JP2017125953A - Radiation-sensitive composition, film, color filter, light blocking film and solid state image senor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition, a film, a color filter, a light blocking film and a solid state image sensor having excellent lithographic performance.SOLUTION: A radiation-sensitive composition comprises a resin, a colorant, a polymerizable compound, and a photopolymerization initiator, where the mass ratio between the resin and the colorant, (resin/colorant), is 1.0-6.0, and the polymerizable compound comprises a polymerizable compound having an acid radical.SELECTED DRAWING: None

Description

  The present invention relates to a radiation sensitive composition. More specifically, the present invention relates to a radiation-sensitive composition that can be used for forming a film (such as a gray film) that can appropriately block light in the visible region. The present invention also 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, pixel miniaturization is progressing with the increase in the number of pixels. On the other hand, the opening becomes small, which causes a decrease in sensitivity. Therefore, attempts have been made to increase the dynamic range of the image sensor by employing gray pixels (a film that appropriately blocks light in the visible region).

  As radiation-sensitive compositions for forming a cured film that appropriately shields light in the visible region, for example, those described in Patent Documents 1 and 2 are known.

JP 2002-71911 A JP 2014-111734 A

  When manufacturing a cured film using a radiation sensitive composition, it may carry out by raising exposure illumination intensity in order to shorten the exposure time at the time of pattern formation. However, as the exposure illuminance is increased, it tends to be difficult to obtain a desired pattern. For this reason, in recent years, further improvement in the lithographic properties of the radiation-sensitive composition has been demanded. In particular, in a radiation-sensitive composition used for production of a cured film or the like that appropriately transmits light in the visible region, it is often difficult to adjust sensitivity, and further improvement in lithography is required.

  Accordingly, an object of the present invention is to provide a radiation-sensitive composition, a film, a color filter, a light-shielding film, and a solid-state imaging device that are excellent in lithographic properties.

As a result of detailed studies, the inventors have found that the above object can be achieved by adopting the following configuration, and have completed the present invention. That is, the present invention is as follows.
<1> A resin, a colorant, a polymerizable compound, and a photopolymerization initiator,
The resin / colorant, which is the mass ratio of resin to colorant, is 1.0 to 6.0,
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 according to <1>, wherein the resin / colorant, which is a mass ratio of the resin and the colorant, 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 to 50% by mass of the pigment with respect to the total solid content of the radiation-sensitive composition.
<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 contains an alkali-soluble resin, and the ethylenically unsaturated bond equivalent of the alkali-soluble resin is 1.0 mmol / g or less. .
<6> The radiation-sensitive composition according to any one of <1> to <5>, further comprising 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> When a 0.5 μm-thick film is formed using the radiation-sensitive composition,
Absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm of the film is 0.1 to 0.8,
The standard deviation of the transmittance in the wavelength range of 400 to 700 nm of the film is 10% or less,
Ab ³⁶⁵ / Ab ⁵⁵⁰ , which is a ratio of absorbance Ab ³⁶⁵ with respect to light with a wavelength of 365 nm of the film and absorbance Ab ⁵⁵⁰ with respect to light with a wavelength of 550 nm of the film, is 1.7 to 3.7, <1> to <7> The radiation sensitive composition in any one of.
<9> When a film having a thickness of 0.5 μm is formed using the radiation-sensitive composition, the refractive index of light having a wavelength of 633 nm is 1.20 to 1.65, <1> to <8> The radiation sensitive composition in any one.
<10> A film using the radiation-sensitive composition according to any one of <1> to <9>.
<11> Absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm of the film is 0.1 to 0.8,
The standard deviation of the transmittance in the wavelength range of 400 to 700 nm of the film is 10% or less,
A film having Ab ³⁶⁵ / Ab ⁵⁵⁰ of 1.7 to 3.7, which is a ratio of absorbance Ab ³⁶⁵ with respect to light having a wavelength of 365 nm and absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm.
<12> The film according to <10> or <11>, wherein the film has a refractive index of 1.20 to 1.65 with respect to light having a wavelength of 633 nm.
<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 device having a cured film using the radiation-sensitive composition according to any one of <1> to <9>.

According to the present invention, it has become possible to provide a radiation-sensitive composition, a film, a color filter, a light-shielding film, and a solid-state imaging device that are excellent in lithographic properties.
In addition, the film of the present invention having the above-described spectral characteristics has good lithographic properties and does not exhibit excessive absorption at a specific wavelength, in other words, a good gray film having small wavelength dependency of light absorption. For example, when used as a gray pixel of a solid-state imaging device, good performance with no bias in transmittance can be realized.

It is a figure which shows one Embodiment of the color filter using the cured film of this invention. It is a figure which shows one Embodiment of the color filter using the cured film of this invention. It is a figure which shows one Embodiment of the color filter using the cured film of this invention.

Hereinafter, the contents of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the group (atomic group) having a substituent together with the group (atomic group) having no substituent. is there. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, light means actinic rays or radiation. “Actinic light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
In this specification, “exposure” means not only exposure using a mercury lamp emission line spectrum, far ultraviolet rays typified by an excimer laser, X-rays, EUV light, etc. Drawing using particle beams is also included in the exposure.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ") Allyl" represents both and / or allyl and methallyl, and "(meth) acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value measured by gel permeation chromatography (GPC).

<Radiation sensitive composition>
The radiation-sensitive composition of the present invention contains a resin, a colorant, a polymerizable compound, and a photopolymerization initiator, and the resin / colorant, which is a mass ratio of the resin and the colorant, is 1. The polymerizable compound includes a polymerizable compound having at least one group selected from a hydroxyl group and an acid group. The resin / colorant means the mass ratio of resin to colorant (resin mass / colorant mass). When the radiation sensitive composition contains two or more types of resins, the mass of the resin is the sum of the two or more types of resins. Moreover, when a radiation sensitive composition contains 2 or more types of colorants, the mass of a colorant is the sum of 2 or more types of colorants.

  According to this invention, it can be set as the radiation sensitive composition excellent in lithography property by setting it as the structure mentioned above. That is, coloring in the composition by using a polymerizable compound having a resin / coloring agent mass ratio of 1.0 to 6.0 and having at least one group selected from a hydroxyl group and an acid group. The sensitivity can be adjusted moderately while improving the dispersibility of the agent, and excellent lithographic properties can be obtained.

In addition, when the resin / colorant mass ratio is 1.0 to 6.0 and the polymerizable compound having an acid group is included, the cleaning property with respect to the cleaning liquid is good and the maintenance property of the coating apparatus is excellent. . That is, the radiation-sensitive composition of the present invention has a high resin content and contains a polymerizable compound having an acid group, so that it has good solubility in a cleaning liquid and adheres to, for example, a nozzle of a coating apparatus. Dirt and the like can be easily cleaned with a cleaning solution such as a solvent.
Moreover, since the resin / colorant mass ratio is 1.0 to 6.0 and the above polymerizable compound is included, the wettability to the coated substrate is improved, so that the coating property can be improved. . In particular, the effect is remarkable at the edge portion of the coating, and the coating uniformity at the edge portion of the film is excellent.

  The radiation-sensitive composition of the present invention preferably uses a colorant containing a black pigment. According to this aspect, a radiation-sensitive composition suitable for production of a cured film that appropriately transmits light in the visible region can be obtained.

  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. When producing a cured film that appropriately transmits light in the visible region, the i-line transmittance of the film is high, so that the sensitivity tends to be high when exposed to high illumination. In contrast, by using an alkali-soluble resin having 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 exposure illuminance can be increased. , A desired pattern can be easily formed. For this reason, it is easy to obtain excellent lithographic properties. In particular, when a colorant containing a black pigment is used, excellent lithographic properties are easily obtained.

  The radiation-sensitive composition of the present invention preferably uses an α-aminoketone compound as a photopolymerization initiator. When producing a cured film that appropriately transmits light in the visible region, the i-line transmittance of the film is high, so that the sensitivity tends to be high when exposed to high illumination. On the other hand, by using an α-aminoketone compound as a photopolymerization initiator, the sensitivity can be appropriately adjusted, and a desired pattern can be easily formed even if the exposure illuminance is increased. For this reason, it is easy to obtain excellent lithographic properties. In particular, when a colorant containing a black pigment is used, excellent lithographic properties are easily obtained.

When the radiation-sensitive composition of the present invention forms a film having a thickness of 0.5 μm using the radiation-sensitive composition, the absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm is 0.1 to 0.8. The standard deviation of the film in the wavelength range of 400 to 700 nm is 10% or less, and Ab is the ratio of the absorbance Ab ³⁶⁵ with respect to the light with a wavelength of 365 nm and the absorbance Ab ⁵⁵⁰ with respect to the light with a wavelength of 550 nm. It is preferable that ³⁶⁵ / Ab ⁵⁵⁰ is 1.7 to 3.7. Note that the above-described film is a film in a state before exposure. That is, the above-described spectral characteristics are spectral characteristics with respect to a film in a state before exposure.

By using the radiation-sensitive composition having the above-described properties, a cured film that appropriately transmits light in the visible region can be formed. That is, the film having the above characteristics has low transmittance in the wavelength range of 400 to 700 nm, does not have an excessive absorption peak at a specific wavelength in this wavelength range, and is flat in the entire region. Presents a transmission spectrum. For this reason, it can be set as the favorable gray film which does not show excessive absorption by the specific wavelength in a visible region by hardening said film | membrane by exposure etc. For example, when used as a gray pixel of a solid-state imaging device, it is possible to realize good performance with no bias in transmittance. For this reason, for example, a cured film obtained by curing a film obtained using the radiation-sensitive composition of the present invention has good image recognizability when used in combination with colored pixels of a color filter. It is easy to be done. Further, since the Ab ³⁶⁵ / Ab ⁵⁵⁰ of the film of the present invention is 1.7 to 3.7, the absorbance of light with a wavelength of 365 nm is relatively high. That is, this film is also a film having a low transmittance for light having a wavelength of 365 nm. For this reason, the i-line transmittance is moderately low, the handling during exposure is good, and the lithographic properties are excellent.

When the radiation-sensitive composition of the present invention forms a film having a thickness of 0.5 μm using the radiation-sensitive composition, the refractive index of light having a wavelength of 633 nm is 1.20 to 1.65. preferable. By using the radiation-sensitive composition having this characteristic, reflection of light at the film surface or at the interface with other layers can be suppressed. For this reason, for example, when a cured film obtained using the radiation-sensitive composition of the present invention is used in combination with colored pixels of a color filter, etc., the film surface and other layers (for example, colored pixels) It is easy to obtain good image recognizability or the like by suppressing the reflection of light at the interface.
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. The colorant may be a chromatic colorant or a black colorant. It is preferable to include at least a black colorant. The colorant may be a pigment or a dye. Pigments are preferred. By using the pigment, it is easy to produce a film having a small standard deviation of transmittance in the wavelength range of 400 to 700 nm. In particular, when a black pigment is used as the pigment, it is easy to produce a film having a standard deviation of transmittance within the above range of 10% or less.

(Pigment)
Examples of the pigment include various conventionally known pigments.
Examples of the chromatic organic pigment include the following. However, the present invention is not limited to these.
Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 72,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279
C. I. Pigment Green 7, 10, 36, 37, 58, 59
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80
Further, as the green pigment, a zinc halide phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, bromine atoms of 8 to 12 and chlorine atoms of 2 to 5 on average is used. Is also possible. Specific examples include the compounds described in WO2015 / 118720.
These organic pigments can be used alone or in various combinations in order to increase color purity.

  Various known black pigments can be used as the black pigment. Examples thereof include carbon black and the following black metal-containing inorganic pigments. As the black metal-containing inorganic pigment, a metal oxide or metal containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag Nitrogen can be mentioned. These may be used alone or as a mixture of two or more. Moreover, you may prepare so that it may have desired light-shielding property by using in combination with the inorganic pigment of another hue further to a black pigment. Examples of specific inorganic pigments that can be used in combination include, for example, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead , Zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, victoria green, bitumen blue (Prussian blue) ), Vanadium zirconium blue, chrome tin pink, pottery red, salmon pink and the like. In particular, these black pigments and other inorganic pigments having other hues are used not only independently but also in combination with a plurality of types of pigments for the purpose of expressing light-shielding properties in a wide wavelength range from ultraviolet to infrared. Is possible.

  The black pigment is preferably carbon black or tiran black, and titanium black is particularly preferred from the viewpoint of light-shielding properties in a wide wavelength range from ultraviolet to infrared. Titanium black is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. Although not particularly limited, examples of titanium oxynitride include WO2008 / 123097, JP2009-58946, JP2010-14848, JP2010-97210, and JP2011-2274670. Or a mixture of titanium oxynitride and titanium carbide described in JP 2010-95716 A can be used. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water repellent material as disclosed in JP-A-2007-302836. . Titanium black is a composite oxide such as Cu, Fe, Mn, V, Ni, etc., and one or more black pigments such as cobalt oxide, iron oxide, and carbon black for the purpose of adjusting dispersibility and colorability. You may contain in combination.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. JP-A-61-201610), and 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 (JP-A-61-201610). However, the present invention is not limited to these.

Although the specific surface area of titanium black is not particularly limited, BET (Brunauer, Emmett, Teller ) is preferably measured value is less than 5 m ² / g or more 150 meters ² / g by method, 20 m ² / g or more 120 m ² / More preferably, it is g or less.
Examples of titanium black commercial products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

  The black pigment preferably has an average primary particle size of 5 nm or more, and 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 even more preferably 100 nm or less. The average primary particle diameter of the black pigment is a value measured by the following method. A mixed liquid containing a black pigment is diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted liquid is measured using a dynamic light scattering method. This measurement shall be the average particle diameter obtained by using Microtrack (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd.

(dye)
Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, and U.S. Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-51115. The pigment | dye currently disclosed by 194828 gazette etc. can be used. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

(Preferable combination of colorants)
Preferred embodiments of the colorant include the following (1) to (3). By using the following colorant, when a film having a thickness of 0.5 μm is formed using the radiation-sensitive composition of the present invention, the absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm is 0.1 to 0. The standard deviation in the wavelength range of 400 to 700 nm of the film is 10% or less, and the ratio of the absorbance Ab ³⁶⁵ with respect to light having a wavelength of 365 nm and the absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm. , Ab ³⁶⁵ / Ab ⁵⁵⁰ can provide a radiation-sensitive composition suitable for production of a film or the like that satisfies the condition of 1.7 to 3.7.

(1) A colorant containing a black pigment is used, and the black pigment is 7 to 50% by mass (preferably 10 to 40% by mass, more preferably 12 to 30%) based on the total solid content of the radiation-sensitive composition. (Mass%).
(2) A colorant containing one or more black pigments and one or more chromatic pigments is used, and the black pigment is 5.8 to 43.7 based on the total solid content of the radiation-sensitive composition. 1% by mass (preferably 8.3 to 39.3% by mass, more preferably 10.0 to 35.0% by mass), and the chromatic pigment is added to the total solid content of the radiation-sensitive composition by 1. 5 to 17.5 mass% (preferably 2.1 to 15.7 mass%, more preferably 2.5 to 14.0 mass%) is contained.

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

  The aspect (2) is preferably a colorant containing 50 to 99% by mass of black pigment and 1 to 50% by mass of chromatic pigment, 60 to 90% by mass of black pigment, and 10 to 40 of chromatic color pigment. A colorant containing mass% is more preferred. The black pigment is preferably carbon black and titanium black, more preferably titanium black. The chromatic pigment is preferably at least one pigment selected from a red pigment, an orange pigment, and a yellow pigment.

As for content of a coloring agent, 7-50 mass% is preferable with respect to the total solid of a 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 colorant preferably has a pigment content of 80% by mass or more, and more preferably 90% by mass or more.
Moreover, 7-50 mass% is preferable with respect to the total solid of a radiation sensitive composition. The lower limit is preferably 10% by mass or more, and more preferably 12% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
Moreover, 7-50 mass% is preferable with respect to the total solid of a radiation sensitive composition. The lower limit is preferably 10% by mass or more, and more preferably 12% by mass or more. The upper limit is preferably 40% by mass or less, and 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 having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond, and 3 groups having an ethylenically unsaturated bond. A compound having at least one is more preferable. The upper limit of the group having an ethylenically unsaturated bond is, for example, preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include vinyl group, styryl group, (meth) allyl group, (meth) acryloyl group, (meth) acryloyloxy group and the like.

  The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred. 100-3000 are preferable and, as for the molecular weight of a polymeric compound, 250-1500 are more preferable. The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (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 if the solid content other than the colorant in the composition is large, it has excellent developability and excellent lithographic properties. can get. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferable.

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

  As the polymerizable compound having at least one group selected from a hydroxyl group and an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is non-aromatic. A polymerizable compound having an acid group by reacting with a carboxylic acid anhydride is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

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 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) acryloyloxy group. Represents an integer of 1 or more, and n2 represents an integer of 1 or more.)

Examples of the acid group represented by A include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable.
L represents a (n1 + n2) -valent group containing at least a carbon atom and a hydrogen atom. For example, —CH ₂ —, —O—, —S—, —C (═O) —, —COO—, —NR—, —CONR—, —OCO—, —SO—, —SO ₂ — and these Examples include groups formed by linking two or more. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. L is, -CH ₂ - at least comprises groups preferred. The number of carbon atoms constituting L is preferably 3 to 100, and more preferably 6 to 50.
n1 is preferably 1 or 2, and more preferably 1. n2 is preferably 1 to 6, and more preferably 2 to 5.

一般式（１１）中、Ｒ¹、Ｔ¹、及びＸ¹は、各々独立に、Ｒ¹、Ｔ¹、又はＸ¹として以下に示す基の何れかを表す。ｎは、０〜１４の整数を表す。

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 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 of 0 to 14.

In General Formula (12), Z ¹ and G ¹ each independently represent any of the groups shown below as Z ¹ or G ¹ . W ¹ is synonymous with the group represented by R ¹ or X ¹ in the general formula (11), and 3 or more of 6 W ¹ represent R ¹ , and one or more represents X ¹ . . p represents an integer of 0 to 14.

  Among the compounds represented by the general formula (11) or the general formula (12), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.

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 compounds described in paragraphs 0093 to 0096 of JP2009-221114A can also be used. This content is incorporated herein.

  The radiation-sensitive composition of the present invention may further contain a polymerizable compound having no hydroxyl group and no acid group (hereinafter also referred to as other polymerizable compound), and may contain other polymerizable compound. preferable. The other polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred. The molecular weight of the other polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500. The other polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound. Specific examples of these compounds include paragraph numbers [0095] to [0108] of JP-A-2009-288705, paragraph 0227 of JP-A-2013-29760, and paragraph number 0254 to JP-A-2008-292970. The compounds described in 0257 can be referred to, the contents of which are incorporated herein.

Other polymerizable compounds include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku ( Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, commercially available from Sartomer) SR454, SR499) are preferred. These oligomer types can also be used. KAYARAD RP-1040 and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. Moreover, the following compounds can also be used.

  As another polymerizable compound, a compound having a caprolactone structure is also a preferred embodiment. Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

  As the other polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups. A hexafunctional (meth) acrylate compound is more preferable.

Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups. Moreover, the following compounds can also be used.

Other polymerizable compounds include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Is also preferable.
Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like can be mentioned.

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 having no acid group) is the total solid content of the radiation-sensitive composition. On the other hand, 10-70 mass% is preferable. The lower limit is, for example, more preferably 15% by mass or more, and still more preferably 20% by mass or more. For example, the upper limit is more preferably 60% by mass or less, and still more preferably 50% by mass or less.
Moreover, it is preferable that it is 9-50 mass% with respect to the total solid of a radiation sensitive composition, and, as for content of the polymeric compound which has an acid group, it is more preferable that it is 12-40 mass%.
Moreover, it is preferable that it is 10-90 mass%, and, as for the ratio of the polymeric compound which has an acid group among all the polymeric compounds, it is more preferable that it is 20-80 mass%.
The polymerizable compound having an acid group may be only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.

（式（Ｔ１）中、ｎは２〜４の整数を表し、Ｌは２〜４価の連結基を表す。） << Curing accelerator >>
The radiation-sensitive composition of the present invention may contain a curing accelerator for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature. Examples of the curing accelerator include polyfunctional thiol compounds (polyfunctional mercapto compounds) having two or more mercapto groups in the molecule. The polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
General formula (T1)

(In the formula (T1), n represents an integer of 2 to 4, and L represents a 2 to 4 valent linking group.)

  In the general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiols can be used alone or in combination.

  Further, the curing accelerator may be a methylol compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963), an amine, a phosphonium salt, an amidine salt, an amide compound (for example, a special compound). Of the curing agent described in paragraph 0186 of JP 2013-411165 A, a base generator (for example, an ionic compound described in JP-A-2014-55114), and a cyanate compound (for example, JP-A-2012-150180). A compound described in paragraph 0071), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP2011-255304A), an onium salt compound (for example, paragraph 0216 in JP2015-34963A). Compounds exemplified as acid generators, JP2009- Compounds described in JP 80 949) can also be used.

  When this radiation sensitive composition contains a hardening accelerator, 0.3-8.9 mass% is preferable with respect to the total solid of a radiation sensitive composition, and content of a hardening accelerator is 0.8. 8 to 6.4% by mass is more preferable.

<< Compound having epoxy group >>
The radiation-sensitive composition of the present invention preferably contains a compound having an epoxy group.
As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. The number of epoxy groups is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 3 in one molecule.

As the compound having an epoxy group, a compound having a structure in which two benzene rings are connected by a hydrocarbon group can also be used. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.
Moreover, it is preferable that the epoxy group is connected via a connecting group. As the linking group, an alkylene group, an arylene group, -O-, -NR '-(R' is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. And a group containing at least one selected from a structure represented by —SO ₂ —, —CO—, —O— and —S—.

  The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / eq or less, more preferably from 100 to 400 g / eq, and from 100 to 300 g. More preferably, it is / eq.

The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). 200-100000 are preferable and, as for the weight average molecular weight of the compound which has an epoxy group, 500-50000 are more preferable.
Compounds having an epoxy group are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. The prepared compounds can also be used. These contents are incorporated herein.
Examples of commercially available products include “EHPE3150, manufactured by Daicel Corporation”, “EPICLON N660 (manufactured by DIC Corporation)”, and the like.

  When the radiation sensitive composition of this invention contains the compound which has an epoxy group, 0.1-40 mass% is preferable with respect to the total solid of a radiation sensitive composition as for content of the compound which has an epoxy group. . For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. The compound which has an epoxy group may be single 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<< Resin >>
The radiation sensitive composition of this invention contains resin. The resin is blended, for example, for the purpose of dispersing the colorant in the composition or the purpose of the binder. Note that a resin mainly used for dispersing a colorant is also referred to as a dispersant. However, such use of the resin is merely an example, and the resin can be used for other purposes.

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

  The ethylenically unsaturated bond equivalent of the resin is preferably 1.5 mmol / g or less, and more preferably 1.0 mmol / g or less. When 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 handling property is excellent. Therefore, good lithographic properties can be obtained. Particularly when a colorant containing a black pigment is used, good lithographic properties can be obtained.

In the radiation-sensitive composition of the present invention, the resin content is preferably 5 to 50% by mass, more preferably 15 to 35% by mass, based on the total solid content of the radiation-sensitive composition.
Moreover, the mass ratio (resin / colorant) of the resin and the colorant in the radiation-sensitive composition is 1.0 to 6.0, preferably 1.5 to 4.0, and 1.5 to 3 0.0 is more preferable. 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 spectrum of the present invention can be formed.
The composition of the present invention may contain only one type of resin or two or more types of resins. When two or more types are included, the total amount is preferably within the above range.

  In the present invention, the content of the resin having an ethylenically unsaturated bond equivalent of more than 1.0 mmol / g is preferably 70% by mass or less, and 40% by mass or less, based on the total mass of the resin. More preferably, it is more preferably 10% by mass or less, and even more preferably not.

(Alkali-soluble resin)
The radiation sensitive composition of this invention contains alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formability are improved. The alkali-soluble resin can also be used as a dispersant or a binder.

The molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5,000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000.
The alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.

The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.

  The ethylenically unsaturated bond equivalent of the alkali-soluble resin is preferably 1.5 mmol / g or less, and more preferably 1.0 mmol / g or less. When 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, a desired pattern can be easily formed and handled. Excellent in properties. Therefore, good lithographic properties can be obtained. In particular, when a black pigment is used, good lithographic properties can be obtained. In the present invention, the ethylenically unsaturated bond equivalent (double bond equivalent) is defined by the ratio of the number of moles of ethylenically unsaturated groups to the resin mass.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used. Examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 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 A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used. Moreover, as a commercial item, FF-426 (made by Fujikura Kasei Co., Ltd.) etc. can also be used, for example.

  The alkali-soluble resin is a monomer containing a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerizing the components.

一般式（ＥＤ２）中、Ｒは、水素原子または炭素数１〜３０の有機基を表す。一般式（ＥＤ２）の具体例としては、特開２０１０−１６８５３９号公報の記載を参酌できる。 In General Formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In 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), the description of JP 2010-168539 A can be referred to.

In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n -Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl , Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  As a specific example of the ether dimer, for example, paragraph 0317 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

式（Ｘ）において、Ｒ₁は、水素原子またはメチル基を表し、Ｒ₂は炭素数２〜１０のアルキレン基を表し、Ｒ₃は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。 The alkali-soluble resin may contain a structural unit derived from a compound represented by the 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 a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the formula (X), the number of carbon atoms of the alkylene group R ₂ is preferably 2-3. Although the carbon number of the alkyl group of R ₃ is 1 to 20, more preferably 1 to 10, alkyl group of R ₃ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

Specific examples of the alkali-soluble resin include the following. In the following structural formulas, Me represents a methyl group.

Regarding the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. It is incorporated herein.
Furthermore, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, No. 024934, paragraph numbers 0132 to 0143 described in paragraphs 0132 to 0143 and the binder resins used in the examples, JP 2011-242752A paragraphs 0092 to 0098 and the binder resins used in the examples, Paragraph No. of Kokai 2012-032770 It is also possible to use a binder resin according to 030-0072. These contents are incorporated herein.

  The acid value of the alkali-soluble resin is preferably 30 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 even more preferably 120 mgKOH / g or less.

  As for content of alkali-soluble resin, 0.1-20 mass% is preferable with respect to the total solid of a radiation sensitive composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more. As for an upper limit, 12 mass% or less is more preferable, and 10 mass% or less is still more preferable. The radiation sensitive composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

(Dispersant)
The radiation sensitive composition of this invention can contain a dispersing agent as resin. In particular, when a pigment is used, it is preferable to include a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). The dispersant preferably includes at least an acidic dispersant, and 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, pattern formation can be suitably performed by photolithography. In addition, it is preferable that content of an acidic dispersing agent is 99 mass% or more in the total mass of a dispersing agent, for example that a dispersing agent is only an acidic dispersing agent, and shall be 99.9 mass% or more. You can also.

Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
The basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups accounts for 50 mol% or more when the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amine.
The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.

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

  The resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity for the solvent by the graft chain, it is excellent in the dispersibility of the colorant and the dispersion stability after aging. In addition, since the composition has an affinity with a polymerizable compound or an alkali-soluble resin due to the presence of the graft chain, a residue can be hardly generated by alkali development. In the present invention, the graft copolymer means a resin having a graft chain. The graft chain means from the base 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 is preferably a resin having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. Moreover, 40-10000 are preferable, as for the number of atoms except the hydrogen atom per graft chain, 50-2000 are more preferable, and 60-500 are still more preferable.

Examples of the main chain structure of the graft copolymer include (meth) acrylic resin, polyester resin, polyurethane resin, polyurea resin, polyamide resin, and polyether resin. Of these, a (meth) acrylic resin is preferable.
The graft chain of the graft copolymer is a graft chain having poly (meth) acrylic, polyester, or polyether in order to improve the interaction between the graft site and the solvent and thereby increase dispersibility. Is preferable, and a graft chain having polyester or polyether is more preferable.
The graft copolymer preferably contains a repeating unit having a graft chain in a range of 2 to 90% by mass, and in a range of 5 to 30% by mass, based on the total mass of the graft copolymer. Is more preferable. When the content of the repeating unit having a graft chain is within this range, the dispersibility of the colorant is good.

In this invention, the copolymer containing the repeating unit represented by either of following formula (1)-formula (4) can also be used as a graft copolymer. This graft copolymer can be particularly preferably used as a dispersant for a black pigment.

In the 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 the formulas (1) to (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 each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each independently a hydrogen atom or a methyl group. More preferred is a methyl group.

In the formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following (Y-1) to (Y-21) linking groups. . In the structure shown below, A and B each represent a binding site with the left terminal group and the right terminal group in Formulas (1) to (4).

In the 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 an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Is mentioned. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Of these, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

In Formula (1)-Formula (4), n, m, p, and q are the integers of 1 to 500 each independently.
Moreover, in Formula (1) and Formula (2), j and k represent the integer of 2-8 each independently. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoints of dispersion stability and developability.

In Formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same as or different from each other.
In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, 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 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

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

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

Wherein (1A), X ^1, Y ^1, Z ¹ and n are as defined X ^1, Y ^1, Z ¹ and n in Formula (1), and preferred ranges are also the same.
Wherein (2A), X ^2, Y ^2, Z ² and m are as defined X ^2, Y ^2, Z ² and m in the formula (2), and preferred ranges are also the same.
Wherein (3A) or (3B), X ^3, Y ^3, Z ³ and p are as defined X ^3, Y ^3, Z ³ and p in formula (3), and preferred ranges are also the same.

  Moreover, it is also preferable that the graft copolymer mentioned above has a hydrophobic repeating unit other than the repeating unit represented by Formula (1)-(4) mentioned above. However, in the present invention, the hydrophobic repeating unit is a repeating unit having no acid group (for example, carboxyl group, sulfo group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.

log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented 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 aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

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

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1-6. An alkyl group (for example, a methyl group, an ethyl group, a propyl group, 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 a hydrogen atom.

  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, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), 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 thereof.
L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene 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, and more preferably an integer of 2 to 10.

Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, arylene group, substituted arylene group), heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, where R ³¹ is an aliphatic group, aromatic group or heterocyclic group), carbonyl Examples include a group (—CO—) or a combination thereof.

The aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring and other tricyclic hydrocarbon rings, tetracyclo [4 4.0.1, ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

  6-20 are preferable, as for the carbon atom number of an aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. 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. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is aliphatic. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms ( For example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ is represented. Here, L and Z are as defined above. R ⁴ , R ⁵ , and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

The monomer represented by the general formula (i) is a divalent linking group in which 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 an oxyalkylene structure. A compound in which X is an oxygen atom or imino group and Z is an aliphatic group, heterocyclic group or aromatic group is preferred. The monomer represented by the general formula (ii) is 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. preferable. 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 typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like. As examples of the compounds represented by formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are incorporated herein. .

  In the graft copolymer, the hydrophobic repeating unit is preferably contained in the range of 10 to 90% by mass, and in the range of 20 to 80% by mass, based on the total mass of the graft copolymer. Is more preferable. When the content is in the above range, sufficient pattern formation can be obtained.

  The graft copolymer described above preferably includes a repeating unit having a functional group capable of forming an interaction with a colorant or the like in addition to the repeating unit represented by the above formulas (1) to (4).

  Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable. By having a carboxyl group, the adsorptive power to a colorant such as a black pigment is good, and the dispersibility of the black pigment can be improved.

The graft copolymer may have one or more repeating units having an acid group.
The graft copolymer may or may not contain a repeating unit having an acid group, but when it is contained, the content of the repeating unit having an acid group is calculated in terms of mass to the total mass of the graft copolymer. On the other hand, 5-80 mass% is preferable, More preferably, it is 10-60 mass%.

Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, an amide group, and the like, and particularly preferable is adsorption to a colorant. It is a tertiary amino group having good strength and high dispersibility. The graft copolymer can have one or more of these basic groups.
The graft copolymer may or may not contain a repeating unit having a basic group. However, when it is contained, the content of the repeating unit having a basic group is the total amount of the graft copolymer in terms of mass. Preferably it is 0.01-50 mass% with respect to the mass, More preferably, it is 0.01-30 mass% from a viewpoint of developability inhibition suppression.

Examples of the coordinating group and reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, acid chloride and the like. Particularly preferred is an acetylacetoxy group that has a good adsorptive power to the colorant and a high dispersibility. The graft copolymer may have one or more of these groups.
The graft copolymer may or may not contain a repeating unit having a coordinating group or a repeating unit having a reactive functional group, but when it is contained, the content of these repeating units is In terms of mass, it is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass from the viewpoint of inhibiting developability inhibition, with respect to the total mass of the graft copolymer.

  When the graft copolymer has a functional group capable of forming an interaction with the colorant in addition to the graft chain, there is no particular limitation on how these functional groups are introduced. It is preferable to have one or more types of repeating units selected from repeating units derived from monomers represented by the following general formulas (iv) to (vi).

In general formula (iv) to general formula (vi), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom. An alkyl group having 1 to 6 numbers (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
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 Are each independently a hydrogen atom or a methyl group. In the general formula (iv), R ¹² and R ¹³ are each particularly preferably a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (v) represents a methine group or a nitrogen atom.

L < ₁ > in general formula (iv)-general formula (v) represents a single bond or a bivalent coupling group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR ³¹ ′ — Here, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.

L ₁ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene 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, and more preferably an integer of 2 to 10.

In general formula (iv) to general formula (vi), Z ₁ represents a functional group capable of forming an interaction with the colorant in addition to the graft chain, and is preferably a carboxyl group or a tertiary amino group. More preferably, it is a group.

In the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, , methyl group, ethyl group, propyl group, etc.), - represents a Z _1, or -L ₁ -Z _1. Wherein L ₁ and Z ₁ are the same meaning as L ₁ and Z ₁ in the above, it is the preferable examples. R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

The monomer represented by the general formula (iv) is a divalent linking group in which 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 an oxyalkylene structure. A compound in which X is an oxygen atom or imino group and Z is a carboxylic acid group is preferable. The monomer represented by the general formula (v) is 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. Is preferred. In the monomer represented by the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z is a carboxylic acid group. Is preferred.

Specific examples of the graft copolymer include the following. Moreover, resin of Unexamined-Japanese-Patent No. 2014-111734 of the paragraphs 0121-0130 is mentioned, The content shall be integrated in this-application specification.

  In addition, as the resin (dispersant), an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain can also be used. The oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less, and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain. A resin having at least one basic nitrogen atom is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

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

The dispersant is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid). Ester), 110 (copolymer containing an acid group), 111 (phosphate dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”, “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), manufactured by EFKA” “EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate) , 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate) , 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) manufactured by Kyoeisha Chemical Co., Ltd. ”,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether) manufactured by Enomoto Kasei Co., Ltd. Ester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin heavy) manufactured by Kao Corporation Condensate) ”,“ homogenol L-18 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative) ”manufactured by Nippon Lubrizol Co., Ltd., 22000 (azo) Pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ", manufactured by Nikko Chemical “Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)”, Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. Nosiloxane polymer KP341, “W001: cationic surfactant” manufactured by Yusho Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonyl Nonionic surfactants such as phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as “W004, W005, W017”, “EFKA-46, manufactured by Morishita Sangyo Co., Ltd.” EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ”, manufactured by San Nopco Co., Ltd. , Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100, etc., "ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77 manufactured by ADEKA Corporation , P84, F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Chemical Co., Ltd., and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
In addition, resin demonstrated with the said dispersing agent can also be used for uses other than a dispersing agent. For example, it can be used as a binder.

<< 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 a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer. The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a 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. For example, (bis) acylphosphine oxide or its esters, acetophenone compounds, α-aminoketone compounds, benzophenone compounds, benzoin ether compounds , Ketal derivative compounds, thioxanthone compounds, oxime ester compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds And onium salt compounds such as metallocene compounds, organic boron salt compounds, and disulfone compounds. From the viewpoint of sensitivity, oxime ester compounds, acylphosphine oxide compounds, acetophenone compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and thiol compounds are preferable, and α-aminoketone compounds are more preferable. When a black pigment is used as the colorant, excellent lithographic properties can be easily obtained by using an α-aminoketone compound as a photopolymerization initiator.

Examples of the α-aminoketone compound include compounds represented by the following formula (AK-1).

In the formula, Ar represents a phenyl group substituted with —SR ¹³ or —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 having 2 to 9 carbon atoms.
The alkyl group represented by R ^1D and R ^2D may be linear, branched or 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 the substituent, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen ^{atom, -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 the} like. 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. In particular, one of R ^1D and R ^2D is preferably an unsubstituted alkyl group, and the other is preferably an alkyl group substituted with an aryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As for carbon number of the alkyl group which R ^{< Y1>} and R ^<Y2> represent, 1-20 are preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
6-20 are preferable, as for carbon number of the aryl group which ^RY1 and ^RY2 represent as a substituent, 6-15 are more preferable, and 6-10 are still more preferable. 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 single ring or a condensed ring. 3-30 are preferable, as for the number of the carbon atoms which comprise a heterocyclic group, 3-18 are more preferable, and 3-12 are more preferable. As for the number of the hetero atoms which comprise a heterocyclic group, 1-3 are preferable. 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 having 1 to 12 carbon atoms, an alkoxy group having 2 to 4 carbon atoms substituted with 1 to 4 carbon atoms, or 3 to 5 carbon atoms. Represents an alkenyl group. R ^3D and R ^4D may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group contains —O— or —N (R ¹² ) — in the alkylene chain. It may be. R ¹² represents an alkyl group having 1 to 4 carbon atoms.

R ^7E and R ^8E are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or an alkyl group having 3 to 5 carbon atoms. Represents an alkenyl group. 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 contains —O— or —N (R ¹² ) — in the alkylene chain. It may be. 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 and 2-methyl-1- [4- (hexyl) phenyl] -2. -Morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like.
Examples of commercially available products include IRGACURE907, IRGACURE369, and IRGACURE379 (trade names: all manufactured by BASF).

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3. -One, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2 -Ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products. Also, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles NC 930 (manufactured by ADEKA) can also be used.

  Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used. Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

  In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.

  In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP 2013-164471 A ( C-3). This content is incorporated herein.

  In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and ADEKA. Arcles NCI-831 (made by ADEKA) is mentioned.

  When the oxime compound is used in a low illuminance region, it is preferable to reduce the amount of the oxime compound added or use in combination with two or more photopolymerization initiators having different sensitivities. An oxime compound may be used in combination, or an oxime compound and another photopolymerization initiator compound may be used in combination. Examples also include oxime compounds and α-aminoketone compounds.

  Specific examples of the oxime compound are shown below, but the present invention is not limited thereto.

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

In the photopolymerization initiator, the molar extinction coefficient at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000 from the viewpoint of sensitivity, and 5,000. Particularly preferred is ~ 200,000. A known method can be used to measure the molar extinction coefficient of the compound. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is used and an ethyl acetate solvent is used. It is preferable to measure at a concentration of 0.01 g / L.
You may use a photoinitiator in combination of 2 or more type as needed.

As for content of a photoinitiator, 0.1-50 mass% is preferable with respect to the total solid of a radiation sensitive composition, More preferably, it is 0.5-30 mass%, More preferably, it is 1-20 mass. %. Within this range, better sensitivity and pattern formability can be obtained.
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. The upper limit may be 100% by mass, 99.5% by mass or less, or 99% by mass or less.
The mass ratio of the photopolymerization initiator to the colorant is preferably photopolymerization initiator / colorant = 0.1 to 1.0, more preferably 0.1 to 0.8, and 0.1 to 0. 6 is more preferable, and 0.1 to 0.5 is particularly preferable. So long as the mass ratio of the above photopolymerization initiator and a colorant, in a state before exposure to film, and the absorbance Ab ³⁶⁵ against wavelength 365nm of light film, the absorbance Ab ⁵⁵⁰ for light having a wavelength 550nm membrane It is easy to adjust Ab ³⁶⁵ / Ab ⁵⁵⁰ which is the ratio of 1.7 to 3.7. In particular, when a colorant containing a black pigment is used, Ab ³⁶⁵ / Ab ⁵⁵⁰ is adjusted to 1.7 to 3.7 by adjusting the mass ratio of the photopolymerization initiator and the colorant within the above range. It's easy to do.
The radiation-sensitive composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Solvent >>
The radiation-sensitive composition of the present invention preferably contains a solvent. The solvent is preferably an organic solvent. A solvent will not be restrict | limited especially if the solubility of each component and the applicability | paintability of a radiation sensitive composition are satisfied.

  Examples of the organic solvent include the following. Esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxy Alkyl acetates (for example, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (For example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc. ), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate) Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2- Methyl methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2- Ethyl oxobutanoate, etc. Examples include 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, etc., and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons Preferred examples include toluene and xylene.

  An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more organic solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid are particularly preferable. It is a mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

  In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

  The amount of the solvent is preferably such that the total solid content of the radiation-sensitive composition is 5 to 80% by 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 further preferably 40% by mass or less.

<< Pigment derivative >>
The radiation-sensitive composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl group. Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like. Moreover, as an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its quaternary ammonium base are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group. Specific examples of the pigment derivative include the following compounds. In addition, the description of paragraphs 0162 to 0183 in JP 2011-252065 A can be referred to, and the contents thereof are incorporated in this specification.

  1-30 mass% is preferable with respect to the total mass of a pigment, and, as for content of the pigment derivative in the radiation sensitive composition of this invention, 3-20 mass% is more preferable. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<< Surfactant >>
The radiation-sensitive composition of the present invention may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

  By including a fluorosurfactant in the radiation-sensitive composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the coating thickness uniformity and liquid-saving properties are improved. It can be improved further. That is, in the case of forming a film using a coating liquid to which a radiation-sensitive composition containing a fluorosurfactant is applied, the interfacial tension between the surface to be coated and the coating liquid decreases, and the surface to the surface to be coated is reduced. The wettability is improved and the coating property to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

上記の化合物の重量平均分子量は、好ましくは３，０００〜５０，０００であり、例えば、１４，０００である。
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開２０１０−１６４９６５号公報００５０〜００９０段落および０２８９〜０２９５段落に記載された化合物、例えばＤＩＣ社製のメガファックＲＳ−１０１、ＲＳ−１０２、ＲＳ−７１８Ｋ等が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, RS-72-K (above, DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
As the fluorosurfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain can be used as the fluorosurfactant. Specific examples thereof include compounds described in JP2010-164965A paragraphs 0050-0090 and 0289-0295, such as MegaFac RS-101, RS-102 and RS-718K manufactured by DIC.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Lubrizol Japan Ltd.) and the like. Further, the product of Wako Pure Chemical Industries, Ltd., may be used NCW-101, NCW-1001, NCW-1002.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

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

  Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

Only one type of surfactant may be used, or two or more types may be combined.
0.001-2.0 mass% is preferable with respect to the total solid of a radiation sensitive composition, and, as for content of surfactant, 0.005-1.0 mass% is more preferable.

<< Silane coupling agent >>
The radiation sensitive composition of the present invention can contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having at least two functional groups having different reactivity in one molecule. For example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-methacryloxy Propyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, and the like can be given. Regarding the details of the silane coupling agent, the description of paragraph numbers 0155 to 0158 of JP2013-254047A can be referred to, and the contents thereof are incorporated in the present specification.

  When the radiation sensitive composition of this invention contains a silane coupling agent, 0.5-30 mass% of content of a silane coupling agent is preferable with respect to the total solid of a radiation sensitive composition. The lower limit is preferably 0.7% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. The radiation-sensitive composition of the present invention may contain only one type of silane coupling agent or two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
The radiation sensitive composition of the present invention preferably contains a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned.

  In the radiation-sensitive composition of the present invention, when a polymerization inhibitor is used, subsequent development performance fluctuations when exposed to low illumination are suppressed, and pattern formability such as pattern line width, film thickness, spectral spectrum, etc. The exposure illuminance dependence related to can be more effectively suppressed. Furthermore, even when used for a film through which a certain amount of light is transmitted, unnecessary curing of unexposed portions and curing by light other than intended exposure may be suppressed.

When the radiation sensitive composition of this invention contains a polymerization inhibitor, 0.01-5 mass% of content of a polymerization inhibitor is preferable with respect to the total solid of a radiation sensitive composition. The radiation sensitive composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . As for the addition amount of a higher fatty acid derivative, 0.5-10 mass% is preferable with respect to the mass of a radiation sensitive composition.

<< UV absorber >>
The radiation sensitive composition of the present invention may contain an ultraviolet absorber. By containing an ultraviolet absorber, the transmittance of light having a wavelength of 365 nm can be adjusted, and a radiation-sensitive composition having excellent lithography properties can be obtained. The ultraviolet absorber is preferably a conjugated diene compound, more preferably a compound represented by the following general formula (1). When this conjugated diene compound is used, fluctuations in development performance after exposure, especially when low-illuminance exposure is performed, can be suppressed, and exposure illuminance dependence related to pattern formability such as pattern line width, film thickness, and spectral spectrum can be reduced. It can suppress more effectively.

R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² may be the same or different from each other. However, it does not represent a hydrogen atom at the same time.
R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is a group having Hammett's substituent constant σp value (hereinafter, simply referred to as “σp value”) of 0.20 or more and 1.0 or less. A group having a σp value of 0.30 or more and 0.8 or less is preferable. R ³ and R ⁴ are preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group, particularly an acyl group. A carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferred.
Regarding the general formula (1), the description of paragraph numbers 0148 to 0158 of JP 2010-049029 A can be referred to, and the contents thereof are incorporated in the present specification.

Specific examples of the compound represented by the general formula (1) include the following compounds. Moreover, it is mentioned in the compound of Unexamined-Japanese-Patent No. 2010-049029, paragraph number 0160-0162, and this content shall be integrated in this-application specification.

0.01-10 mass% is preferable with respect to the total solid of a radiation sensitive composition, and, as for content of a ultraviolet absorber, 0.01-5 mass% is more preferable.
The mass ratio between the ultraviolet absorber and the colorant is preferably ultraviolet absorber / colorant = 0.1 to 1.2, more preferably 0.1 to 1.0, and 0.1 to 0.8. Further preferred is 0.1 to 0.7. So long as the mass ratio of the above and the colorant UV absorber, in a state before exposure to film, and the absorbance Ab ³⁶⁵ with respect to light having a wavelength of 365nm in film, the absorbance Ab ⁵⁵⁰ for light having a wavelength 550nm membrane It is easy to adjust the ratio Ab ³⁶⁵ / Ab ⁵⁵⁰ to 1.7 to 3.7. In particular, when a colorant containing a black pigment is used, Ab ³⁶⁵ / Ab ⁵⁵⁰ is adjusted to 1.7 to 3.7 by adjusting the mass ratio of the ultraviolet absorber and the colorant within the above range. Cheap. Two or more kinds 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 radical generation efficiency of the photopolymerization initiator and increasing the photosensitive wavelength. As the sensitizer, those that are sensitized by an electron transfer mechanism or an energy transfer mechanism to the photopolymerization initiator used in combination are preferable. Preferable examples of the sensitizer include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395. The content of the sensitizer is preferably in the range of 0.1 to 30% by mass and more preferably in the range of 1 to 20% by mass with respect to the total solid content of the radiation-sensitive composition from the viewpoints of sensitivity and storage stability. The range of 2 to 15% by mass is more preferable.

<< Other additives >>
Various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the radiation-sensitive composition of the present invention as necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A No. 2004-295116, the contents of which are incorporated herein. As the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in JP 2011-90147 0042 paragraph), a thioether compound, or the like can be used. Examples of commercially available products include ADEKA Corporation's ADK STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330). Two or more antioxidants may be mixed and used. The radiation-sensitive composition of the present invention can contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A-2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the publication. .

  Depending on the raw materials used, the radiation-sensitive composition may contain metal elements, but from the viewpoint of suppressing the occurrence of defects, the content of Group 2 elements (calcium, magnesium, etc.) in the radiation-sensitive composition is It is preferable that it is 50 ppm or less, and it is preferable to control to 0.01-10 ppm. Further, the total amount of the inorganic metal salt in the radiation-sensitive composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.

  In the radiation-sensitive composition of the present invention, the content of the high refractive index particles is preferably less than 5% by mass with respect to the total solid content of the radiation-sensitive composition, and preferably 3% by mass or less. More preferred is 1% by mass or less. It can also be set as the aspect which does not contain a high refractive index folding particle substantially. It is preferable that the content of the high refractive index folding particles is substantially 0.5% by mass or less based on the total solid content of the radiation-sensitive composition. More preferably, it is less than mass%, and it is still more preferable not to contain. When the content of the high refractive index folded 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 highly refractive particles include materials having a refractive index of 1.8 or more. The lower limit can be 1.9 or more, and can be 2 or more. The upper limit can be 3 or less, can be 2.9 or less, and can be 2.8 or less. Examples of the high refractive index particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. And particles containing a metal oxide having the above element. Specific examples thereof include particles of titanium dioxide, zirconium oxide, tin oxide, indium oxide, zinc oxide, indium tin oxide (ITO), silica, aluminum oxide, magnesium oxide, vanadium oxide, and niobium oxide. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

<Method for preparing radiation-sensitive composition>
The radiation-sensitive composition of the present invention can be prepared by mixing the aforementioned components.
In preparing the radiation-sensitive composition, the components constituting the radiation-sensitive composition may be blended together, or may be blended sequentially after each component is dissolved and / or dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and / or dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions or dispersions at the time of use ( These may be mixed at the time of application) to prepare as a composition.
The radiation-sensitive composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. The filter using is mentioned. Among these materials, polypropylene (including high density polypropylene) is preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth radiation sensitive composition in a post process.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. can do.
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

<Film, cured film>
Next, the film | membrane and cured film of this invention are demonstrated. The film and cured film of the present invention are formed using the radiation-sensitive composition of the present invention. The film of the present invention is also a film having the following characteristics. The “film” in the present invention means a film before exposure. In addition, the “cured film” in the present invention means a film after performing a curing treatment such as exposure.
Absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm of the film is 0.1 to 0.8,
The standard deviation of the transmittance in the wavelength range of 400 to 700 nm of the film is 10% or less,
Ab ³⁶⁵ / Ab ⁵⁵⁰ , which is the ratio of the absorbance Ab ³⁶⁵ for light with a wavelength of 365 nm of the film and the absorbance Ab ⁵⁵⁰ for light with a wavelength of 550 nm of the film, is 1.7 to 3.7.

Ab ³⁶⁵ / Ab ⁵⁵⁰ of the film of the present invention (film before exposure) is 1.7 to 3.7, preferably 1.8 to 3.5, more preferably 1.8 to 3.4. .9 to 3.3 are more preferable. When Ab ³⁶⁵ / Ab ⁵⁵⁰ is within the above range, lithography performance with high adhesion and high resolution 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, 0.18 -0.50 is more preferable, and 0.20-0.30 is more preferable. 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 region can be moderately shielded. And if the said standard deviation is 10% or less, it will not have an excessive absorption peak in the specific wavelength of the above-mentioned wavelength range, and will exhibit the transmission spectrum of a flat state in the whole area | region. Therefore, by setting Ab ⁵⁵⁰ to 0.1 to 0.8 and the standard deviation to be 10% or less, a good gray film that does not exhibit excessive absorption at a specific wavelength can be obtained. When used as a gray pixel of a solid-state imaging device, it is possible to achieve good performance with no bias in transmittance.

  The refractive index of the film of the present invention (film before exposure) and the cured film of the present invention (film after exposure) is preferably 1.20 to 1.65 with respect to light having a wavelength of 633 nm. More preferably, it is -1.60, and 1.20-1.58 are still more preferable. If the refractive index of light having a wavelength of 633 nm is in the above range, reflection of light can be suppressed, so that reflection of light on the film surface can be suppressed. For this reason, when the cured film of the present invention is used in combination with colored pixels of a color filter, 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). It is easy to obtain good image recognizability or the like by suppressing the reflection of light or the like.

  The film | membrane and cured film which have the above-mentioned characteristic can be manufactured using the radiation sensitive composition of this invention.

  In addition, the film having the above characteristics and the cured film may have a single layer film (single layer film) having the above-mentioned spectral characteristics, and the above-mentioned spectral characteristics may be obtained by a multilayer film in which two or more layers are combined. It may be satisfied. When two or more films are combined to satisfy the above spectral characteristics, for example, the concentration of the colorant in each layer can be increased, and the film thickness of the entire film can be made thinner than in the case of a single layer film. Moreover, the freedom degree of material design can be raised.

<< Single layer film >>
The monolayer film can be achieved by adjusting the type and blending amount of the colorant and the blending amount of the ultraviolet absorber. For example, Ab ⁵⁵⁰ of the film before exposure and the film after exposure (cured film) can be adjusted by changing the content of the colorant. Moreover, the standard deviation of the transmittance | permeability in the wavelength range of 400-700 nm of the film | membrane before exposure and the film | membrane (cured film) after exposure can be adjusted by changing the kind of coloring agent.
Further, the ratio of Ab ³⁶⁵ / Ab ⁵⁵⁰ of the film before exposure can be adjusted by changing the composition of each main component. For example, the ratio of Ab ³⁶⁵ / Ab ⁵⁵⁰ can be adjusted by changing the type and content of the colorant, ultraviolet absorber, and photopolymerization initiator.

  For example, by using the radiation sensitive composition of any one of the following (1) to (2), a film having the above spectral characteristics (film before exposure) and a cured film (film after exposure) are manufactured. Can do. Preferably, in any one of the embodiments (1) to (2), the coloring agent is 7 to 50% by mass (preferably 10 to 45% by mass, more preferably, based on the total solid content of the radiation-sensitive composition. , 12 to 40% by mass). About compositions other than the coloring agent of a radiation sensitive composition, what was demonstrated by the photosensitive composition of this invention mentioned above can be used, and a preferable aspect is also the same.

(1) A colorant containing a black pigment is used, and the black pigment is 7 to 50% by mass (preferably 10 to 40% by mass, more preferably 12 to 30%) based on the total solid content of the radiation-sensitive composition. (Mass%).
(2) A colorant containing at least one black pigment and at least one chromatic pigment is used, and the black pigment is 5.8 to 43.7 based on the total solid content of the radiation-sensitive composition. 1% by mass (preferably 8.3 to 39.3% by mass, more preferably 10.0 to 35.0% by mass), and the chromatic pigment is 1. 5 to 17.5 mass% (preferably 2.1 to 15.7 mass%, more preferably 2.5 to 15.7 mass%) is contained.

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

  The aspect (2) is preferably a colorant containing 50 to 99% by mass of black pigment and 1 to 50% by mass of chromatic pigment, 60 to 90% by mass of black pigment, and 10 to 40 of chromatic color pigment. A colorant containing mass% is more preferred. The black pigment is preferably carbon black and titanium black, more preferably titanium black. The chromatic pigment is preferably at least one pigment selected from a red pigment, an orange pigment, and a yellow pigment.

In the above aspects (1) and (2), the content of the ultraviolet absorber is preferably 0.01 to 10% by mass with respect to the total solid content of the radiation-sensitive composition. More preferably, the content is 0.01 to 5% by mass. The ratio of Ab ³⁶⁵ / Ab ⁵⁵⁰ can also be adjusted by adjusting the content of the ultraviolet absorber. When Ab ³⁶⁵ / Ab ⁵⁵⁰ is too low, the ratio of Ab ³⁶⁵ / Ab ⁵⁵⁰ can be increased by increasing the content of the ultraviolet absorber. If Ab ³⁶⁵ / Ab ⁵⁵⁰ is too high, the ratio of Ab ³⁶⁵ / Ab ⁵⁵⁰ can be reduced by reducing the content of the ultraviolet absorber. The mass ratio of the UV absorber to the colorant is preferably UV absorber / colorant = 0.1 to 1.2, more preferably 0.1 to 1.0, and even more preferably 0.1 to 0.8. 0.1 to 0.7 is particularly preferable.

In the above 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 the case Ab ³⁶⁵ / Ab ⁵⁵⁰ is too high, by reducing the content of the photopolymerization initiator, it is possible to reduce the ratio of Ab ³⁶⁵ / Ab ^550. The mass ratio of the photopolymerization initiator to the colorant is preferably photopolymerization initiator / colorant = 0.1 to 1.0, more preferably 0.1 to 0.8, and 0.1 to 0.6. Further preferred is 0.1 to 0.5.

  In order to adjust the refractive index of light having a wavelength of 633 nm to 1.20 to 1.65, for example, the content of the high refractive index particles is 5% by mass with respect to the total solid content of the radiation-sensitive composition. It can be produced using a radiation-sensitive composition that is less than (preferably 3% by mass or less, more preferably 1% by mass or less).

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

<< Multilayer film >>
When the film of the present invention satisfies the above spectral characteristics by combining two or more films, for example, a first radiation-sensitive composition using a colorant A containing a black pigment and a black pigment or a chromatic color pigment It can manufacture using the 2nd radiation sensitive composition using the coloring agent B which contains. About compositions other than the colorant of each radiation sensitive composition, what was demonstrated by the photosensitive composition of this invention mentioned above can be used, and a preferable aspect is also the same.
In addition, when the colorant B is a colorant containing a black pigment, the black pigment included in the colorant A and the black pigment included in the colorant B are preferably different types. For example, the colorant A preferably uses titanium black as a black pigment, and the colorant B preferably uses carbon black as a black pigment.

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

The first radiation-sensitive composition preferably contains a black pigment in an amount of 8 to 50% by mass, more preferably 12 to 45% by mass, more preferably 15 to 40% by mass with respect to the total solid content of the radiation-sensitive composition. % Is more preferable. The colorant A may further contain a chromatic pigment. In the first radiation-sensitive composition, the following (a1) and (a2) are mentioned as preferred embodiments.
(A1) It is preferable to contain 8-50 mass% of titanium black with respect to the total solid of a radiation sensitive composition, it is more preferable to contain 12-45 mass%, and it is further more preferable to contain 15-40 mass%.
(A2) It is preferable to contain 8-50 mass% of carbon black with respect to the total solid of a radiation sensitive composition, it is more preferable to contain 12-45 mass%, and it is further more preferable to contain 15-40 mass%.

The second radiation-sensitive composition preferably contains a black pigment or a chromatic color pigment in an amount of 2 to 26% by mass, more preferably 3 to 24% by mass, based on the total solid content of the radiation-sensitive composition. It is more preferable to contain 4-22 mass%. In the second radiation-sensitive composition, the following (b1) to (b3) are mentioned as preferred embodiments.
(B1) The chromatic pigment is preferably contained in an amount of 2 to 26% by mass, more preferably 3 to 24% by mass, and still more preferably 4 to 22% by mass based on the total solid content of the radiation-sensitive composition. .
(B2) It is preferable to contain 3-23 mass% of titanium black with respect to the total solid of a radiation sensitive composition, It is more preferable to contain 4-21 mass%, It is further more preferable to contain 5-19 mass%.
(B3) It is preferable to contain 3-23 mass% of carbon black with respect to the total solid of a radiation sensitive composition, It is more preferable to contain 4-21 mass%, It is further more preferable to contain 5-19 mass%.

The cured film of the present invention can be used for a color filter. When using the cured film of this invention for a color filter, the coloring pixel of a color filter and the cured film of this invention can be used in combination. According to this aspect, it is easy to obtain an image having a clearer color.
For example, when using the cured film of this invention for a color filter, the structure where the colored pixel of the color filter and the cured film of this invention adjoined is mentioned. The cured film of the present invention may be in contact with the colored pixels in the thickness direction to form a laminate of the cured film of the present invention and the colored pixels. In the laminate, as shown in FIG. 1, the colored pixel 10 may be closer to the incident light A side of the light than the cured film 11 of the present invention, and the cured film of the present invention as shown in FIG. 11 may be provided on the incident light A side of the light from the colored pixel 10. Thus, by laminating and using the cured film of the present invention and the colored pixels, the effect of reducing transmitted light evenly can be expected.
In addition, the cured film of the present invention and the colored pixels may be in contact with each other in the direction perpendicular to the thickness. That is, as shown in FIG. 3, the cured film 11 of the present invention and the colored pixel 10 may be arranged on the same plane and may be in contact with each other. According to this aspect, it is possible to expect an effect of suppressing a reduction in sensitivity (sensitivity improvement) accompanying an increase in resolution accompanying an improvement in resolution of an image sensor (CCD, CMOS, etc.).
In the figure, 12 is a support.

  The color filter can be suitably used for a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), and is particularly suitable for a high-resolution CCD or CMOS that exceeds 1 million pixels. It is. The color filter can be used by being disposed, for example, between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for collecting light. The color filter can be preferably used for an organic electroluminescence (organic EL) element. As the organic EL element, a white organic EL element is preferable. The organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, “The Forefront of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. Examples of the tandem structure of the organic EL element include a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmittance on one surface of a substrate. The lower electrode is preferably made of a material having a sufficient reflectance in the visible light wavelength region. The organic EL layer preferably includes a plurality of light emitting layers and has a stacked structure (tandem structure) in which the plurality of light emitting layers are stacked. For example, the organic EL layer may include a red light emitting layer, a green light emitting layer, and a blue light emitting layer in the plurality of light emitting layers. And it is preferable that they have a some light emission auxiliary layer for light-emitting a light emitting layer together with a some light emitting layer. The organic EL layer can have, for example, a stacked structure in which light emitting layers and light emitting auxiliary layers are alternately stacked. An organic EL element having an organic EL layer having such a structure can emit white light. In that case, the spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable. By combining an organic EL element that emits white light (white organic EL element) and the color filter of the present invention, a spectrum excellent in color reproducibility can be obtained, and a clearer image or image can be displayed.

The film thickness of the colored pattern (colored pixel) in the color filter is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.
Further, 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, for example, 0.1 μm or more, and can also be 0.2 μm or more.

  The cured film of the present invention can also be used as a light shielding film. The light shielding film is formed and used on various members in an image display device or a sensor module (for example, an infrared light cut filter, an outer peripheral portion of a solid-state imaging device, an outer peripheral portion of a wafer level lens, a rear surface of a solid-state imaging device, etc.). it can. Moreover, it is good also as an infrared light cut filter with a light shielding film by forming a light shielding film in at least one part on the surface of an infrared light cut filter. Although the thickness in particular of a light shielding film is not restrict | limited, 0.2-25 micrometers is preferable and 1.0-10 micrometers is more preferable. The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of any five or more points of the light shielding film and arithmetically averaging them.

  In addition, the cured film of the present invention is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, or a digital camera; an OA (Office Automation) device such as a printer multifunction device or a scanner; a monitoring camera, a barcode reader, or an automatic cash deposit Industrial equipment such as payment machines (ATM), high-speed cameras, identity authentication using facial image authentication; in-vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters; biosensors, biotechnology It can be used in space equipment such as sensors, military reconnaissance cameras, stereoscopic map cameras, weather / ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets.

<Pattern formation method>
Next, the pattern forming method of the present invention will be described.
The pattern forming method of the present invention includes 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 an unexposed portion. And developing the pattern to form a pattern. Furthermore, you may provide the process (prebaking process) of baking a radiation sensitive composition layer, and the process (post-baking process) of baking the developed pattern as needed. Details of each step will be described below.

<< The process of forming a radiation sensitive composition layer >>
In the step of forming the radiation-sensitive composition layer, the radiation-sensitive composition layer is formed on the support using the radiation-sensitive composition of the present invention.

Examples of the support include transparent substrates such as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. A thin film transistor for driving the organic EL element may be formed on these transparent substrates.
In addition, a solid-state imaging device substrate in which a solid-state imaging device (light receiving device) such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) is provided on the substrate can be used.

  As a method for applying the radiation-sensitive composition of the present invention on the support, various methods such as slit coating, ink jet 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 (prebaked). The heating is preferably performed at 120 ° C. or less, more preferably 50 to 120 ° C., further preferably 80 to 110 ° C., and particularly preferably 90 to 105 ° C. By performing heating at 120 ° C. or lower, these characteristics are more effectively maintained when an organic EL element is used as the light source of the image display device or when the photoelectric conversion film of the image sensor is made of an organic material. can do.
The heating time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Heating can be performed with a hot plate, oven, or the like.

<<< Exposure process >>>
Next, the radiation sensitive composition layer formed on the support is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing a radiation-sensitive composition layer formed on a support using a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 30~1500mJ / cm ^2, more preferably 50~1000mJ / cm ^2, and most preferably 50 to 500 mJ / cm ^2. The above range is preferable from the viewpoint of achieving both low energy production and stable manufacturability.
The oxygen concentration at the time of exposure can be appropriately selected. For example, the exposure may be performed in a low oxygen atmosphere (for example, 15% by volume, 5% by volume, substantially oxygen-free) having an oxygen concentration of 19% by volume or less. The exposure may be performed in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, and 50% by volume) in which the oxygen concentration exceeds 21% by volume. Also, illuminance of the exposure energy is possible to appropriately set typically ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) selected from the range of Can do. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration 25% by volume can be, eg illuminance 25000W / m ^2.

<<< Development process >>>
Next, the unexposed portion is developed and removed to form a pattern. The development removal of the unexposed portion can be performed using a developer. Thereby, the radiation sensitive composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. The development time is preferably 20 to 180 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
Moreover, you may use an inorganic alkali for a developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
Further, a surfactant may be used for the developer. Examples of the surfactant include the above-described surfactants, and nonionic surfactants are preferable.
In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it is preferable to wash | clean (rinse) with a pure water after image development.

It is preferable to perform heat treatment (post-bake) after development and drying.
Post-baking is a heat treatment after development for promoting curing, and the heating temperature is preferably, for example, 100 to 240 ° C. Further, when an organic electroluminescence (organic EL) element is used as the light source of the image display device, or when the photoelectric conversion film of the image sensor is made of an organic material, 50 to 120 ° C. (more preferably 80 to 100 ° C.). More preferably, the heat treatment (post-bake) is preferably performed at 80 to 90 ° C.
The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so that the film after development is in the above condition. it can.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the above-described cured film (color filter, light shielding film, etc.) of the present invention. The configuration of the solid-state imaging device 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 device, and examples thereof include the following configurations.

  The support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.). A light-shielding film having an opening only in the light-receiving portion, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion, and a color filter on the device protective film It is the structure which has. Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protection layer and under the color filter (on the side close to the support), a structure having the light condensing means on the color filter, etc. It may be. In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the imaging apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.

<Image display device>
The cured film (color filter, light-shielding film, etc.) of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device. For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling liquid, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. Have been described.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Unless otherwise specified, “%” and “parts” are based on mass.

(Measurement of weight average molecular weight)
The weight average molecular weight was measured by gel permeation chromatography under the following conditions.
Column type: TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID (inner diameter) × 15.0 cm)
Developing solvent: 10 mmol / L Lithium bromide NMP (N-methylpyrrolidinone) solution Column temperature: 25 ° C.
Flow rate (sample injection amount): 0.6 mL / min
Device name: HLC-8220 (manufactured by Tosoh Corporation)
Calibration curve base resin: Polystyrene resin

<Preparation of dispersion>
(Dispersion 1)
The components shown in the following composition 1 were mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion mixture.
<< Composition 1 >>
Titanium black (Mitsubishi Materials 13M-T (powder)): 24 parts Dispersant (resin) 1 30% by weight propylene glycol monomethyl ether acetate (PGMEA) solution: 25 parts Propylene glycol monomethyl ether acetate: 25 parts・ Butyl acetate: 26 parts

Dispersant 1: Structure below (weight average molecular weight = 35000, acid value = 85 mg KOH / g

The dispersion mixture thus obtained was subjected to a dispersion treatment under the following conditions using a bead mill NPM manufactured by Shinmaru Enterprises Co., Ltd. and a circulating pipe and a charging tank, whereby a dispersion 1 was obtained.
<< dispersion condition >>
Bead diameter: 0.05mm diameter
Bead filling rate: 60% by volume
Mill peripheral speed: 10m / sec
Liquid mixture amount to be dispersed: 5000 g
Circulation flow rate (pump supply amount): 30 kg / hour
Treatment liquid temperature: 25 ° C to 30 ° C
Cooling water: Tap water Treatment time: 30 passes

(Dispersion 2)
The component shown in the following composition 2 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion mixture. The obtained dispersion mixture was subjected to a dispersion treatment under the same conditions as the dispersion conditions of Dispersion 1 to obtain Dispersion 2.

<< Composition 2 >>
Carbon black (carbon black MA-100R (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)): 19 parts 45% by mass PGMEA solution of dispersant (resin) 2: 18 parts PGMEA: 63 parts

Dispersant 2: The following structure

(Dispersion 3)
Dispersion 3 was prepared in the same manner as Dispersion 1 except that Dispersant (resin) 3 (the following structure, weight average molecular weight = 20000) was used instead of Dispersant (resin) 1 in Dispersion 1. Obtained.

(Dispersion 4)
C. I. Pigment Red 254, 9.6 parts, C.I. I. Pigment Yellow 139, 4.3 parts, dispersant (resin) (Disperbyk-161, manufactured by BYK Chemie) 6.8 parts, propylene glycol methyl ether acetate (hereinafter referred to as “PGMEA”) 79.3 parts. The mixed solution was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter) to prepare a dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a dispersion 4.

(Dispersion 5)
C. I. Pigment Orange 71 (12.3 parts), pigment derivative (structure below) 1.1 parts, dispersant (resin) 4 (5.0 parts), and PGMEA (81.6 parts) were mixed in a bead mill (zirconia beads 0 The pigment dispersion was prepared by mixing and dispersing for 3 hours. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a dispersion 5.

Pigment derivative:

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

<Preparation of radiation-sensitive composition>
The materials shown in the following table were mixed and stirred at the ratio (mass%) shown in Table 1 below, and then filtered through a nylon filter having a pore diameter of 0.45 μm (manufactured by Nippon Pole Co., Ltd., DFA4201NXEY) to give radiation sensitivity. A sex composition was prepared.

<Evaluation method>
(Lithography)
Each radiation sensitive composition obtained above was applied onto a silicon wafer by spin coating so that the film thickness after application was 0.5 μm, and then heated at 100 ° C. for 2 minutes on a hot plate. Thus, a composition layer was obtained. Next, the obtained composition layer was exposed through a mask having an island pattern of 1.1 μm × 1.1 μm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). Next, paddle development was performed on the composition layer after exposure using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water, and the pattern was obtained.
The shape of the obtained pattern was observed 30000 times from the top of the silicon wafer using a length measuring SEM (trade name: S-7800H, manufactured by Hitachi, Ltd.), and lithographic properties were evaluated according to the following criteria.
A: amount of exposure is line width 1.1μm pattern 1000 mJ / cm ² or more 2,500 mJ / cm ² or less. The amount of residue is less than 1% of the total area of the base, 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 base, and there is no problem with pattern adhesion and pattern shape.
C: The exposure amount at which the line width of the pattern becomes 1.1 μm is less than 200 mJ / cm ² . The amount of residue is less than 1% of the total area of the base, and there is no problem with pattern adhesion and pattern shape.
D: Poor pattern adhesion after lithography.
E: an exposure amount as the line width 1.1μm pattern 1000 mJ / cm ² or more 2,500 mJ / cm ² or less. The amount of residue is 1% or more of the total ground area.
F: Unevenness was observed on the pattern after lithography.

<Evaluation of stability over time>
Each radiation-sensitive composition was applied onto a silicon wafer so that the film thickness after application was 0.5 μm, and then heated at 100 ° C. for 2 minutes on a hot plate. The substrate was exposed at an exposure dose of 1000 mJ / cm ² . Furthermore, it heated at 200 degreeC for 8 minute (s) on the hotplate, and manufactured the cured film. The obtained cured film was allowed to stand at 40 ° C. under white light for 4 months, and then the absorbance (OD1) at a wavelength of 550 nm was measured with a spectroscope “UV-3600 (trade name)” manufactured by Shimadzu Corporation. did. For each cured film before standing, the absorbance (OD0) was measured in the same manner as that after standing. The ratio of absorbance before and after stationary storage was calculated according to the following formula.
Rate of change (%) = (absorbance OD0 at 550 nm after standing / absorbance OD1 at 550 nm before standing) × 100
The stability over time was evaluated according to the following evaluation criteria.
A: Change rate is less than 5% B: Change rate is 5% or more and less than 10% C: Change rate is 10% or more

(Applicability)
Each radiation-sensitive composition is applied to a wafer to form a coating film having a thickness of 0.5 μm, spin-dried at 200 rpm for 60 seconds, and then rotated at 1500 rpm for 15 seconds while propylene glycol monomethyl ether acetate / EBR cleaning (end surface cleaning) was performed with a mixed solution of propylene glycol monomethyl ether = 1/1 (mass ratio), and coating properties were evaluated according to the following criteria.
A: There is no problem in the shape of the coating film at the edge.
B: The coating film shape at the edge part is partially disturbed.
C: The coating film at the edge part remains without being partially removed.

As shown in the above table, the examples were excellent in lithographic properties. Furthermore, the applicability was also good. In addition, when CLEAN TRACK ACT8 manufactured by Tokyo Electron was used, the composition of the example was applied to 200 wafers, and then the coater cup was immersed in cyclohexanone for 24 hours. It was confirmed that the device has maintainability.
On the other hand, the comparative example was inferior in lithographic properties. Furthermore, the applicability was also poor. In addition, when the composition of the comparative example was applied to 200 wafers, and then the coater cup was immersed in cyclohexanone for 24 hours, a partially adhered stain remained. For this reason, apparatus maintainability was inferior compared with the Example.

  The materials shown in the above table are as follows.

(Subsequent resin)
B-1: The following structure (weight average molecular weight = 14000, acid value = 77 mgKOH / g)
B-2: The following structure (weight average molecular weight = 11000, acid value = 69 mg KOH / g, ethylenically unsaturated bond equivalent = 1.4 mmol / g)
B-3: The following structure (weight average molecular weight = 12000, acid value = 37 mgKOH / g, ethylenically unsaturated bond equivalent = 1.1 mmol / g)

Ｍ−４： 東亜合成社製アロニックスＭ−５１０ (Polymerizable compound)
M-1 to M-3: Compounds having the following structures

M-4: Aronix M-510 manufactured by Toa Gosei Co., Ltd.

(Photopolymerization initiator)
C-1 to C-4: Compounds having the following structure

(UV absorber)
D-1: The following structure

(Polymerization inhibitor)
E-1: p-methoxyphenol (surfactant)
F-1: The following mixture (Mw = 14000)

(Organic solvent)
G-1: Cyclohexanone

<Manufacture of membrane>
(Examples 1-14, Comparative Examples 1-4)
The radiation-sensitive composition shown in the following table was applied on a silicon wafer so that the film thickness after application was 0.5 μm, and then heated at 100 ° C. for 2 minutes on a hot plate. The substrate was exposed at an exposure dose of 1000 mJ / cm ² . Furthermore, it heated at 200 degreeC for 8 minute (s) on the hotplate, and manufactured the cured film.

(Examples 15 and 16)
The first layer of the radiation sensitive composition shown in the following table was applied on a silicon wafer so that the film thickness after application was 0.25 μm, and then heated at 100 ° C. for 2 minutes on a hot plate. The substrate was exposed at an exposure dose of 1000 mJ / cm ² . Furthermore, it heated on 200 degreeC on the hotplate for 8 minutes, and the film | membrane was manufactured. Then, the radiation sensitive composition of the 2nd layer shown in the following table | surface is apply | coated so that the film thickness after application | coating may be set to 0.25 micrometer, Then, it is 100 minutes at 100 degreeC on a hotplate. Heated. The substrate was exposed at an exposure dose of 1000 mJ / cm ² . Furthermore, it heated at 200 degreeC for 8 minute (s) on the hotplate, and manufactured the cured film.

(Measurement of refractive index)
The refractive index of the cured film was measured using ellipsometry VUV-VASE (manufactured by JA Woollam Japan). The measurement temperature was room temperature (25 ° C.), and the measurement wavelength was 633 nm.

(Evaluation of spectral performance)
Spectral transmittance and absorbance of the film (film before exposure) and the cured film (film after exposure) were measured using a spectrometer UV3600 manufactured by Shimadzu Corporation. The measurement temperature was room temperature (25 ° C.).
Standard deviation was evaluated according to the following criteria.
A: Standard deviation of transmittance in a wavelength range of 400 to 700 nm is 3% or less B: Standard deviation of transmittance in a wavelength range of 400 to 700 nm is more than 3% and 5% or less C: Transmission in a wavelength range of 400 to 700 nm The standard deviation of the rate exceeds 5% and is 10% or less. D: The standard deviation of the transmittance exceeds 10% in the wavelength range of 400 to 700 nm. The spectral evaluation was evaluated according to the following criteria.
A: Absorbance at a wavelength of 550 nm of the cured film is 0.1 to 0.8, an absorbance ratio of the wavelength of 350 nm to 550 nm of the film before exposure is 1.7 to 3.5, and a standard deviation of the cured film The evaluation is A.
B: The absorbance of the cured film at a wavelength of 550 nm is 0.1 to 0.8, the ratio of absorbance of the film before exposure to 350 nm and 550 nm is 1.7 to 3.5, and the standard deviation of the cured film is evaluated. Is B.
C: 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 350 nm and 550 nm of the film before exposure is 1.7 to 3.5. Evaluation of the standard deviation of the cured film Is C.
D: The absorbance of the cured film at a wavelength of 550 nm is 0.1 to 0.8, but the ratio of absorbance of the film at a wavelength of 350 nm and 550 nm before exposure is out of 1.7 to 3.5.
E: Absorbance of the cured film at a wavelength of 550 nm deviates from 0.1 to 0.8.

As shown in the above table, the examples were excellent in spectral characteristics. It could be suitably used as a gray pixel. On the other hand, the comparative example was inferior in spectral characteristics as compared with the example.
In addition, when the cured films of the examples and comparative examples were incorporated into the solid-state imaging device, the solid-state imaging device incorporating the cured films of the examples had better images than the solid-state imaging device incorporated with the cured film of the comparative example. It was recognizable.

  About the composition 14 used in Example 14, it is the same as that of Example 14 except having changed the organic solvent G-1 (cyclohexanone) into 3-ethoxypropionate (made by Tokyo Chemical Industry Co., Ltd.). As a result of evaluation, the same evaluation results as in Example 14 were obtained. Moreover, about the composition 14 used for Example 14, except having used the organic solvent G-1 (cyclohexanone) and the solvent which mixed cyclohexanone and 3-ethoxy propionate by 50:50 by mass ratio, When evaluation was performed in the same manner as in Example 14, the same evaluation results as in Example 14 were obtained. From this result, it is expected that good results can be obtained even when other organic solvents or organic solvents are used in combination.

上記結果より、膜厚を変化させても、優れたリソグラフィ性、経時安定性および塗布性を有していた。 About the composition 2 used in Example 2, the film thickness after coating is 0.1 μm, 0.2 μm, 0.4 μm, 0.5 μm, 0.7 μm, 0.9 μm, and 1.1 μm. A cured film was produced in the same manner as described above, and evaluated in the same manner as in Example 2. The evaluation results are shown below.

From the above results, even when the film thickness was changed, the film had excellent lithographic properties, stability over time, and coating properties.

10: Colored pixel 11: Cured film 12: Support

Claims (15)

A resin, a colorant, a polymerizable compound, and a photopolymerization initiator,
The resin / colorant, which is the mass ratio of the resin and the colorant, is 1.0 to 6.0,
The polymerizable compound is a radiation-sensitive composition containing a polymerizable compound having at least one group selected from a hydroxyl group and an acid group.   The radiation sensitive composition of Claim 1 whose resin / colorant which is mass ratio of the said resin and the said colorant is 1.5-4.0.   The radiation-sensitive composition according to claim 1 or 2, wherein the colorant contains a pigment and contains 7 to 50% by mass of the pigment with respect to the total solid content of the radiation-sensitive composition.   The radiation-sensitive composition according to claim 3, wherein the pigment contains a black pigment.   The radiation-sensitive composition according to any one of claims 1 to 4, wherein the resin contains an alkali-soluble resin, and the ethylenically unsaturated bond equivalent of the alkali-soluble resin is 1.0 mmol / g or less.   Furthermore, the radiation sensitive composition of any one of Claims 1-5 containing a ultraviolet absorber.   The radiation sensitive composition according to any one of claims 1 to 6, wherein the photopolymerization initiator includes an α-aminoketone compound. When a film having a thickness of 0.5 μm was formed using the radiation-sensitive composition,
Absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm of the film is 0.1 to 0.8,
The standard deviation of the transmittance in the wavelength range of 400 to 700 nm of the film is 10% or less,
Absorbance Ab ³⁶⁵ against wavelength 365nm of the light of the film, which is the ratio between the absorbance Ab ⁵⁵⁰ for light having a wavelength 550nm of the film, Ab ³⁶⁵ / Ab ⁵⁵⁰ is a 1.7 to 3.7, according to claim 1 The radiation sensitive composition of any one of -7.   The refractive index of light having a wavelength of 633 nm is 1.20 to 1.65 when a film having a thickness of 0.5 μm is formed using the radiation-sensitive composition, according to any one of claims 1 to 8. The radiation-sensitive composition described.   The film | membrane using the radiation sensitive composition of any one of Claims 1-9. Absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm of the film is 0.1 to 0.8,
The standard deviation of the transmittance in the range of 400 to 700 nm of the film is 10% or less,
A film having Ab ³⁶⁵ / Ab ⁵⁵⁰ of 1.7 to 3.7, which is a ratio of absorbance Ab ³⁶⁵ with respect to light having a wavelength of 365 nm and absorbance Ab ⁵⁵⁰ with respect to light having a wavelength of 550 nm.   The film | membrane of Claim 10 or 11 whose refractive index with respect to the light of wavelength 633nm of a film | membrane is 1.20-1.65.   The color filter which has a cured film using the radiation sensitive composition of any one of Claims 1-9.   The light shielding film which has a cured film using the radiation sensitive composition of any one of Claims 1-9.   The solid-state image sensor which has a cured film using the radiation sensitive composition of any one of Claims 1-9.

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