydrophenanthrene A condensed ring formed by condensing multiple 5-membered to 8-membered cycloalkane rings such as perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene ring. As for the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

The number of carbon atoms of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. In addition, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. Among them, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. It is also possible to condense other heterocycles, aliphatic rings or aromatic rings on the heterocycle. In addition, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), substituted imino groups (=NR ³² , this Where, R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Among them, the heterocyclic group does not have an acid group as a substituent.

In the formula (iii), R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkane having 1 to 6 carbon atoms Group (e.g., methyl, ethyl, propyl, etc.), Z, or -LZ. Here, the meanings of L and Z are the same as those described above. R ⁴ , R ⁵ , and R ^{6 are} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

The monomer represented by the general formula (i) is preferably: R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L is a single bond or an alkylene group or a divalent compound containing an oxyalkylene structure As the linking group, X is an oxygen atom or an imino group, and Z is a compound in which an aliphatic group, a heterocyclic group, or an aromatic group is used. The monomer represented by the general formula (ii) is preferably a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. The monomer represented by the general formula (iii) is preferably a compound in which R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group.

Examples of representative compounds represented by formula (i) to formula (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes, and the like. In addition, as an example of the compound represented by formula (i) to formula (iii), reference may be made to the compound described in paragraph 0089 to paragraph 0093 of Japanese Patent Laid-Open No. 2013-249417, and these contents are incorporated herein In the manual.

In the graft copolymer, the hydrophobic repeating unit is preferably calculated in terms of mass, relative to the total mass of the graft copolymer, and contained in the range of 10% by mass to 90% by mass, and more preferably in the range of 20% by mass to 80% by mass. The range of mass% is included. When the content is in the above range, sufficient pattern formation is obtained.

The graft copolymer preferably includes a repeating unit having a functional group that can interact with a coloring agent and the like in addition to the repeating units represented by the formulas (1) to (4).

As the acid group, there are, for example, a carboxyl group, a sulfo group, a phosphoric acid group, etc., and a carboxyl group is preferred. By having a carboxyl group, it has good adsorption power to colorants such as black pigments and can improve the dispersibility of black pigments and the like.

The graft copolymer may also contain one or two or more repeating units having an acid group.

The graft copolymer may contain a repeating unit having an acid group, or may not contain a repeating unit having an acid group. If it contains, the content of the repeating unit having an acid group is calculated by mass and is relative to the total amount of the graft copolymer. The quality is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 60% by mass.

As the basic group, there are, for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing a N atom, an amide group, etc., and particularly preferable ones are that the colorant has good adsorption power and dispersibility. High tertiary amine group. The graft copolymer may have one or two or more of these basic groups.

The graft copolymer may contain a repeating unit with a basic group, or may not contain a repeating unit with a basic group. When it contains, the content of the repeating unit with a basic group is calculated by mass, relative to the graft copolymer The total mass of the product is preferably 0.01% by mass to 50% by mass, and more preferably 0.01% by mass to 30% by mass from the viewpoint of suppressing the developmental hindrance.

Examples of the coordinating group and the reactive functional group include an acetoxyacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride group, and an acylochloride group. Particularly preferred is an acetoxy acetoxy group which has good adsorption power to the colorant and high dispersibility. The graft copolymer may have one or two or more of these groups.

The graft copolymer may contain a repeating unit having a coordinating group, or a repeating unit including a reactive functional group, or may not contain the repeating unit. If it contains, the content of these repeating units is calculated by mass In total, it is preferably 10% by mass to 80% by mass relative to the total mass of the graft copolymer, and more preferably 20% by mass to 60% by mass from the viewpoint of inhibiting developmental hindrance.

In the case where the graft copolymer has functional groups that can interact with the coloring agent in addition to the graft chain, there is no particular limitation on how these functional groups are introduced, and the graft copolymer preferably has functional groups selected from One or more repeating units derived from repeating units of the monomer represented by the following general formula (iv) to general formula (vi).

In general formula (iv) to general formula (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or the number of carbon atoms is 1 to 6 alkyl groups (for example, methyl, ethyl, propyl, etc.).

In general formula (iv) to general formula (vi), R ¹¹ , R ¹² , and R ^{13 are more} preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably each independently It is a hydrogen atom or a methyl group. In the general formula (iv), it is ^{particularly preferable that R 12} and R ¹³ are each a hydrogen atom.

_{X 1} in the general formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

Y in the general formula (v) represents a methine group or a nitrogen atom.

_{L 1 in} general formula (iv) to general formula (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include: divalent aliphatic groups (for example, alkylene groups, substituted alkylene groups, alkenylene groups, substituted alkenylene groups, alkynylene groups, and substituted alkylene groups. Alkynyl group), divalent aromatic group (for example, arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), a substituted imino group (-NR ³¹ '-, where, R ^31' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), or the plurality of group The combination and so on.

L _{1 is} preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. The oxyethylene structure is more preferably an oxyethylene structure or an oxyethylene structure. In addition, L ₁ may also include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. The polyoxyethylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by -(OCH ₂ CH ₂ ) _n -, and n is preferably an integer of 2 or more, more preferably an integer of 2-10.

In general formula (iv) to general formula (vi), Z ₁ represents a functional group that can interact with the coloring agent in addition to the graft chain, and is preferably a carboxyl group or a tertiary amino group, and more preferably a carboxyl group.

In the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( e.g., methyl, ethyl, propyl, etc.), - Z _1, or -L ₁ -Z _1. , L ₁ and Z the meanings and L ₁ and Z ₁ is identical with ₁ herein, preferred embodiments are also the same. R ¹⁴ , R ¹⁵ , and R ^{16 are} preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

The monomer represented by the general formula (iv) is preferably: R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is an alkylene group or a divalent link containing an oxyalkylene structure A compound in which X ₁ is an oxygen atom or an imino group, and Z ₁ is a carboxylic acid group. The monomer represented by the general formula (v) is preferably a compound in which R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group. The monomer represented by the general formula (vi) is preferably: R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z ₁ is a carboxylic acid group compound of.

As a specific example of the said graft copolymer, the following can be mentioned. In addition, the resins described in paragraph 0121 to paragraph 0130 of JP 2014-111734 A can be cited, and this content is incorporated in this specification.

In addition, the resin (dispersant) can also be used for an oligoimine-based dispersant in which at least one of the main chain and the side chain contains a nitrogen atom. The oligoimine-based dispersant is preferably a resin having a repeating unit and a side chain, and having a basic nitrogen atom in at least one of the main chain and the side chain, and the repeating unit contains a moiety having a functional group having a pKa of 14 or less Structure X, the side chain includes a side chain Y with 40 to 10,000 atoms. The so-called basic nitrogen atom, As long as it is a basic nitrogen atom, it is not particularly limited.

Regarding the oligoimine-based dispersant, the description of paragraph 0102 to paragraph 0174 of JP 2012-255128 A can be referred to, and the content is incorporated into this specification. As specific examples of the oligoimine-based dispersant, the following resins or the resins described in paragraphs 0168 to 0174 of JP 2012-255128 A can be used.

The dispersant can also be obtained as a commercially available product. Specific examples of this include: "DA-7301" manufactured by Kusumoto Chemical Co., Ltd.; "Disperbyk (Disperbyk)" manufactured by BYK Chemie Co., Ltd. 101 (polyamide phosphate), 107 (carboxylate), 110 (acid group-containing copolymer), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)"; "EFKA" manufactured by EFKA 4047, 4050-4165 (polyurethane series), EFKA (EFKA) 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo Pigment Derivatives)"; "Ajisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno; "Flo" manufactured by Kyoeisha Chemical Co., Ltd. Blue (Flowlen) TG-710 (urethane oligomer), Polyflow (Polyflow) No.50E, No.300 (acrylic copolymer)"; "Desbalone" manufactured by Kusumoto Chemical Co., Ltd. (Disparlon) KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725"; "Dai Demol RN, N (formalin naphthalene sulfonate condensation polymer), MS, C, SN-B (aromatic sulfonate formalin condensation polymer), Homogenol L-18 (high polymer Carboxylic acid), Emulgen 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether), ``Acetamin 86 (stearyl amine acetate) "; "Solsperse 5000 (Phthalocyanine Derivative), 22000 (Azo Pigment Derivative), 13240 (Polyesteramine), 3000, 12000, 17000 manufactured by Lubrizol, Japan , 20000, 27000 (polymers with functional parts at the end), 24000, 28000, 32000, 38500 (grafted polymers)"; "Nikkol T106 ("Nikkol") manufactured by Nikko Chemicals Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene ethylene monostearate)"; Kawaken Fine Chemical (Kawaken Fine Chemical) company "Sinocote ( Hinoact) T-8000E" etc.; "Organic siloxane polymer KP341" manufactured by Shin-Etsu Chemical Co., Ltd.; "W001: Cationic surfactant" manufactured by Yushang Company; Polyoxyethylene lauryl ether, polyoxyethylene Ethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurel Nonionic surfactants such as acid esters, polyethylene glycol distearate, and sorbitan fatty acid esters; anionic surfactants such as "W004, W005, and W017"; and "Eve" manufactured by Morishita Sangyo Co., Ltd. EFKA-46, EFKA-47, EFKA-47EA, EFKA (EFKA) polymer 100, EFKA (EFKA) polymer 400, EFKA (EFKA) ) Polymer 401, EFKA polymer 450"; "Disperse Aid 6, Disperse Aid" manufactured by San Nopco 8. Disperse Aid 15, Disperse Aid 9100" and other polymer dispersants; "Adeka Adeka" manufactured by ADEKA Pluronic) L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123"; and "Iou" manufactured by Sanyo Chemical Co., Ltd. "Ionet (trade name) S-20" and so on. In addition, Acrybase FFS-6752, Acrybase FFS-187 (the above are manufactured by Fujikura Kasei), Acrycure-RD-F8 ( Nippon Shokubai Co., Ltd.), Cyclomer P (made by Daicel).

Furthermore, the resin described in the section of the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as an adhesive.

<<Photopolymerization initiator>>

The radiation-sensitive composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, it is better to UV The light from the area to the visible area is photosensitive. In addition, it may be an active agent that generates active radicals by generating a certain effect with a sensitizer excited by light, or may be an initiator that initiates cationic polymerization according to the type of monomer. In addition, the photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably, 330 nm to 500 nm).

The photopolymerization initiator is preferably a compound having at least an aromatic group, and examples thereof include (bis) phosphine oxide or its esters, acetophenone-based compounds, α-amino ketone compounds, and benzophenone-based compounds. Compounds, benzoin ether compounds, ketal derivatives, thioxanthone compounds, oxime ester compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, Onium salt compounds such as iodonium compounds, aronium compounds, azinium compounds, and metallocene compounds, organic boron salt compounds, dioxin compounds, and the like. From the viewpoint of sensitivity, oxime ester compounds, acetoxyphosphine oxide compounds, acetophenone compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and sulfur compounds are preferred. The ether compound is more preferably an α-aminoketone compound. In the case of using a black pigment as a colorant, by using an α-aminoketone compound as a photopolymerization initiator, it is easy to obtain excellent lithographic properties.

As an α-amino ketone compound, the compound represented by the following formula (AK-1) is mentioned.

[化21]

In the formula, Ar represents -SR ¹³ or a phenyl group substituted with -N(R ^7E )(R ^{8E ), and R 13} represents a hydrogen atom or an alkyl group.

R ^1D and R ^2D each independently represent an alkyl group having 1 to 8 carbon atoms. R ^1D and R ^2D may be bonded to each other to form an alkylene group with 2-9 carbon atoms.

The alkyl group represented by R ^1D and R ^2D may be linear, branched, and cyclic, and is preferably linear or branched.

The alkyl group represented by R ^1D and R ^2D may be unsubstituted or may have a substituent. Examples of substituents include aryl groups, heterocyclic groups, nitro groups, cyano groups, halogen atoms, -OR ^Y1 , -SR ^Y1 , -COR ^Y1 , -COOR ^Y1 , -OCOR ^Y1 , -NR ^Y1 R ^Y2 ,- NHCOR ^Y1 , -CONR ^Y1 R ^Y2 , -NHCONR ^Y1 R ^Y2 , -NHCOOR ^Y1 , -SO ₂ R ^Y1 , -SO ₂ OR ^Y1 , -NHSO ₂ R ^Y1 and so on. R ^Y1 and R ^Y2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The substituent is preferably an aryl group. It is particularly ^{preferable that one of R 1D} and R ^2D is an unsubstituted alkyl group, and the other is an aryl group substituted alkyl group.

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

The number of carbon atoms in the alkyl group represented by ^{R Y1} and R ^{Y2 is preferably 1-20.} The alkyl group may be any of linear, branched, and cyclic, and is preferably linear or branched.

The number of carbon atoms in the aryl group as a substituent and the aryl group ^{represented by R Y1} and R ^Y2 is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The aryl group may be a single ring or a condensed ring.

The heterocyclic group represented by R ^Y1 and R ^Y2 is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3-30, more preferably 3-18, and still more preferably 3-12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

R ^3D and R ^4D each independently represent a hydrogen atom, an alkyl group with 1 to 12 carbons, an alkyl group with 2 to 4 carbons substituted by an alkoxy group with 1 to 4 carbons, or an alkene with 3 to 5 carbons. base. R ^3D and R ^4D may be bonded to each other to form an alkylene group with a carbon number of 3-7, and the alkylene group may also be one containing -O- or -N(R ¹² )- in the alkylene chain. R ¹² represents an alkyl group having 1 to 4 carbon atoms.

R ^7E and R ^8E each independently represent a hydrogen atom, an alkyl group with 1 to 12 carbons, an alkyl group with 2 to 4 carbons substituted by an alkoxy group with 1 to 4 carbons, or an alkene with 3 to 5 carbons. base. R ^7E and R ^8E may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group may also be one containing -O- or -N(R ¹² )- in the alkylene chain. Here, R ^{12 has} the same meaning as described above.

Examples of the compound represented by the formula (AK-1) include: 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(hexyl )Phenyl)-2-morpholinopropane-1-one, 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 1,2-benzyl -2-Dimethylamino-1-(4-morpholinylphenyl)-butanone, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]-1-butanone and the like.

Commercial products include: IRGACURE 907, IRGACURE 907, IRGACURE 907, IRGACURE 907, IRGACURE (IRGACURE) 369, and IRGACURE 379 (trade names, all manufactured by BASF), etc.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the phosphine-based initiator described in Japanese Patent No. 4225898 can also be used.

As a hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-184 IRGACURE-127 (trade name, all manufactured by BASF). As the aminoacetophenone-based initiator, commercially available products such as IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names, both are available). For BASF (BASF) company manufacture). As the aminoacetophenone-based initiator, the compound described in Japanese Patent Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wavelength light source such as 365 nm or 405 nm can also be used. In addition, as the phosphine-based initiator, commercially available products such as IRGACURE-819 or DAROCUR-TPO (brand names, both manufactured by BASF) can be used.

As specific examples of the oxime compound, the compound described in Japanese Patent Laid-Open No. 2001-233842, the compound described in Japanese Patent Laid-Open No. 2000-80068, and the compound described in Japanese Patent Laid-Open No. 2006-342166 can be used. . As a specific example of the oxime compound, for example, 3-benzyloxy Oxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionoxyiminobutan-2-one, 2-acetoxyiminobutan-2-one Aminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-Toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc.

Examples of oxime compounds include "Journal of the British Chemical Society-Pulkin II (JCSPerkin II)" ((1979) pages 1653-1660), "Journal of the British Chemical Society-Pulkin II (JCSPerkin II)" )'' ((1979) pages 156~162), “Journal of Photopolymer Science and Technology” ((1995) pages 202~232), Japanese Patent Publication 2000-66385 The compounds described in Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2004-534797, and Japanese Patent Application Publication No. 2006-342166, and the like.

Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be preferably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO. , LTD) manufacturing), Adeka Arkls (Adeka Arkls) NCI-930 (Adeka (ADEKA) company manufacturing).

In addition, as oxime compounds other than those described above, it can also be used for carbazole The compound described in Japanese Patent Publication No. 2009-519904 with an oxime linked to the N-position of the ring, the compound described in U.S. Patent No. 7626957 with a heterosubstituent introduced into the benzophenone site, and the compound described in the dye site The nitro compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Application Publication No. 2009-292039, the ketoxime compound described in International Publication WO2009/131189, contains a triazine skeleton in the same molecule The compound described in U.S. Patent No. 7556910 having an oxime skeleton, the compound described in Japanese Patent Laid-Open No. 2009-221114, etc. having a maximum absorption wavelength at 405 nm and having good sensitivity to a g-ray light source. Preferably, for example, paragraph 0274 to paragraph 0275 of JP 2013-29760 A can be referred to, and the content can be incorporated into this specification.

In the present invention, an oxime compound having a sulphur ring can also be used as a photopolymerization initiator. As a specific example of the oxime compound which has a sulphur ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466 is mentioned. Incorporate this content into this manual.

In the present invention, aliphatic compounds having fluorine atoms can also be used as photopolymerization initiators. Specific examples of the oxime compound having a fluorine atom include the compound described in Japanese Patent Laid-Open No. 2010-262028, the compound 24 described in the Japanese Patent Publication No. 2014-500852, the compound 36 to the compound 40, and the Japanese Patent The compound (C-3) described in JP 2013-164471 A, etc. Incorporate this content into this manual.

In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. As a specific example of the oxime compound having a nitro group, Paragraph 0031 to Paragraph 0047 of Japanese Patent Laid-Open No. 2013-114249 and Japanese Patent Laid-Open The compound described in paragraph 0008 to paragraph 0012 of paragraph 0070 to paragraph 0079 of 2014-137466 publication, or Adeka Arkls NCI-831 (manufactured by ADEKA).

In the case of using an oxime compound in a low-illuminance region, it is preferable to reduce the addition amount of the oxime compound or to use two or more photopolymerization initiators different in sensitivity. The oxime compound may be used in combination, or the oxime compound may be used in combination with other photopolymerization initiator compounds. An oxime compound, an α-aminoketone compound, etc. may also be mentioned.

Specific examples of oxime compounds are shown below, but the present invention is not limited to these.

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[化23]

The photopolymerization initiator is preferably a compound having a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably a compound having high absorbance at 365 nm and 405 nm .

From the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm of the photopolymerization initiator is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is preferred. spectrophotometer)) and use ethyl acetate solvent and measure at a concentration of 0.01g/L.

The photopolymerization initiator can also be used in combination of two or more types if necessary.

Relative to the total solid content of the radiation-sensitive composition, the content of the photopolymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and still more preferably 1% by mass to 20% by mass %. Within this range, better sensitivity and pattern formation can be obtained.

In addition, the photopolymerization initiator preferably contains 50% by mass or more of the α-aminoketone compound, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit may be 100% by mass, may be 99.5% by mass or less, or may be 99% by mass or less.

In addition, the quality comparison of the photopolymerization initiator and the coloring agent is preferably that the photopolymerization initiator/colorant=0.1 to 1.0, more preferably 0.1 to 0.8, further preferably 0.1 to 0.6, and particularly preferably 0.1 to 0.5. If the mass ratio of the photopolymerization initiator to the coloring agent is in the above range, it is easy to compare the absorbance Ab ³⁶⁵ of the film with respect to light with a wavelength of 365 nm in the state before the film is exposed to the light The ratio of absorbance Ab ^{550 , namely Ab 365} /Ab ^{550, is} adjusted to 1.7~3.7. In particular, in the case of using a coloring agent containing a black pigment, by adjusting the mass ratio of the photopolymerization initiator to the coloring agent to the above range, it is easy to ^{adjust Ab 365} /Ab ⁵⁵⁰ to 1.7 to 3.7.

The radiation-sensitive composition of the present invention may include only one type of photopolymerization initiator, or may include two or more types. When two or more are contained, it is preferable that the total amount falls within the said range.

<<Solvent>>

The radiation-sensitive composition of the present invention preferably contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component or the coatability of the radiation-sensitive composition.

As an example of an organic solvent, the following can be mentioned, for example. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. , Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkoxypropionic acid alkyl esters (For example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate (for example: methyl 2-alkoxypropionate, 2-alkoxypropionic acid Ethyl, 2-alkoxy propyl propionate, etc. (for example, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propionate propyl, 2-ethoxy Methyl propionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetyl acetic acid Methyl ester, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.; and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, Diethylene 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 And the like; and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc.; and as aromatic hydrocarbons, for example, preferably Examples include: toluene, xylene, etc.

One kind of organic solvent may be used alone, or two or more kinds may be used in combination. In the case of using two or more organic solvents in combination, it is particularly preferred to include the methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve acetate. , Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol A mixed solution of two or more of acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

In the present invention, the peroxide content of the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.

The content of the solvent is preferably such an amount that the total solid content of the radiation-sensitive composition becomes 5 mass% to 80 mass%. The lower limit is preferably 10% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

<<Pigment Derivatives>>

The radiation-sensitive composition of the present invention may contain a pigment derivative. As the pigment derivative, a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthaliminomethyl group is mentioned. Examples of organic pigments used to constitute pigment derivatives include diketopyrrolopyrrole pigments, azo pigments, Phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perylene pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolines Ketone pigments, quinophthalone pigments, threne pigments, metal complex pigments, etc. In addition, the acidic group possessed by the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group, and a quaternary ammonium salt group thereof, more preferably a carboxylic acid group and a sulfonic acid group, and particularly preferably a sulfonic acid group. The basic group possessed by the pigment derivative is preferably an amino group, and particularly preferably a tertiary amino group. As a specific example of a pigment derivative, the following compounds can be mentioned, for example. In addition, the description of paragraph 0162 to paragraph 0183 of JP 2011-252065 A can be referred to, and the content can be incorporated into this specification.

The content of the pigment derivative in the radiation-sensitive composition of the present invention is preferably 1% by mass to 30% by mass, and more preferably 3% by mass to 20% by mass relative to the total mass of the pigment. Only one type of pigment derivative may be used, or two or more types may be used in combination.

<<Surface active agent>>

From the viewpoint of further improving coatability, the radiation-sensitive composition of the present invention may contain various surfactants. As a surfactant, a fluorine-based interface can be used Various surfactants such as activators, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

Since the radiation-sensitive composition of the present invention contains a fluorine-based surfactant, the solution properties (especially fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness or the liquid-saving property can be further improved. That is, in the case of forming a film using a coating liquid to which a radiation-sensitive composition containing a fluorine-based surfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the coating surface is wetted. The wettability is improved, and the coatability to the coated surface is improved. Therefore, it is possible to better perform film formation with a uniform thickness with small thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid-saving properties, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include: Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac ) F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac RS-72-K (the above are manufactured by DIC); Fluorad )FC430, Fluorad FC431, Fluorad Fluorad FC171 (manufactured by Sumitomo 3M); Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (manufactured by Asahi Glass Company); PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A can also be used. A block polymer can also be used as a fluorine-based surfactant, and as a specific example, for example, the compound described in JP 2011-89090 A can be cited.

Fluorine-based surfactants can also preferably use repeating units derived from (meth)acrylate compounds having fluorine atoms and those derived from alkoxyl groups having two or more (preferably five or more) It is preferably a fluorine-containing polymer compound which is a repeating unit of (meth)acrylate compound of ethoxylate and propoxylate, and the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000.

In the present invention, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as a fluorine-based surfactant. As a specific example, the compounds described in paragraph 0050 to paragraph 0090 and paragraph 0289 to paragraph 0295 of Japanese Patent Laid-Open No. 2010-164965 can be cited, for example, Megafac RS-101 manufactured by DIC Corporation. , RS-102, RS-718K, etc.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propane). Oxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl Phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (manufactured by BASF) Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Solsperse 20000 ( Japan Lubrizol (Lubrizol) company manufacture) and so on. In addition, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) , (Meth) acrylic (co)polymer Polyflow (Polyflow) No.75, No.90, No.95 (Koei Corporation (Made by Yushang Company), W001 (made by Yushang Company), etc.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sanded BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (The above is Toray Dow Corning Corning), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are made by Momentive Performance Materials), KP341, KF6001, KF6002 (the above are Shin-Etsu (Manufactured by Silicone), BYK 307, BYK 323, BYK 330 (the above are manufactured by BYK Chemie), etc.

Only one type of surfactant may be used, or two or more types may be combined.

The content of the surfactant relative to the total solid content of the radiation-sensitive composition is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass.

<<Silane Coupling Agent>>

The radiation-sensitive composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having at least two functional groups with different reactivity in one molecule. Examples include: γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane , 3-methacryloxypropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, preferably γ-methacryloxy Propyl trimethoxy silane, 3-methacryloxy propyl dimethoxy methyl silane, etc. For the details of the silane coupling agent, reference can be made to the description of paragraphs 0155 to 0158 of JP 2013-254047 A, and this content is incorporated into this specification.

When the radiation-sensitive composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.5% by mass to 30% by mass relative to the total solid content of the radiation-sensitive composition. The lower limit is preferably 0.7% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. The radiation-sensitive composition of the present invention may include only one type of silane coupling agent, or may include two or more types. When two or more are contained, it is preferable that the total amount falls within the said range.

<<Polymerization inhibitor>>

The radiation-sensitive composition of the present invention also preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, tertiary butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), N- Nitrophenyl hydroxylamine trivalent cerium salt, etc.

In the radiation-sensitive composition of the present invention, if a polymerization inhibitor is used, the subsequent development performance variation during low-illuminance exposure can be suppressed, thereby being more effective It suppresses the dependence of the exposure illuminance related to the pattern formation properties such as the line width, film thickness, and spectroscopic spectrum of the pattern. Furthermore, even in the case of a film for transmitting a fixed amount of light, it may be possible to suppress unnecessary hardening of the unexposed portion or hardening by light other than the desired exposure.

When the radiation-sensitive composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 5% by mass relative to the total solid content of the radiation-sensitive composition. The radiation-sensitive composition of the present invention may include only one type of polymerization inhibitor, or may include two or more types. When two or more are contained, it is preferable that the total amount falls within the said range.

In addition, if necessary, in order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenamide can also be added to make it biased during the drying process after coating. Exist on the surface of the coating film. The amount of higher fatty acid derivatives added is preferably 0.5% by mass to 10% by mass relative to the mass of the radiation-sensitive composition.

<<Ultraviolet absorber>>

The radiation-sensitive composition of the present invention may also contain an ultraviolet absorber. By containing an ultraviolet absorber, the transmittance of light with a wavelength of 365 nm can be adjusted, so that a radiation-sensitive composition with excellent lithographic properties can be made. The ultraviolet absorber is preferably a conjugated diene compound, and more preferably a compound represented by the following general formula (1). If the conjugated diene compound is used, it is particularly possible to suppress changes in the subsequent development performance during low-illuminance exposure, and it is possible to more effectively suppress the exposure illuminance related to the pattern formation properties such as the line width, film thickness, and spectroscopic spectrum of the pattern. Dependency.

R ¹ and R ² each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms. R ¹ and R ² may be the same or different from each other, and the absence of both represents hydrogen The atomic situation.

R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is a group whose substituent constant σp value of Hammett (hereinafter referred to as "σp value") is 0.20 or more and 1.0 or less. It is preferably a group having a σp value of 0.30 or more and 0.8 or less. R ³ and R ^{4 are} preferably acyl group, carbamethanyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, amine The sulfonyl group is particularly preferably an acyl group, carbamethanyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, and sulfamsulfonyl group.

Regarding the general formula (1), reference can be made to the description of paragraph 0148 to paragraph 0158 of JP 2010-049029 A, and the content is incorporated into this specification.

As specific examples of the compound represented by the general formula (1), the following compounds can be cited. In addition, the compounds described in paragraph 0160 to paragraph 0162 of JP 2010-049029 A can be cited, and this content is incorporated in this specification.

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The content of the ultraviolet absorber is preferably 0.01% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass relative to the total solid content of the radiation-sensitive composition.

In addition, the quality ratio of the ultraviolet absorber and the coloring agent is preferably ultraviolet absorber/colorant=0.1 to 1.2, more preferably 0.1 to 1.0, further preferably 0.1 to 0.8, particularly preferably 0.1 to 0.7. If the mass ratio of the ultraviolet absorber to the coloring agent is in the above range, it is easy to compare the absorbance Ab ³⁶⁵ of the film with respect to light with a wavelength of 365 nm in the state before the film is exposed, and the absorbance Ab of the film with respect to light with a wavelength of 550 nm. The ratio of ^{550 , namely Ab 365} /Ab ^{550, is} adjusted to 1.7 to 3.7. In particular, in the case of using a coloring agent containing a black pigment, by adjusting the mass ratio of the ultraviolet absorber to the coloring agent to the above range, it is easy to ^{adjust Ab 365} /Ab ⁵⁵⁰ to 1.7 to 3.7. Two or more types of ultraviolet absorbers may be used in combination.

<<Sensitizer>>

The radiation-sensitive composition of the present invention may contain a sensitizer for the purpose of improving the efficiency of radical generation of the photopolymerization initiator and increasing the photosensitive wavelength. The sensitizer is preferably a photopolymerization initiator used in combination with an electron transfer mechanism or energy. Those who move the agency for sensitization. As a preferable example of the sensitizer, the compounds described in paragraph 0085 to paragraph 0098 of JP 2008-214395 A can be cited. From the viewpoint of sensitivity and storage stability, the content of the sensitizer is preferably in the range of 0.1% by mass to 30% by mass, and more preferably in the range of 1% by mass to 20% by mass relative to the total solid content of the radiation-sensitive composition The range of% is more preferably the range of 2% by mass to 15% by mass.

<<Other additives>>

In the radiation-sensitive composition of the present invention, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anticoagulants, etc. may be blended as necessary. As these additives, the additives described in paragraph 0155 to paragraph 0156 of JP 2004-295116 A can be cited, and these contents are incorporated in this specification. As the antioxidant, for example, a phenol compound, a phosphorus compound (for example, the compound described in paragraph 0042 of JP 2011-90147 A), a thioether compound, and the like can be used. As a commercially available product, for example, the ADEKASTAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60) manufactured by ADEKA can be cited. , AO-60G, AO-80, AO-330, etc.). Antioxidants can also be used in combination of two or more. The radiation-sensitive composition of the present invention may contain the sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Laid-Open No. 2004-295116, and the heat described in paragraph 0081 of Japanese Patent Laid-Open No. 2004-295116. Polymerization inhibitor.

Metal elements may be included in the radiation-sensitive composition due to the raw materials used, but from the viewpoint of suppressing the occurrence of defects, the radiation-sensitive composition The content of group 2 elements (calcium, magnesium, etc.) in the substance is preferably 50 ppm or less, and is preferably controlled to 0.01 ppm to 10 ppm. In addition, the total amount of the inorganic metal salt in the radiation-sensitive composition is preferably 100 ppm or less, and more preferably controlled to be 0.5 ppm to 50 ppm.

The content of the high refractive index particles in the radiation-sensitive composition of the present invention is preferably less than 5% by mass, more preferably 3% by mass or less, and still more preferably 1% by mass relative to the total solid content of the radiation-sensitive composition. the following. It may also be a state which does not substantially contain high refractive index particles. The content of the high-refractive-index particles is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and more preferably not contained relative to the total solid content of the radiation-sensitive composition. If the content of the high refractive index particles is less than 5% by mass, it is easy to produce a film and a cured film having a characteristic that the refractive index of light having a wavelength of 633 nm is 1.20 to 1.65.

Examples of the high refractive index particles include materials having a refractive index of 1.8 or more. The lower limit can be set to 1.9 or more, or it can be set to 2 or more. The upper limit may be 3 or less, or 2.9 or less, or 2.8 or less. As an example of the high refractive index particles, there can be cited those containing particles selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S At least one element of the metal oxide particles. Specific examples include particles of titanium dioxide, zirconium oxide, tin oxide, indium oxide, zinc oxide, indium tin oxide (ITO), silicon dioxide, aluminum oxide, magnesium oxide, vanadium oxide, and niobium oxide. The metal oxide particles are mainly composed of oxides of these metals, and may further contain other elements. The so-called main component refers to the component with the largest content (% by mass) among the components constituting the particle. As other elements Examples include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

<<Preparation method of radiation-sensitive composition>>

The radiation-sensitive composition of the present invention can be prepared by mixing the above-mentioned components.

In the preparation of the radiation-sensitive composition, the components constituting the radiation-sensitive composition can be blended in batches, or the components can be dissolved and/or dispersed in a solvent and then sequentially blended. In addition, there are no particular restrictions on the order of input or working conditions during deployment. For example, a composition can be prepared by dissolving and/or dispersing all the components in a solvent at the same time. If necessary, each component can be appropriately prepared in advance into two or more solutions or dispersions, and these can be used (during coating). They are mixed to prepare a composition.

For the purpose of removing foreign matter or reducing defects, the radiation-sensitive composition of the present invention is preferably filtered by a filter. As the filter, if it is a filter that has been used for filtration purposes and the like since the past, it can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6, nylon-6, and 6, and polyolefin resins (including high-density resins) such as polyethylene and polypropylene (PP) can be used. Density, ultra-high molecular weight polyolefin resin) and other raw materials filters. Among these raw materials, polypropylene (including high-density polypropylene) is preferred.

The pore size of the filter is suitably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm. By setting it as this range, the fine foreign matter which hinders the preparation of a uniform and smooth radiation-sensitive composition in the following steps can be reliably removed.

When using filters, different filters can also be combined. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more.

In addition, it is also possible to combine first filters having different pore diameters within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, available from Pall (DFA4201NXEY, etc.), Advantec Toyo, Nihon Entegris (formerly Nihon Entegris, etc.) Choose from a variety of filters provided by Mykrolis) or Kitz Microfilter.

As the second filter, a filter formed of the same material as the first filter can be used.

For example, the filtration with the first filter may be performed only with the dispersion liquid, or the second filtration may be performed after mixing other components.

<Film, Cured Film>

Next, the film and cured film of the present invention will be described. The film and the cured film of the present invention are those obtained by using the radiation-sensitive composition of the present invention. In addition, the film of the present invention is also a film having the following characteristics. In addition, the "film" in the present invention refers to a film in a state before exposure. In addition, the "cured film" in the present invention refers to a film that has undergone a curing treatment such as exposure.

^{The absorbance Ab 550} of the film with respect to light at a wavelength of 550 nm is 0.1 to 0.8, the standard deviation of the transmittance in the range of 400 nm to 700 nm of the film is 10% or less, and the absorbance of the film with respect to light at a wavelength of 365 nm Ab ³⁶⁵ , The ratio of Ab ³⁶⁵ /Ab ^{550 to the absorbance Ab 550} of the film with respect to light of a wavelength of 550 nm is 1.7 to 3.7.

^{The Ab 365} /Ab ⁵⁵⁰ of the film (film before exposure) of the present invention is 1.7 to 3.7, preferably 1.8 to 3.5, more preferably 1.8 to 3.4, and still more preferably 1.9 to 3.3. If Ab ³⁶⁵ /Ab ⁵⁵⁰ is in the above-mentioned range, good adhesion and high-resolution lithography performance can be obtained.

^{Ab 550} of the film of the present invention (film before exposure) and the cured film of the present invention (film after exposure) is 0.1 to 0.8, preferably 0.15 to 0.70, more preferably 0.18 to 0.50, and still more preferably 0.20 to 0.30 . In addition, the standard deviation of the film of the present invention (film before exposure) and the cured film of the present invention (film after exposure) is 10% or less, preferably 5% or less, and more preferably 3% or less.

If Ab ⁵⁵⁰ is in the above range, light in the visible area can be blocked appropriately. In addition, if the standard deviation is 10% or less, the specific wavelength in the wavelength range does not have an excessive absorption peak, and the entire transmission spectrum appears in a flat state in the region. Therefore, by setting Ab ⁵⁵⁰ to 0.1 to 0.8 and setting the standard deviation to 10% or less, a good gray film that does not exhibit excessive absorption at a specific wavelength can be produced, for example, as a solid-state imaging device. In the case of gray pixels, good performance without deviation in transmittance can be achieved.

The film of the present invention (the film before exposure) and the cured film of the present invention (the film after exposure) preferably have a refractive index of 1.20 to 1.65 with respect to light having a wavelength of 633 nm, more preferably 1.20 to 1.60, and more preferably It is 1.20~1.58. If the refractive index of light with a wavelength of 633 nm is in the above range, the reflection of light can be suppressed, and therefore the reflection of light on the film surface can be suppressed. Therefore, in the coloring of the cured film of the present invention and the color filter When pixels and the like are used in combination, the surface of the cured film of the present invention or the interface between the cured film of the present invention and other layers (for example, colored pixels, etc.) can be suppressed from light reflection, etc., so that good images can be easily obtained Recognition, etc.

The film and the cured film having the above-mentioned characteristics can be manufactured using the radiation-sensitive composition of the present invention.

In addition, one film (single-layer film) of a film having the above-mentioned characteristics and a cured film may have the above-mentioned spectral characteristics, or a multilayer film formed by combining two or more films can satisfy the above-mentioned spectral characteristics. In the case where the spectroscopic characteristics are satisfied by combining two or more films, for example, the concentration of the coloring agent in each layer can be increased, and the film thickness of the entire film may be further changed compared with the case of a single-layer film. thin. In addition, the degree of freedom of material design can be improved.

<<Single layer film>>

The single-layer film can be achieved by adjusting the type or blending amount of the colorant, the blending amount of the ultraviolet absorber, and the like. ^{For example, the Ab 550} of the film before exposure and the film (cured film) after exposure can be adjusted by changing the content of the colorant. In addition, the standard deviation of the transmittance in the wavelength range of 400 nm to 700 nm of the film before exposure and the film after exposure (cured film) can be adjusted by changing the type of colorant.

^{In addition, the ratio of Ab 365} /Ab ⁵⁵⁰ of the film before exposure can be adjusted by changing the composition of each principal component. For example, the ratio of ^{Ab 365} /Ab ⁵⁵⁰ can be adjusted by changing the type or content of the colorant, ultraviolet absorber, and photopolymerization initiator.

For example, by using any one of the following radiation-sensitive compositions (1) to (2), it is possible to produce a film (film before exposure) and a cured film (exposure) with the above-mentioned spectral characteristics. Film after light). Preferably, in any aspect of (1) to (2), relative to the total solid content of the radiation-sensitive composition, it contains 7% to 50% by mass (preferably 10% to 45% by mass, More preferably, it is a radiation-sensitive composition of a coloring agent of 12% by mass to 40% by mass). Regarding the composition other than the coloring agent of the radiation-sensitive composition, those described in the radiation-sensitive composition of the present invention can be used, and the preferred aspects are also the same.

(1) Use a coloring agent containing a black pigment, and contain 7 mass% to 50 mass% (preferably 10 mass% to 40 mass %, and more preferably 12 mass% relative to the total solid content of the radiation-sensitive composition ~30% by mass) of black pigments.

(2) Use a coloring agent that contains more than one black pigment and more than one color pigment, and contains 5.8% to 43.7% by mass (preferably 8.3% to 39.3% by mass relative to the total solid content of the radiation-sensitive composition Mass%, more preferably 10.0 mass% to 35.0 mass%) of the black pigment containing 1.5 mass% to 17.5% by mass (preferably 2.1 mass% to 15.7% by mass) relative to the total solid content of the radiation sensitive composition, More preferably, it is a color pigment of 2.5% by mass to 15.7% by mass).

The aspect of (1) is preferably a coloring agent containing 60% by mass or more of black pigment, and more preferably a coloring agent containing 80% by mass or more of black pigment. The black pigment is preferably carbon black and titanium black, more preferably titanium black.

The aspect of (2) is preferably a coloring agent containing 50% to 99% by mass of black pigments and 1% to 50% by mass of color pigments, more preferably 60% to 90% by mass of black A coloring agent for pigments and 10% to 40% by mass of color pigments. The black pigment is preferably carbon black and titanium black, more preferably titanium black. Color The material is preferably at least one pigment selected from the group consisting of red pigments, orange pigments and yellow pigments.

In addition, in the aspects (1) and (2), it is preferable that the content of the ultraviolet absorber be 0.01% by mass to 10% by mass relative to the total solid content of the radiation-sensitive composition, and more preferably 0.01% by mass to 5% by mass. By adjusting the content of UV absorber, the ratio of ^{Ab 365} /Ab ^{550 can also be adjusted.} When Ab ³⁶⁵ /Ab ^{550 is} too low, the ratio ^{of Ab 365} /Ab ⁵⁵⁰ can be increased by increasing the content of UV absorbers. In addition, when Ab ³⁶⁵ /Ab ^{550 is} too high, the ratio of ^{Ab 365} /Ab ⁵⁵⁰ can be reduced by reducing the content of UV absorbers. The quality ratio of the UV absorber and the coloring agent is preferably UV absorber/colorant=0.1 to 1.2, more preferably 0.1 to 1.0, further preferably 0.1 to 0.8, particularly preferably 0.1 to 0.7.

In addition, in the aspects (1) and (2), the ratio of ^{Ab 365} /Ab ^{550 can also be adjusted by adjusting the content of the photopolymerization initiator.} When Ab ³⁶⁵ /Ab ^{550 is} too low, the ratio ^{of Ab 365} /Ab ⁵⁵⁰ can be increased by increasing the content of the photopolymerization initiator. In addition, when Ab ³⁶⁵ /Ab ^{550 is} too high, the ratio of ^{Ab 365} /Ab ⁵⁵⁰ can be reduced by reducing the content of the photopolymerization initiator. The quality comparison between the photopolymerization initiator and the coloring agent is preferably that the photopolymerization initiator/colorant=0.1 to 1.0, more preferably 0.1 to 0.8, further preferably 0.1 to 0.6, particularly preferably 0.1 to 0.5.

In addition, in order to adjust the refractive index of light with a wavelength of 633 nm to 1.20 to 165, for example, the content of high refractive index particles may be less than 5% by mass (preferably 3% by mass) relative to the total solid content of the radiation-sensitive composition. Hereinafter, it is more preferable to manufacture a radiation-sensitive composition of 1% by mass or less).

The thickness of the single-layer film (cured film) is not particularly limited, but is preferably 0.2 μm~1.0μm, more preferably 0.3μm~0.7μm.

<<Multilayer film>>

When the film of the present invention is a combination of two or more films to satisfy the spectroscopic characteristics, for example, a first radiation-sensitive composition using a colorant A containing a black pigment, and a first radiation-sensitive composition containing a black pigment or a color pigment can be used. The second radiation-sensitive composition of coloring agent B is produced. Regarding the composition other than the coloring agent of each radiation-sensitive composition, those described in the radiation-sensitive composition of the present invention can be used, and the preferred aspects are also the same.

Furthermore, when the colorant B is a colorant containing a black pigment, it is preferable that the black pigment contained in the colorant A and the black pigment contained in the colorant B are of different types. For example, it is preferable that the colorant A uses titanium black as the black pigment and the colorant B uses carbon black as the black pigment.

The thickness of each layer of the multilayer film (cured film) is not particularly limited, but is preferably 0.2 μm to 1.0 μm, more preferably 0.2 μm to 0.7 μm. The thickness of each film may be the same or different.

The first radiation-sensitive composition preferably contains 8% to 50% by mass of black pigment relative to the total solid content of the radiation-sensitive composition, more preferably contains 12% to 45% by mass, and more preferably contains 15% to 40% by mass. The colorant A may further contain color pigments. The following (a1) and (a2) can be cited as preferred aspects of the first radiation-sensitive composition.

(a1) It is preferable to include 8% by mass to 50% by mass of titanium black relative to the total solid content of the radiation-sensitive composition, more preferably to include 12% to 45% by mass, and more preferably to include 15% by mass to 40% by mass.

(a2) It is preferable to include 8% by mass to 50% by mass of carbon black with respect to the total solid content of the radiation-sensitive composition, more preferably to include 12% to 45% by mass, and still more preferably to include 15% by mass to 40% by mass.

The second radiation-sensitive composition preferably contains a black pigment or a color pigment of 2% to 26% by mass relative to the total solid content of the radiation-sensitive composition, and more preferably contains 3% to 24% by mass, and further Preferably, it contains 4% by mass to 22% by mass. For the second radiation-sensitive composition, the following (b1) to (b3) can be cited as preferred aspects.

(b1) It is preferable to include 2% to 26% by mass of color pigments relative to the total solid content of the radiation-sensitive composition, more preferably to include 3% to 24% by mass, and still more preferably to include 4% to 22% by mass.

(b2) It is preferable to contain 3% by mass to 23% by mass of titanium black relative to the total solid content of the radiation-sensitive composition, more preferably 4% to 21% by mass, and still more preferably 5 mass% to 19% by mass.

(b3) It is preferable to contain 3% to 23% by mass of carbon black relative to the total solid content of the radiation-sensitive composition, more preferably to include 4% to 21% by mass, and still more preferably to include 5% to 19% by mass. The cured film of the present invention can be used for color filters. When the cured film of the present invention is used for a color filter, the colored pixels of the color filter can be used in combination with the cured film of the present invention. According to this aspect, it is easy to obtain an image with clearer colors.

For example, when the cured film of the present invention is used for a color filter, a structure in which the colored pixels of the color filter and the cured film of the present invention are adjacent to each other can be cited. this invention The cured film of is connected to the colored pixels in the thickness direction, and a laminate can be realized by the cured film and the colored pixels of the present invention. As shown in FIG. 1, the laminated body can have colored pixels 10 on the incident light A side of light compared to the cured film 11 of the present invention. As shown in FIG. The incident light A side has the cured film 11 of the present invention. In this way, by laminating the cured film of the present invention and colored pixels and using them, it is expected that the effect of uniformly reducing transmitted light can be expected.

In addition, the cured film of the present invention and the colored pixels are juxtaposed in a direction perpendicular to the thickness, and the two may be in contact with each other. That is, as shown in FIG. 3, the cured film 11 of the present invention and the colored pixels 10 are juxtaposed on the same plane and the two can be connected. According to this aspect, it can be expected that the resolution of the image sensor (Charge Coupled Device (CCD), Complementary Metal Oxide Semiconductor (CMOS), etc.) will increase in resolution. This brings about the effect of suppressing the decrease in sensitivity (increasing the sensitivity).

Furthermore, 12 in the figure is a support body.

Color filters can be preferably used for solid-state imaging devices such as charge coupled devices (CCD) or complementary metal oxide semiconductors (CMOS), and are particularly suitable for high-resolution CCDs or CMOSs with more than 1 million pixels. The color filter can be used, for example, by being disposed between the light receiving portion of each pixel constituting a CCD or CMOS and a micro lens for condensing light. In addition, color filters can be preferably used for organic electroluminescence (EL) devices. The organic EL element is preferably a white organic EL element. The organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, it is described in Japanese Patent Laid-Open No. 2003-45676, Mikami Akira Editor-in-Chief, "The Forefront of Organic EL Technology Development-High Brightness, High Precision, Long Life, Proprietary Technology Collection -", Technical Information Association, pp. 326-328, 2008, etc. As the tandem structure of the organic EL element, for example, a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmissivity on one surface of the substrate. The lower electrode preferably contains a material having sufficient reflectivity in the wavelength region of visible light. The organic EL layer preferably includes a plurality of light-emitting layers and has a layered structure (tandem structure) in which these light-emitting layers are laminated. The organic EL layer may include, for example, a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer as a plurality of light-emitting layers. Furthermore, it is preferable to have a plurality of light-emitting layers, and a plurality of light-emitting auxiliary layers for making these light-emitting layers emit light. The organic EL layer can be, for example, a laminated structure in which a light-emitting layer and a light-emitting auxiliary layer are alternately laminated. The organic EL element having the organic EL layer of the structure can emit white light. In this case, the spectrum of the white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430nm~485nm), green region (530nm~580nm) and yellow region (580nm~620nm) By. More preferably, in addition to these luminescence peaks, the one having the largest luminescence peak in the red region (650 nm to 700 nm) is more preferable. By combining an organic EL element that emits white light (white organic EL element) and the color filter of the present invention, excellent spectroscopic performance in terms of color reproducibility can be obtained, and a clearer image or image can be displayed .

The film thickness of the colored pattern (colored pixels) of the color filter is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less. The lower limit can be set to 0.1 μm or more, or 0.2 μm or more, for example.

In addition, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be set to 0.1 μm or more, or 0.2 μm or more, for example.

The cured film of this invention can also be used for a light-shielding film. The light-shielding film can be formed on various components in the image display device or the sensor module (for example, infrared light cut filter, the outer periphery of the solid-state imaging device, the outer periphery of the wafer-level lens, the back of the solid-state imaging device, etc.), etc. use. In addition, a light-shielding film may be formed on at least a part of the surface of the infrared light-cut filter to form an infrared light-cut filter with a light-shield film. The thickness of the light-shielding film is not particularly limited, but is preferably 0.2 μm to 25 μm, more preferably 1.0 μm to 10 μm. The thickness is an average thickness, and is a value obtained by measuring the thickness of any five or more points of the light-shielding film and arithmetically averaging these.

In addition, the hardened film of the present invention can be used in portable devices such as personal computers, tablets, mobile phones, smart phones, digital cameras, etc.; Office Automation devices such as printers, copiers, scanners, etc.; Industrial equipment such as surveillance cameras, barcode readers, Automated Teller Machines (ATM), high speed cameras, and personal authentication using facial image authentication; Automotive camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, catheters, etc.; body sensors, biosensors, military reconnaissance cameras, three-dimensional Map cameras, meteorological and ocean observation cameras, terrestrial resource exploration cameras, astronomy and exploration cameras for deep space targets in the universe, and other cosmic equipment.

<Pattern Formation Method>

Next, the pattern forming method of the present invention will be described.

The pattern forming method of the present invention can be manufactured through the following steps: a step of forming a radiation-sensitive composition layer on a support using the radiation-sensitive composition of the present invention, a step of exposing the composition layer in a pattern, and The step of developing and removing the unexposed part to form a pattern. Furthermore, if necessary, a step of baking the radiation-sensitive composition layer (pre-baking step) and a step of baking the developed pattern (post-baking step) can also be provided. Hereinafter, each step will be described in detail.

<<Steps to Form Radiation Sensitive Composition Layer>>

In the step of forming the radiation-sensitive composition layer, the radiation-sensitive composition of the present invention is used to form the radiation-sensitive composition layer on the support.

Examples of the support include transparent substrates such as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyimide, and polyimide. It is also possible to form thin film transistors for driving organic EL devices on these transparent substrates.

In addition, a solid-state imaging element substrate provided with a solid-state imaging element (light receiving element) such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS) on the substrate can be used.

As a method of applying the radiation-sensitive composition of the present invention to a support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used.

The radiation-sensitive composition layer formed on the support is preferably heated (pre-baked). Heating is preferably performed below 120°C, more preferably 50°C~120 ℃, more preferably 80℃~110℃, particularly preferably 90℃~105℃. By heating at 120° C. or lower, when an organic EL element is used as a light-emitting light source of an image display device or when a photoelectric conversion film of an image sensor is composed of an organic material, these characteristics can be maintained more effectively.

The heating time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, and still more preferably 80 seconds to 220 seconds. Heating can be carried out by heating plates, ovens, etc.

<<<Exposure Steps>>>

Next, the radiation-sensitive composition layer formed on the support is exposed in a pattern (exposure step). For example, by using an exposure device such as a stepper to expose the radiation-sensitive composition layer formed on the support through a mask having a predetermined mask pattern, pattern exposure can be performed. Thereby, the exposed part can be hardened.

As the radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays (especially i-rays) can be preferably used. The irradiation amount (exposure amount) is, for example, preferably 30 mJ/cm ² to 1500 mJ/cm ² , more preferably 50 mJ/cm ² to 1000 mJ/cm ² , and most preferably 50 mJ/cm ² to 500 mJ/cm ² . From the viewpoint of achieving both low-energy manufacturing and manufacturing stability, the range is preferred.

The oxygen concentration during exposure can be appropriately selected. For example, exposure can be carried out in a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, and substantially no oxygen), or when the oxygen concentration exceeds 21% by volume. Exposure is performed in a vol% high-oxygen environment (for example, 22 vol%, 30 vol%, 50 vol%). Further, illumination may be appropriately set exposure energy, typically ^{1000W / m 2 ~ 100000W / m} 2 ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) selected from the range. The oxygen concentration and the exposure illuminance can be combined with appropriate conditions. For example, an oxygen concentration of 10% by ^{volume and an illuminance of 10,000 W/m 2} , an oxygen concentration of 25% by volume and an illuminance of 25,000 W/m ² can be set.

<<<Development Step>>>

Next, the unexposed part is developed and removed to form a pattern. The development and removal of the unexposed part can be performed using a developer. Thereby, the radiation-sensitive composition layer of the unexposed part in the exposure step is eluted into the developing solution, and only the light-hardened part remains.

As the developer, an organic alkaline developer that does not damage the solid-state imaging element or circuit of the substrate or the like is desirable.

The temperature of the developer is preferably 20°C to 30°C, for example. The developing time is preferably 20 seconds to 180 seconds.

The alkaline agent used in the developer includes, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, hydrogen Tetrabutylammonium oxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0 ]-7-Undecene and other organic basic compounds. The developer can preferably use an alkaline aqueous solution prepared by diluting these alkaline agents with pure water. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass.

In addition, inorganic bases can also be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, etc. are preferred.

In addition, surfactants can also be used in the developer. As an example of a surfactant, the said surfactant is mentioned, Preferably it is a nonionic surfactant.

Furthermore, in the case of using a developer containing such an alkaline aqueous solution, it is generally preferable to wash (rinse) with pure water after development.

It is preferable to perform a heat treatment (post-baking) after the development and drying.

Post-baking is a heat treatment after development to promote hardening, and the heating temperature is preferably 100°C to 240°C, for example. In addition, in the case of using organic electroluminescence (organic EL) elements as the light source of the image display device or in the case of using organic materials to form the photoelectric conversion film of the image sensor, the temperature is preferably 50°C to 120°C (More preferably, 80°C to 100°C, and more preferably 80°C to 90°C) heat treatment (post-baking).

A heating mechanism such as a heating plate, a convection oven (hot air circulation type dryer), a high-frequency heater, etc. can be used to perform post-baking treatment on the developed film in a continuous or batch manner so as to meet the above-mentioned conditions.

<Solid-state imaging device>

The solid-state imaging element of the present invention includes the cured film (color filter, light-shielding film, etc.) of the present invention. The structure of the solid-state imaging element of the present invention is not particularly limited as long as it includes the cured film of the present invention and functions as a solid-state imaging element. For example, the following structures can be cited.

The solid-state imaging element has the following structure: a support body has a plurality of photodiodes (photodiodes) that constitute the light-receiving area of the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) The transmission electrode has a light-shielding film on the photodiode and the transmission electrode that only the light-receiving part of the photodiode is open, and the light-shielding film has a light-shielding film covering the entire surface of the light-shielding film and the light-receiving part of the photodiode The device protective film containing silicon nitride and the like formed by the method has a color filter on the device protective film. Furthermore, it can also be a configuration with a light-condensing mechanism (such as a micro lens, etc.. The same below) on the device protective film and under the color filter (on the side close to the support), or a light-collecting mechanism on the color filter The composition of the organization, etc. In addition, the color filter may have a structure in which the cured film forming the pixels of each color is embedded in a space partitioned into, for example, a lattice shape by a partition wall. In this case, the partition wall preferably has a low refractive index with respect to each color pixel. As an example of an imaging device having such a structure, the devices described in Japanese Patent Laid-Open No. 2012-227478 and Japanese Patent Laid-Open No. 2014-179577 can be cited.

<Image display device>

The cured film (color filter, light-shielding film, etc.) of the present invention can be used in image display devices such as liquid crystal display devices or organic electroluminescence display devices. The definition of display devices or the details of each display device are described in, for example, "Electronic Display Devices (by Sasaki Akio, Industrial Research Council (Stock), issued in 1990)", "Display Devices (by Ibuki Junsho, Industrial Books ( Shares), issued in 1989)” and so on. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Industrial Research Council (Stock), Issued in 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

The color filter of the present invention can also be used in a color thin film transistor (TFT) type liquid crystal display device. Regarding the color TFT type liquid crystal display device, for example, it is described in "Color TFT Liquid Crystal Display (Kyoritsu Co., Ltd.)" Edition (shares), issued in 1996". Furthermore, the present invention can also be applied to liquid crystal displays with enlarged viewing angles such as in-plane switching (IPS) and other lateral electric field driving methods, multi-domain vertical alignment (Multi-domain Vertical Alignment, MVA) and other pixel division methods, etc. Device, or Super-Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching ( fringe field switching, FFS), and reflective optically compensated bend (Reflective Optically Compensated Bend, R-OCB), etc.

In addition, the color filter of the present invention can also be used in a bright and high-definition color filter array (COA) method. In the liquid crystal display device of the COA system, in addition to the above-mentioned general required characteristics for the color filter, the required characteristics for the interlayer insulating film, that is, low dielectric constant and resistance to peeling liquid, are sometimes required. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA-type liquid crystal display device with high resolution and excellent long-term durability. Furthermore, in order to meet the required characteristics of low dielectric constant, a resin coating film may also be provided on the color filter layer.

These image display methods are described in, for example, "EL, Plasma Display Panel (PDP), Liquid Crystal Display (LCD) Display-The latest trends in technology and market-(Toray Research Center) (Toray Research Center) Research and Research Department, issued in 2001)" page 43 and so on.

In addition to the color filter of the present invention, the liquid crystal display device of the present invention also includes various components such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials. The Market of Chemicals (Shima Kentaro, CMC Co., Ltd., issued in 1994)" and "2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2) (Biao Ryoshi, Fuji Camry General Research (shares), issued in 2003)".

The backlight is recorded in "SID (Society for Information Display) meeting Digest" 1380 (2005) (A. Konno et al.), or "Monthly Display" in 2005 In the December issue, pages 18-24 (Yoshihiro Shima), pages 25-30 (Yagi Takaaki), etc. of the document.

[Example]

Hereinafter, the present invention will be described in more detail with examples, and the present invention is not limited to the following examples as long as it does not exceed the gist. Furthermore, as long as there is no special explanation in advance, "%" and "parts" are the quality standards.

(Determination of weight average molecular weight)

The weight average molecular weight was measured by gel permeation chromatography using the following conditions.

Column type: TSKgel Super AWM-H (manufactured by TOSOH (stock), 6.0mm inner diameter (Inner Diameter, ID) × 15.0cm)

Developing solvent: 10mmol/L lithium bromide N-methylpyrrolidone (N-Methylpyrrolidinone, NMP) solution

Column temperature: 25℃

Flow rate (sample injection volume): 0.6mL/min

Device name: HLC-8220 (manufactured by TOSOH (Stock))

Calibration curve base resin: polystyrene resin

<Preparation of dispersion>

(Dispersion 1)

Using a blender (EUROSTAR manufactured by IKA), the ingredients shown in the following composition 1 were mixed for 15 minutes to obtain a dispersed mixture.

<<Composition 1>>

‧Titanium black (13M-T (powder) manufactured by Mitsubishi Materials): 24 copies

‧30% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of dispersant (resin) 1: 25 parts

‧Propylene glycol monomethyl ether acetate: 25 parts

‧Butyl acetate: 26 parts

Dispersant 1: The following structure (weight average molecular weight = 35000, acid value = 85mgKOH/g)

[化28]

Using a bead mill NPM manufactured by Shinmaru Enterprises, a circulating piping, and an input tank, the obtained dispersion mixture was subjected to dispersion treatment under the following conditions to obtain a dispersion liquid 1.

<<Dispersion Conditions>>

‧Bead size: 0.05mm in diameter

‧Bead filling rate: 60% by volume

‧Circumference speed of mill: 10m/sec

‧Amount of mixed liquid for dispersion treatment: 5000g

‧Circulation flow (pump supply): 30kg/hour

‧Processing liquid temperature: 25℃~30℃

‧Cooling water: tap water

‧Processing time: 30 times

(Dispersion 2)

Using a blender (EUROSTAR manufactured by IKA), the ingredients shown in the following composition 2 were mixed for 15 minutes to obtain a dispersed mixture. The obtained dispersion mixture was subjected to the dispersion treatment under the same conditions as the dispersion conditions of the dispersion liquid 1, and the dispersion liquid 2 was obtained.

<<Composition 2>>

‧Carbon black (Carbon Black MA-100R (manufactured by Mitsubishi Chemical Industry Co., Ltd.)): 19 copies

‧45% by mass PGMEA solution of dispersant (resin) 2: 18 parts

‧PGMEA: 63 copies

Dispersant 2: The following structure

(Dispersion 3)

In the dispersion liquid 1, a dispersant (resin) 3 (the following structure, weight average molecular weight=20,000) was used instead of the dispersant (resin) 1, and the dispersion liquid 3 was obtained by the same method as the dispersion liquid 1 except that.

(Dispersion 4)

By the bead mill (the diameter of the zirconia beads is 0.3mm), 9.6 parts of CI Pigment Red 254, 4.3 parts of CI Pigment Yellow 139, 6.8 parts of dispersant (resin) (Disperbyk (Disperbyk) )-161, manufactured by BYK Chemie) and 79.3 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") mixed and dispersed for 3 hours to prepare a dispersion. After that, a high-pressure dispersion machine NANO-3000-10 (manufactured by Japan BEE Co., Ltd.) with a pressure reducing mechanism was used to perform dispersion treatment at a flow rate of 500 g/min under a pressure of ^{2000 kg/cm 3.} This dispersion process was repeated 10 times, and dispersion liquid 4 was obtained.

(Dispersion 5)

By the bead mill (the diameter of the zirconia beads is 0.3mm), it contains 12.3 parts of CI Pigment Orange 71, 1.1 parts of pigment derivatives (the following structure), 5.0 parts of dispersant (resin) 4, and 81.6 Part of the mixture of PGMEA was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure dispersion machine NANO-3000-10 (manufactured by Japan BEE Co., Ltd.) with a pressure reducing mechanism was used to perform dispersion treatment at a flow rate of 500 g/min under a pressure of ^{2000 kg/cm 3.} This dispersion process was repeated 10 times, and dispersion liquid 5 was obtained.

Pigment derivatives: the following structure

[化31]

Dispersant (resin) 4: the following structure (weight average molecular weight = 24000)

<Preparation of Radiation Sensitive Composition>

After mixing and stirring the materials shown in the following table at the ratio (mass%) shown in Table 1 below, they were filtered using a nylon filter with a pore size of 0.45 μm (manufactured by Pall, Japan, DFA4201NXEY). Thus, a radiation-sensitive composition is prepared.

<Evaluation method>

(Limiting)

The radiation-sensitive composition obtained was coated on a silicon wafer by a spin coating method so that the film thickness after coating became 0.5 μm, and then heated on a hot plate at 100°C for 2 minutes. Obtain a composition layer. Then, use the i-ray stepper to expose the device FPA-3000i5+ (manufactured by Canon) was set, and the obtained composition layer was exposed through a mask having an island pattern of 1.1 μm×1.1 μm. Then, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used to develop the exposed composition layer for 60 seconds at 23°C. Afterwards, the rinsing is performed by rotating spray, and then the pattern is obtained by washing with pure water.

Using a scanning electron microscope (Scanning Electron Microscope, SEM) (trade name: S-7800H, manufactured by Hitachi, Ltd.), the shape of the obtained pattern was observed from the silicon wafer at 30000 times, and the following The benchmark to evaluate the lithography.

A: the line width of the pattern becomes the exposure amount is 1.1μm or less and the range of ² 2500mJ / cm ² or more 1000mJ / cm. The amount of residue is less than 1% of the total area of the substrate, and there is no problem with pattern adhesion and pattern shape.

B: The exposure amount at which the line width of the pattern becomes 1.1 μm is 200 mJ/cm ² or more and less than 1000 mJ/cm ² . The amount of residue is less than 1% of the total area of the substrate, and there is no problem with pattern adhesion and pattern shape.

C: The line width of the pattern becomes 1.1 μm and the exposure amount is less than 200 mJ/cm ² . The amount of residue is less than 1% of the total area of the substrate, and there is no problem with pattern adhesion and pattern shape.

D: Pattern adhesion after lithography is poor.

E: an exposure amount becomes the pattern width is 1.1μm ² or less and 2500mJ / cm ² or more 1000mJ / cm. The amount of residue is more than 1% of the total area of the substrate.

F: Unevenness is observed on the pattern after lithography.

<Evaluation of stability over time>

Each radiation-sensitive composition was coated on the silicon wafer so that the film thickness after coating became 0.5 μm, and then heated on a hot plate at 100° C. for 2 minutes. Expose the substrate with an exposure amount of 1000 mJ/cm ^2. Furthermore, it heated at 200 degreeC for 8 minutes on a hotplate, and produced the cured film. After leaving the obtained cured film at 40°C under white light for 4 months, the absorbance (OD1) at a wavelength of 550 nm was measured using a spectrometer "UV-3600 (trade name)" manufactured by Shimadzu Corporation. . For each cured film before standing, the absorbance (OD0) was measured in the same manner as each cured film after standing. The ratio of the absorbance before and after the static storage was calculated according to the following equation.

Rate of change (%) = (Absorbance at 550nm after standing OD0/Absorbance at 550nm before standing OD1)×100

The stability over time was evaluated based on the following evaluation criteria.

A: The rate of change is less than 5%

B: The rate of change is more than 5% and less than 10%

C: The rate of change is more than 10%

(Coatability)

Each radiation-sensitive composition was coated on a wafer to form a coating film with a thickness of 0.5 μm. After spin-drying at 200 rpm for 60 seconds, the wafer was rotated at 1500 rpm for 15 seconds. The mixed solution of ether acetate/propylene glycol monomethyl ether = 1/1 (mass ratio) was used to implement Edge bead remove (EBR) cleaning (end surface cleaning), and the coating was evaluated according to the following criteria cloth Sex.

A: There is no problem with the shape of the coating film at the edge.

B: A part of the shape of the coating film at the edge is disordered.

C: A part of the coating film at the edge portion is not removed but remains.

[Table 1]

[Table 2]

As shown in the table, the example has excellent lithography properties. Furthermore, the coatability is also good. In addition, the composition of the example was applied to 200 wafers using CLEAN TRACK ACT8 manufactured by Tokyo Electronics, and then the coater cup was immersed in cyclohexanone for 24 hours As a result, it can be confirmed that the attached dirt can be removed well and the device maintainability is good.

On the other hand, the comparative example has poor lithography. Furthermore, coatability is also poor. In addition, the composition of the comparative example was applied to 200 wafers, and then the coater cup was immersed in cyclohexanone for 24 hours. As a result, a part of adhered dirt remained. Therefore, compared with the embodiment, the maintainability of the device is poor.

The materials shown in the table are as follows.

(Add resin afterwards)

B-1: The following structure (weight average molecular weight = 14000, acid value = 77mgKOH/g)

B-2: The following structure (weight average molecular weight=11000, acid value=69mgKOH/g, ethylenically unsaturated bond equivalent=1.4mmol/g)

B-3: The following structure (weight average molecular weight=12000, acid value=37mgKOH/g, ethylenically unsaturated bond equivalent=1.1mmol/g)

[化33]

(Polymerizable compound)

M-1~M-3: Compounds of the following structures

M-4: Aronix M-510 manufactured by Toagosei

(Photopolymerization initiator)

C-1~C-4: Compounds of the following structures

(Ultraviolet absorber)

D-1: The following structure

(Polymerization inhibitor)

E-1: p-methoxyphenol

(Surfactant)

F-1: The following mixture (Mw=14000)

(Organic solvents)

G-1: Cyclohexanone

<Production of Film>

(Example 1 to Example 14, Comparative Example 1 to Comparative Example 4)

The radiation-sensitive composition shown in the following table was coated on the silicon wafer so that the film thickness after coating became 0.5 μm, and then heated on a hot plate at 100° C. for 2 minutes. Expose the substrate with an exposure amount of 1000 mJ/cm ^2. Furthermore, it heated at 200 degreeC for 8 minutes on a hotplate, and produced the cured film.

(Example 15, Example 16)

The radiation-sensitive composition of the first layer shown in the following table was coated on the silicon wafer so that the film thickness after coating became 0.25 μm, and then heated on a hot plate at 100° C. for 2 minutes. Expose the substrate with an exposure amount of 1000 mJ/cm ^2. Furthermore, it heated at 200 degreeC for 8 minutes on a hotplate, and produced the film. Next, the second layer of radiation-sensitive composition shown in the following table was coated on the silicon wafer so that the film thickness after coating became 0.25 μm, and then heated on a hot plate at 100°C for 2 minute. Expose the substrate with an exposure amount of 1000 mJ/cm ^2. Furthermore, it heated at 200 degreeC for 8 minutes on a hotplate, and produced the cured film.

(Measurement of refractive index)

An ellipsometer VUV-VASE (manufactured by J.A. Woollam Japan) was used to measure the refractive index of the cured film. The measurement temperature was set to room temperature (25°C), and the measurement wavelength was set to 633 nm.

(Evaluation of Spectroscopic Performance)

The spectrometer UV3600 manufactured by Shimadzu Corporation was used to measure the spectral transmittance and absorbance of the film (film before exposure) and the cured film (film after exposure). The measurement temperature was set to room temperature (25°C).

The standard deviation is evaluated based on the following criteria.

A: The standard deviation of the transmittance in the wavelength range of 400nm to 700nm is 3% or less

B: The standard deviation of the transmittance in the wavelength range of 400nm to 700nm exceeds 3% and is 5% or less

C: The standard deviation of the transmittance in the wavelength range of 400nm to 700nm exceeds 5% and is 10% or less

D: The standard deviation of the transmittance in the wavelength range of 400nm to 700nm exceeds 10%

The spectroscopic evaluation is based on the following criteria.

A: The absorbance at a wavelength of 550 nm of the cured film is 0.1 to 0.8, the ratio of the absorbance at a wavelength of 350 nm to 550 nm of the film before exposure is 1.7 to 3.5, and the standard deviation of the cured film is evaluated as A.

B: The absorbance at a wavelength of 550 nm of the cured film is 0.1 to 0.8, the ratio of the absorbance at a wavelength of 350 nm to 550 nm of the film before exposure is 1.7 to 3.5, and the standard deviation of the cured film is evaluated as B.

C: The absorbance at a wavelength of 550 nm of the cured film is 0.1 to 0.8, the ratio of the absorbance at a wavelength of 350 nm to 550 nm of the film before exposure is 1.7 to 3.5, and the standard deviation of the cured film is evaluated as C.

D: The absorbance at a wavelength of 550 nm of the cured film is 0.1 to 0.8, and the ratio of the absorbance at a wavelength of 350 nm to 550 nm of the film before exposure deviates from the range of 1.7 to 3.5.

E: The absorbance of the cured film at a wavelength of 550 nm deviates from the range of 0.1 to 0.8.

[table 3]

As shown in the table, the spectral characteristics of the examples are excellent. It can be preferably used as a gray pixel. On the other hand, the spectral characteristics of the comparative example are inferior compared with the examples.

In addition, the cured films of the examples and comparative examples were incorporated into the solid-state imaging element. As a result, compared with the solid-state imaging element incorporating the cured film of the comparative example, the solid-state imaging element incorporating the cured film of the example has Good image recognition.

Regarding the composition 14 used in Example 14, the organic solvent G-1 (cyclohexanone) was changed to 3-ethoxypropionate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the same as in Example 14 except that The evaluation was performed, and as a result, the same evaluation result as in Example 14 was obtained. Regarding the composition 14 used in Example 14, the organic solvent G-1 (cyclohexanone) was changed to a mixture of cyclohexanone and 3-ethoxypropionate at a mass ratio of 50:50. The solvent was evaluated in the same manner as in Example 14 except for this, and as a result, the same evaluation result as in Example 14 was obtained. Based on this result, it is predicted that good results can be obtained even in the case of other organic solvents or a combination of organic solvents.

Regarding the composition 2 used in Example 2, coating was applied so that the film thickness after coating became 0.1 μm, 0.2 μm, 0.4 μm, 0.5 μm, 0.7 μm, 0.9 μm, and 1.1 μm. The cured film was produced in the same manner, and evaluated in the same manner as in Example 2. The evaluation results are shown below.

According to the above results, even if the film thickness is changed, it has excellent lithography, stability over time, and coatability.

Claims (23)

A radiation-sensitive composition comprising: a resin, a colorant, a polymerizable compound, and a photopolymerization initiator; the mass ratio of the resin to the colorant, that is, the resin/colorant is 1.0 to 6.0, and the polymerization The sexual compound includes a polymerizable compound having at least one group selected from a hydroxyl group and an acid group, and the content of high refractive index particles having a refractive index of 1.8 or more relative to the total solid content of the radiation-sensitive composition is 0.5% by mass the following. The radiation-sensitive composition according to the first item of the scope of patent application, wherein the mass ratio of the resin to the colorant, that is, the resin/colorant is 1.5 to 4.0. The radiation-sensitive composition according to item 1 or item 2 of the scope of patent application, wherein the colorant contains a pigment and contains 7 to 50% by mass relative to the total solid content of the radiation-sensitive composition pigment. The radiation-sensitive composition according to item 3 of the scope of patent application, wherein the pigment includes a black pigment. The radiation-sensitive composition according to item 1 or item 2 of the scope of patent application, wherein the resin includes an alkali-soluble resin, and the alkali-soluble resin has an ethylenically unsaturated bond equivalent of 1.0 mmol/g or less. The radiation-sensitive composition described in item 1 or item 2 of the scope of patent application further includes an ultraviolet absorber. The radiation-sensitive composition according to item 1 or item 2 of the scope of patent application, wherein the photopolymerization initiator comprises an α-aminoketone compound. The radiation-sensitive composition described in item 1 or item 2 of the scope of patent application, wherein when the radiation-sensitive composition is used to form a film with a thickness of 0.5 μm, the absorbance of the film with respect to light with a wavelength of 550 nm Ab ⁵⁵⁰ is 0.1 to 0.8, the standard deviation of the transmittance in the wavelength range of 400 nm to 700 nm of the film is 10% or less, and the absorbance Ab ^{365 of} the film with respect to light with a wavelength of 365 nm is relative to that of the film ^{The ratio of Ab 550} , which is Ab ³⁶⁵ /Ab ^550, of the absorbance of light with a wavelength of 550 nm is 1.7 to 3.7. In the radiation-sensitive composition described in item 1 or item 2 of the scope of patent application, when the radiation-sensitive composition is used to form a film with a thickness of 0.5 μm, the refractive index of light with a wavelength of 633 nm is 1.20 to 1.65. The radiation-sensitive composition described in item 1 or item 2 of the scope of patent application, wherein when the radiation-sensitive composition is used to form a film with a thickness of 0.5 μm, the refractive index of light with a wavelength of 633 nm is 1.20~ 1.58. The radiation-sensitive composition according to item 1 or item 2 of the scope of patent application, wherein the colorant contains a black pigment, and the content of the black pigment is relative to the total solid content of the radiation-sensitive composition It is 10% by mass to 40% by mass. The radiation-sensitive composition according to item 1 or item 2 of the scope of the patent application, wherein the colorant contains more than one black pigment and more than one color pigment, and is relative to the total amount of the radiation-sensitive composition Solid content, the content of the black pigment is 10% to 35% by mass, and the content of the color pigment is 2.5 Mass%~14% by mass. The radiation-sensitive composition according to item 1 or item 2 of the scope of patent application, wherein the colorant includes an orange pigment. The radiation-sensitive composition according to item 1 or item 2 of the scope of patent application, wherein the high refractive index particles are selected from titanium dioxide, zirconium oxide, tin oxide, indium oxide, zinc oxide, indium tin oxide, and At least one of particles of silicon, aluminum oxide, magnesium oxide, vanadium oxide, and niobium oxide. A film using the radiation-sensitive composition as described in any one of items 1 to 9 of the scope of patent application. The film described in item 15 of the scope of patent application, wherein the refractive index of the film relative to light with a wavelength of 633 nm is 1.20 to 1.65. The film as described in item 15 of the scope of patent application, wherein the refractive index of the film with respect to light with a wavelength of 633 nm is 1.20 to 1.58. A multilayer film comprising two or more layers of the film according to any one of items 15 to 17. The film described in item 15 of the scope of patent application, wherein the absorbance Ab ⁵⁵⁰ of the film with respect to light with a wavelength of 550 nm is 0.1 to 0.8, and the standard deviation of the transmittance in the range of the film with a wavelength of 400 nm to 700 nm is 10% or less, The ratio of the absorbance Ab ^{365 of the film with respect to light having a wavelength of 365 nm to the absorbance Ab 550} of the film with respect to the light having a wavelength of 550 nm, that is, Ab ³⁶⁵ /Ab ⁵⁵⁰ is 1.7 to 3.7. The film as described in item 19 of the scope of patent application, wherein the film is relative to The refractive index of light with a wavelength of 633 nm is 1.20 to 1.65. A color filter having a cured film using the radiation-sensitive composition described in any one of items 1 to 14 in the scope of the patent application. A light-shielding film having a cured film using the radiation-sensitive composition described in any one of items 1 to 14 in the scope of the patent application. A solid-state imaging element having a cured film using the radiation-sensitive composition described in any one of items 1 to 14 in the scope of the patent application.

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