WO2018123462A1 - Pattern manufacturing method, color filter manufacturing method, method of manufacturing sold state imaging element, and method of manufacturing image display device - Google Patents

Abstract

Provided are a pattern manufacturing method having a wide process window, a color filter manufacturing method, a method of manufacturing a solid-state imaging element, and a method of manufacturing an image display device. The pattern manufacturing method includes the steps of: utilizing a negative photosensitive composition and forming a negative photosensitive composition layer on a support medium; exposing the negative photosensitive composition layer via a mask having a pattern; and developing the negative photosensitive composition layer after removing an unexposed portion thereof. The optical density of the mask to light of a wavelength used for exposure is 3.6 or greater.

Description

Pattern manufacturing method, color filter manufacturing method, solid-state imaging device manufacturing method, and image display device manufacturing method

The present invention relates to a pattern manufacturing method. More specifically, the present invention relates to a method for producing a pattern by a photolithography method using a negative photosensitive composition. The present invention also relates to a color filter manufacturing method, a solid-state imaging device manufacturing method, and an image display device manufacturing method.

In a pattern manufacturing method using a photolithography method, a photosensitive composition layer is formed on a support by applying a photosensitive composition layer, and a photosensitive composition layer is passed through a mask having a pattern. And a step of developing the photosensitive composition layer after exposure.

In the method for producing a pattern using a photolithography method, the pattern formation method differs depending on whether a positive photosensitive composition or a negative photosensitive composition is used as the photosensitive composition. That is, in the positive photosensitive composition, when the exposure energy exceeds the threshold value, the solubility in the developer increases rapidly. For this reason, when a positive photosensitive composition is used as the photosensitive composition, the photosensitive composition layer is exposed to light through a mask, and the photosensitive composition layer in the exposed portion is dissolved in the developer. After enhancing the properties, the photosensitive composition layer in the exposed area is removed using a developer to form a pattern (see, for example, Patent Documents 1 to 4).

On the other hand, in the negative photosensitive composition, the reaction gradually proceeds according to the exposure energy, and the solubility in the developer is lowered. For this reason, when a negative photosensitive composition is used as the photosensitive composition, the photosensitive composition layer is exposed to light through a mask, and the photosensitive composition layer in the exposed area is dissolved in the developer. Then, the photosensitive composition layer in the unexposed area is removed using a developer to form a pattern (see, for example, Patent Document 5).

JP 2012-003152 A JP 2014-206729 A JP 2010-237426 A JP 2002-313696 A JP2015-52753A

In the case of producing a pattern using a negative photosensitive composition, the negative photosensitive composition layer is exposed through a mask having a pattern. At this time, even in the portion covered with the mask, the mask is transmitted through the mask. The reaction may proceed due to the small amount of light. For this reason, when exposure is performed with the exposure energy higher than the optimum exposure energy, the reaction proceeds even in the portion covered with the mask, the solubility in the developer is lowered, and the line width of the resulting pattern is a desired value. In some cases, the residue was thicker or a residue was formed between the patterns. Here, the optimum exposure energy is a condition of exposure energy that can form a pattern according to the design dimension of the mask.

Accordingly, an object of the present invention is to provide a process window, particularly a pattern manufacturing method, a color filter manufacturing method, a solid-state imaging device manufacturing method, and an image having a wide allowable range (margin) of exposure energy and a wide allowable range of focus depth (margin). The object is to provide a method for manufacturing a display device.

Attempts to improve the process window in pattern formation using a negative photosensitive composition have been mainly focused on the composition formulation and development conditions. Has never been done before. As a result of various studies, the present inventor has found that the above object can be achieved by performing exposure using a mask having an optical density of 3.6 or more with respect to light having a wavelength used for exposure, and has completed the present invention. . The present invention provides the following.
<1> forming a negative photosensitive composition layer by applying a negative photosensitive composition on a support;
Exposing the negative photosensitive composition layer through a mask having a pattern;
Removing the negative photosensitive composition layer in the unexposed area and developing;
A method for producing a pattern including:
The mask is a pattern manufacturing method in which an optical density with respect to light having a wavelength used for exposure is 3.6 or more.
<2> The method for producing a pattern according to <1>, wherein the mask has an optical density of 3.6 or more with respect to light having a wavelength of 365 nm.
<3> The pattern production method according to <1> or <2>, wherein the mask includes at least one selected from chromium and a chromium compound.
<4> The method for producing a pattern according to any one of <1> to <3>, wherein the negative photosensitive composition contains a photopolymerization initiator and a radical polymerizable compound.
<5> The method for producing a pattern according to any one of <1> to <4>, wherein the negative photosensitive composition contains a colorant.
<6> The method for producing a pattern according to any one of <1> to <5>, wherein the negative photosensitive composition contains transparent particles.
<7> The method for producing a pattern according to any one of <1> to <6>, wherein the negative photosensitive composition is a negative photosensitive composition for forming a pixel of a color filter.
<8> The method for producing a pattern according to any one of <1> to <7>, wherein the exposure illuminance is 5000 to 50000 W / m ² in the exposure.
<9> The method for producing a pattern according to any one of <1> to <8>, wherein the oxygen concentration in exposure is 21% or more.
<10> The method for producing a pattern according to any one of <1> to <9>, wherein, in the development, a developer is spray-coated on the negative photosensitive composition layer.
<11> A method for producing a color filter, comprising the method for producing a pattern according to any one of <1> to <10>.
<12> A method of manufacturing a color filter having a plurality of color pixels, wherein the pattern manufacturing method according to any one of <1> to <10> A method for producing a color filter using the method.
<13> A method for manufacturing a solid-state imaging device, including the method for manufacturing a pattern according to any one of <1> to <10>.
<14> A method for manufacturing an image display device, including the method for manufacturing a pattern according to any one of <1> to <10>.

According to the present invention, it is possible to provide a method for manufacturing a pattern having a wide process window such as an allowable range (margin) of exposure energy and an allowable range (margin) of focal depth. It is also possible to provide a color filter manufacturing method, a solid-state imaging device manufacturing method, and an image display device manufacturing method.

It is explanatory drawing which shows typically one Embodiment of exposure apparatus. It is explanatory drawing which shows the undercut width in Test Example 5.

Hereinafter, the contents of the present invention will be described in detail.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent. 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 the present specification, “exposure” means not only exposure using light unless otherwise specified, but also exposure using particle beam such as electron beam and ion beam is included in exposure. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
In this 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 amount of components excluding the solvent from all the components 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” not only means an independent process, but also if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes, include.
In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Pattern manufacturing method>
The pattern production method of the present invention comprises:
Applying a negative photosensitive composition on a support to form a negative photosensitive composition layer (hereinafter also referred to as a negative photosensitive composition layer forming step);
A step of exposing the negative photosensitive composition layer through a mask having a pattern (hereinafter also referred to as an exposure step);
Removing the negative photosensitive composition layer in the unexposed area and developing (hereinafter also referred to as a developing process);
A method for producing a pattern including:
The mask is characterized by having an optical density of 3.6 or more with respect to light having a wavelength used for exposure.

According to the present invention, in the exposure process, a mask having an optical density of 3.6 or more with respect to light having a wavelength used for exposure is used. Therefore, in the portion (unexposed portion) covered with the mask in the negative photosensitive composition layer. The light shielding property is high, and curing in the unexposed area can be effectively suppressed even when exposure is performed with an increased exposure energy. That is, the optical contrast in the part (unexposed part) covered with the mask in the negative photosensitive composition layer and the part (exposed part) exposed from the mask can be improved. For this reason, according to the present invention, the allowable range (margin) of exposure energy can be expanded. Moreover, since hardening of an unexposed part can be suppressed effectively, generation | occurrence | production of the residue between patterns can also be suppressed effectively. Further, even when the focus is deviated during exposure, it is possible to suppress an increase in the line width of the pattern and to increase the allowable range (margin) of the depth of focus (DOF). This is presumed to be because the amount of light transmitted from the light shielding portion of the mask is extremely small, so that the light when the focus is shifted does not adversely affect the image formation. Moreover, by using said mask, hardening of the negative photosensitive composition layer of the unexposed part in a mask peripheral part can also be suppressed effectively, and the pattern excellent in the rectangularity is easy to be obtained.

In the mask used in the present invention, the optical density with respect to light having a wavelength used for exposure is 3.6 or more, preferably 3.7 or more, more preferably 4 or more, and further more preferably 5 or more. preferable. The upper limit is not particularly limited and is preferably 8.0 or less, more preferably 7.5 or less, and even more preferably 7 or less. For example, if the optical density of the mask is 7 or less, the effect of reducing the process load during blanking (easier mask fabrication) can be expected.

The optical density (OD: Optical Density) is a value that is expressed by the following formula, and is a value that represents the degree of absorption in logarithm.
OD (λ) = Log ₁₀ [T (λ) / I (λ)]
λ represents a wavelength, T (λ) represents a transmitted light amount at the wavelength λ, I (λ) represents an incident light amount at the wavelength λ, and OD (λ) represents an optical density at the wavelength λ.

In the present invention, the value of the optical density of the mask is preferably a value for light having a wavelength of 365 nm. In other words, the mask preferably has an optical density of 3.6 or more with respect to light having a wavelength of 365 nm.

There is no particular limitation on the material of the mask used in the present invention. Examples thereof include chromium, chromium compounds, tantalum, tantalum compounds (TaN, TaO, etc.), and chromium and / or chromium compounds are preferred. Examples of the chromium compound include chromium oxide, chromium nitride, and an alloy containing chromium, and chromium oxide is preferable.

An example of a mask is a laminated film of a chromium film and a chromium oxide film. For example, in this laminated film, the optical density can be adjusted by adjusting the film thickness of the chromium film. For example, the optical density can be increased by increasing the thickness of the chromium film, and the optical density can be decreased by decreasing the thickness of the chromium film.

The mask manufacturing method is not particularly limited, and a conventionally known method can be used. For example, a mask material layer is formed on the support by sputtering, vapor deposition (vacuum vapor deposition, chemical vapor deposition, physical vapor deposition, etc.), plating, etc., and this layer is etched to form a pattern. Can be manufactured.

The negative photosensitive composition used in the pattern production method of the present invention is preferably a negative photosensitive composition for forming a pixel of a color filter. That is, the pattern manufactured by the pattern manufacturing method of the present invention is preferably a pixel of a color filter. Here, as a method of improving the optical contrast between the unexposed portion and the exposed portion, a method of performing exposure using a projection lens technique such as annular illumination or a method of using a halftone photomask is known. However, in the negative photosensitive composition for forming the pixel of the color filter, when these techniques are applied, the light transmission part contributes to the polymerization, and conversely, the process window is narrowed, which is an adverse effect. Since the negative photosensitive composition for forming a pixel of a color filter may contain a colorant, transparent particles, or the like, there is a limit to improving contrast depending on illumination conditions during exposure. This is because the irradiated light is scattered in the film by components such as a colorant. In the present invention, even when a negative photosensitive composition for forming a pixel of a color filter is used, an allowable range (margin) of exposure energy can be expanded. Further, the color filter pixels are required to be precise in terms of pattern dimensions. In the present invention, even when a negative photosensitive composition for forming a pixel of a color filter is used, the allowable range (margin) of exposure energy can be widened. Even if variations occur, a pattern as designed can be formed. For this reason, the pattern manufacturing method of the present invention is particularly effective when forming the color filter pixels using the negative photosensitive composition for forming the color filter pixels.

Hereinafter, each step of the pattern manufacturing method of the present invention will be described in detail.

In the negative photosensitive composition layer forming step, the negative photosensitive composition layer is formed by applying the negative photosensitive composition on the support. There is no limitation in particular as a support body which applies a negative photosensitive composition, According to a use, it can select suitably. For example, a glass substrate, a silicon substrate, etc. are mentioned. A substrate for a solid-state imaging device 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 a substrate (for example, a silicon substrate) can also be used. . The pattern may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface). A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate. Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface. The support may be provided with a partition wall. The partition is preferably formed of a material having a refractive index smaller than that of a pattern obtained from the negative photosensitive composition. The partition wall can suppress leakage of light from the pattern to the adjacent pattern. As specific examples of the material of the partition wall, various inorganic materials and organic materials can be used. For example, examples of the organic material include acrylic resin, polystyrene resin, polyimide resin, organic SOG (Spin On Glass) resin, siloxane resin, and fluorine resin. Examples of the inorganic material include porous silica, polycrystalline silicon, colloidal silica particles, silicon oxide, silicon nitride, and metal materials such as tungsten and aluminum.

As a method for applying the negative photosensitive composition 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 film thickness of the negative photosensitive composition layer is preferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm, still more preferably from 0.2 to 3 μm.

The negative photosensitive composition layer formed on the support may be dried (prebaked). When a pattern is formed by a low temperature process, pre-baking may not be performed. When prebaking is performed, the prebaking temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, and further preferably 105 ° C. or lower. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. The prebake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed with a hot plate, an oven, or the like.

In the exposure step, the negative photosensitive composition layer is exposed through a mask having a pattern. In the present invention, a mask having an optical density of 3.6 or more with respect to light having a wavelength used for exposure is used. For example, the negative photosensitive composition layer can be exposed in a pattern by exposing it through a mask having a predetermined pattern using an exposure apparatus such as a stepper. Thereby, an exposure part can be hardened. Moreover, in the part (unexposed part) covered with the mask in a negative photosensitive composition layer, hardening of a negative photosensitive composition layer can be suppressed effectively.

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 energy), for example, preferably 0.03 ~ 2.5J / cm ^2, more preferably 0.05 ~ 1.0J / cm ^2.

The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere (oxygen concentration 20% by volume), the oxygen concentration may be performed in an atmosphere having a lower oxygen concentration than the atmosphere, and the oxygen concentration is higher than that in the atmosphere. It may be performed in an atmosphere. The oxygen concentration at the time of exposure is preferably 15% by volume or more, and more preferably 21% by volume or more. The upper limit is preferably 50% by volume or less. The exposure intensity is can be set appropriately, preferably 1000 ~ 100000W / ^{m 2,} more preferably 5000 ~ 50000W / ^{m 2.} If the exposure illuminance is in the above range, a good pattern resolution is easily obtained.

In the exposure process, the exposure may be performed by dividing the exposure into a plurality of times. By dividing the exposure, the exposure amount per one divided exposure (for example, each of the first exposure, the second exposure, and the third exposure) decreases. When a negative photosensitive composition containing a photopolymerization initiator and a radical polymerizable compound is used as an example, the exposure amount per divided exposure is reduced by dividing the exposure. It is considered that the lateral diffusion of radicals and the like in the type photosensitive composition layer can be suppressed. Further, by performing additional exposure (second exposure, third exposure, etc.) at the same coordinate with a time interval, radicals in the vicinity of the center in the negative photosensitive composition layer in the exposure area were retained by the exposure residual heat. Further exposure is performed in a state where oxygen is not deactivated (promoting radical generation). For this reason, it is considered that radical diffusion toward the support is promoted and adhesion to the support is improved. Moreover, it is considered that radicals generated by the first exposure near the exposure area are deactivated by oxygen in the negative photosensitive composition layer and the surface of the layer, and lateral diffusion is suppressed. It is considered that the same phenomenon occurs in the second exposure. For this reason, it is possible to more effectively suppress an increase in the line width of the pattern (such as an increase in the line width when the amount of exposure is large or an increase in the line width when the focus is shifted).

FIG. 1 is an explanatory view schematically showing an embodiment of an exposure apparatus used in the present invention. As shown in FIG. 1, in this exposure apparatus, light emitted from a specific light source (not shown) is incident on a projection lens (projection lens) 2 via a condenser lens 1 and a reticle 5. Although not shown, a mask with a predetermined pattern may be installed before or after the condenser lens 1 so that the light with the predetermined pattern reaches the projection lens 2. Here, the numerical aperture on the condenser lens side is NA _1, and the numerical aperture on the projection lens side is NA ₂ . The light transmitted through the projection lens (projection lens) 2 is irradiated onto the work 4. Incidentally, the numerical aperture of the emission side of the projection lens with NA _3. Incidentally, just when expressed as NA means the NA _3.

The numerical aperture NA ₃ is preferably 0.5 or more, more preferably 0.55 or more, and particularly preferably 0.6 or more. There is no particular upper limit, and it is practical that NA is 0.65 or less in the stepper in the batch exposure method. In general, it is understood that the resolving power is in a relationship of k × λ / NA (k: optical constant, λ: wavelength). Therefore, the limit resolution improves as the NA increases. On the other hand, the depth of focus (DOF) has a relationship of DOF = k · λ / NA. The DOF decreases as the NA increases. k is a value that varies depending on the illumination conditions of the exposure apparatus, and is not fixed.

The coherence factor σ, which is the ratio of the numerical apertures NA ₁ and NA ₂ (NA ₁ / NA ₂ ), is preferably 0.9 or less, more preferably 0.6 or less, and 0.5 or less. It is particularly preferred. There is no particular lower limit, and it is practical that it is 0.38 or more. When the coherent factor (σ) is small, the contrast of the image to be formed is improved. This improvement in contrast is thought to contribute to an improvement in DOF.
In this description, the batch exposure apparatus has been described. However, the scanning stepper that performs scanning exposure in synchronism with the reticle and the stage, and the exposure apparatus that performs image transfer 1: 1 with the mask pattern (proximity exposure, batch exposure). It can also be applied to a projection exposure apparatus).

In the developing process, the negative photosensitive composition layer in the unexposed area is removed and developed. The removal of the unexposed portion of the negative photosensitive composition layer can be performed using a developer. As the developer, an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable. The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

As the developer, an alkaline aqueous solution obtained by diluting an alkaline agent with pure water is preferably used. Examples of the alkaline agent include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxy. Organic alkaline compounds such as water, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, water Inorganic acids such as sodium oxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate Potassium compounds may be mentioned. 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. Further, the developer may further contain a surfactant. Examples of the surfactant include surfactants described in the section of the negative photosensitive composition described later, and nonionic surfactants are preferable. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it is preferable to wash | clean (rinse) with a pure water after image development. Further, the developer may be once produced as a concentrated solution and diluted to a necessary concentration at the time of use from the viewpoint of transportation and storage. The dilution factor is not particularly limited, and can be set, for example, in the range of 1.5 to 100 times.

As the developing method, a known method can be used. Examples include immersion development, paddle development, shower development, spray development, ultrasonic development, dip development, and the like. Among them, spray development is preferable because it has a high effect of removing a weakly polymerized portion, suppresses residues between patterns, and easily obtains a pattern with good rectangularity. In addition, spray development can further widen a process window such as an exposure energy margin and a focal depth margin. Here, the spray development is a method in which development is performed by discharging a developer applied with a gas such as N ₂ or air from a nozzle and spraying the developer onto a target. In spray development, spray-like developer discharged from a nozzle is deposited on the target, and the target is developed by spray pressure.

The flow rate of the developer in spray development, the flow rate ratio between the developer and gas, the spray pressure, etc. can be adjusted as appropriate. For example, the flow rate of the developer is preferably 100 to 500 mL / min, more preferably 150 to 400 mL / min, and further preferably 200 to 350 mL / min. The flow rate ratio between the developer and gas is, for example, preferably developer: gas = 1: 1.5 to 1:10, more preferably 1: 2 to 1: 5. : 2.5 to 1: 4 is more preferable. The spray pressure is preferably 3 to 15 Mpa, more preferably 5 to 12 Mpa, and even more preferably 7 to 9 Mpa.

Developed, dried and then heat-treated (post-baked). Post-baking is a heat treatment after development for complete film (pixel) curing. When performing post-baking, the post-baking temperature is preferably 240 ° C. or lower, more preferably 230 ° C. or lower, still more preferably 220 ° C. or lower, even more preferably 200 ° C. or lower, and particularly preferably 190 ° C. or lower. There is no particular lower limit, and considering an efficient and effective treatment, 50 ° C. or higher is preferable, and 100 ° C. or higher is more preferable. The Young's modulus of the film after post-baking is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa. Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. .

Post bake may be performed in a low oxygen concentration atmosphere. For example, the oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, still more preferably 10% by volume or less, and even more preferably 7% by volume or less. 3% by volume or less is particularly preferable. There is no particular lower limit, and for example, it can be 10 ppm by volume or more.

In the present invention, after development, after drying, exposure (also referred to as post-exposure) may be performed to cure the film. In this case, in the first exposure step, exposure is performed with light having a wavelength of more than 350 nm and not more than 380 nm (preferably, light having a wavelength of 355 to 370 nm, particularly preferably i-line). The exposure is preferably performed with light having a wavelength of 254 nm. The exposure amount in the post-exposure (exposure energy), preferably 30 ~ 4000mJ / cm ^2, more preferably 50 ~ 3500mJ / cm ^2. For example, an ozone-less mercury lamp is preferable as the exposure light source. Further, post-baking may be performed after post-exposure.

<Negative photosensitive composition>
Next, the negative photosensitive composition used in the pattern manufacturing method of the present invention will be described. The negative photosensitive composition used in the pattern production method of the present invention is not particularly limited, and a known negative photosensitive composition can be used. Further, it can also be applied to a photoresist that is polymerized by light to form an image, a polyimide resin composition, a solder resist, and the like. Specific examples of the negative photosensitive composition containing a polyimide resin include the compositions described in JP-A-2014-201695. The negative photosensitive composition used in the pattern production method of the present invention is preferably a composition containing a radical polymerizable compound and a photopolymerization initiator. Hereinafter, each component used for a negative photosensitive composition is demonstrated.

<< Radically polymerizable compound >>
The negative photosensitive composition in the present invention preferably contains a radical polymerizable compound. The radical polymerizable compound may be any of chemical forms such as a monomer, a prepolymer, and an oligomer, but is preferably a monomer. The molecular weight of the radical polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more.

The radically polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound. Specific examples of these compounds include those described in paragraph Nos. 0095 to 0108 in JP-A-2009-288705, paragraph 0227 in JP-A-2013-29760, and paragraph numbers 0254 to 0257 in JP-A-2008-292970. Compounds, the contents of which are incorporated herein.

The radical polymerizable compounds are 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 (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercial product; Nippon Kayaku) Co., Ltd., NK ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues ( For example, SR commercially available from Sartomer 454, SR499). These oligomer types can also be used. Further, KAYARAD RP-1040 and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used as the radical polymerizable compound.
In addition, as a radical polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) It is also preferable to use a trifunctional (meth) acrylate compound such as acrylate or pentaerythritol tri (meth) acrylate. Commercially available products of trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.

As the radically polymerizable compound, a compound having an acid group can also be used. By using such a radically polymerizable compound, the radically polymerizable compound in the unexposed area is easily removed during development, and the generation of development residues can be more effectively suppressed. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferable. Commercially available products of radically polymerizable compounds having acid groups include Aronix M-510, M-520, TO-2349 (above, manufactured by Toagosei Co., Ltd.) and the like.

The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. If the acid value of the radically polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling.

The radical polymerizable compound is also preferably a compound having a caprolactone structure. Radical 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 radical polymerizable compound, a radical polymerizable compound having an alkyleneoxy group can also be used. The radical polymerizable compound having an alkyleneoxy group is preferably a radical polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a radical polymerizable compound having an ethyleneoxy group. A tri- to hexa-functional (meth) acrylate compound having 4 to 20 groups is more preferable. Examples of commercially available radical polymerizable compounds having an alkyleneoxy group include SR-494, a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meta) having three isobutyleneoxy groups. ) KAYARAD TPA-330 which is an acrylate.

Examples of the radical polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, and the like. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is also preferable to use radically 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. . 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 (Kyoeisha Chemical Co., Ltd.) and the like.

The content of the radical polymerizable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the negative photosensitive composition. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less. One radically polymerizable compound may be used alone, or two or more kinds thereof may be used in combination. When using 2 or more types together, it is preferable that a sum total becomes the said range.

<< photopolymerization initiator >>
The negative photosensitive composition in the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a radical polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable. Moreover, the compound which produces | generates a certain action with the photosensitized sensitizer and produces | generates an active radical may be sufficient.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton and compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone compounds, and the like. As photopolymerization initiators, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls. Imidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound, and 3-aryl substituted coumarin compound are preferred, oxime compound, α-hydroxyketone compound , Α-aminoketone compounds and acylphosphine compounds are more preferred, and oxime compounds are even more preferred. As the photopolymerization initiator, descriptions in paragraphs 0065 to 0111 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF). Examples of commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE-819 and IRGACURE-TPO (above, manufactured by BASF).

Examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2016-21012. These compounds can be used. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3- ON, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one. In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Use the compounds described in 202-232, the compounds described in JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, etc. You can also. As commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF) are also preferably used. Also, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcs NCI-30 Adekaoptomer N-1919 (photopolymerization initiator 2 of JP2012-14052A) (manufactured by ADEKA Co., Ltd.) can be used.

Further, as oxime compounds other than the above, compounds described in JP-A-2009-519904 in which an oxime is linked to the N-position of the carbazole ring, and compounds described in US Pat. A compound described in JP 2010-15025 A and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety; Using the compound described in US Pat. No. 7,556,910 contained in the molecule, the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source Also good. Preferably, for example, paragraph numbers 0274 to 0306 in JP 2013-29760 A can be referred to, the contents of which are incorporated herein.

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-2014-137466. This content is incorporated herein. In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include compounds OE-01 to OE-75 described in International Publication No. 2015/036910. 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 JP-A 2013-164471. Compound (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. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of No. 4223071, ADEKA ARKLES NCI-831 (manufactured by ADEKA Corporation), and the like.

Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.

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

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and more preferably 5,000 to 200,000 from the viewpoint of sensitivity. 000 is particularly preferred. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
You may use a photoinitiator in combination of 2 or more type as needed.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass with respect to the total solid content of the negative photosensitive composition. . When the content of the photopolymerization initiator is within the above range, good sensitivity and good pattern formability can be obtained. The negative photosensitive composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above range.

<< Colorant >>
The negative photosensitive composition in the present invention can contain a colorant. A negative photosensitive composition containing a colorant can be preferably used for forming colored pixels of a color filter.

The colorant may be either a dye or a pigment, or a combination of both. Examples of the pigment include conventionally known various inorganic pigments or organic pigments. The average particle diameter of the pigment is preferably from 0.01 to 0.1 μm, more preferably from 0.01 to 0.05 μm. As the colorant, a pigment is preferable, and an organic pigment is more preferable.

Examples of inorganic pigments include black pigments such as carbon black and titanium black; metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal complex salts.

Examples of the organic pigment include the following.
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 (or more, and yellow pigments);
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 ( Above, orange pigment);
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 (above, red pigment) );
C. I. Pigment Green 7, 10, 36, 37, 58, 59 (above, green pigment);
C. I. Pigment Violet 1,19,23,27,32,37,42,58,59 (above, purple pigment);
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 (above, blue pigment).
Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, a bromine atom number of 8 to 12 and an average number of chlorine atoms of 2 to 5 is used. It is also possible to use it. Specific examples include the compounds described in International Publication No. 2015/118720.
Moreover, the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP2012-247491A and paragraph number 0047 of JP2011-157478A.
These organic pigments may be used alone or in various combinations.

Examples of the dye include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, US Pat. No. 4,808,501, US Pat. Examples thereof include dyes disclosed in Japanese Patent No. 5667920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, and the like. When classified as a chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Is mentioned.

In addition, a dye multimer may be used as a colorant. The dye multimer is preferably a dye used by being dissolved in a solvent, but may form particles. When the dye multimer is a particle, the dye multimer is dispersed in a solvent or the like. The dye multimer in the particle state can be obtained, for example, by emulsion polymerization. Examples of the dye multimer in the particle state include compounds described in JP-A-2015-214682. Further, as the dye multimer, compounds described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, and the like can also be used. .

Further, as yellow colorants, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP2013-54339A, quinophthalone compounds described in paragraph numbers 0013 to 0058 of JP2014-26228A, and the like can also be used. .

Further, as the colorant, at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomer structure thereof, a metal ion containing at least Zn ²⁺ and Cu ²⁺ , A metal azo pigment containing the compound represented by (II) can also be used.

Wherein R ¹ and R ² are each independently OH or NR ⁵ R ⁶ , R ³ and R ⁴ are each independently ═O or ═NR ⁷ , and R ⁵ to R ⁷ are each Independently, it is a hydrogen atom or an alkyl group.

In the formula, R ¹¹ to R ¹³ each independently represents a hydrogen atom or an alkyl group.

The metal azo pigment preferably contains 95 to 100 mol% of Zn ²⁺ and Cu ²⁺ in total, more preferably 98 to 100 mol%, based on 1 mol of all metal ions of the metal azo pigment. The content is preferably 99.9 to 100 mol%, more preferably 100 mol%. The molar ratio of Zn ²⁺ to Cu ^{2+ in} the metal azo pigment is preferably Zn ²⁺ : Cu ²⁺ = 199: 1 to 1:15, and preferably 19: 1 to 1: 1. More preferably, it is 9: 1 to 2: 1.

The metal azo pigment may further contain a divalent or trivalent metal ion (hereinafter also referred to as other metal ions) other than Zn ²⁺ and Cu ²⁺ . Other metal ions include Ni ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ^{3+, Gd 3+, Tb 3+,} Dy 3+, Ho 3+, Yb 2+, Yb 3+, Er 3+, Tm 3+, Mg 2+, Ca 2+, Sr 2+, Mn 2+, Y 3+, Sc 3+, Ti 2+, Ti 3+, Nb ^<3+> , Mo ^<2+> , Mo ^<3+> , V ^<2+> , V ^<3+> , Zr <^2+> , Zr ^<3+> , Cd <^2+> , Cr ^<3+> , Pb <^2+> , Ba ^<2+> is mentioned. The amount of these other metal ions is preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 0.1 mol%, based on 1 mol of all metal ions of the metal azo pigment. More preferably, it is as follows.

In the metal azo pigment, an adduct is preferably formed of a metal azo compound composed of the anion and metal ion and a compound represented by the formula (II). An adduct is understood to mean a molecular assembly. The bond between these molecules may be, for example, due to intermolecular interaction, may be due to Lewis acid-base interaction, or may be due to coordination bond or chain bond. Further, the adduct may have a structure such as an inclusion compound (clathrate) in which a guest molecule is incorporated in a lattice constituting a host molecule. Further, the adduct may have a structure such as a composite interlayer crystal (including an interstitial compound). A composite interlayer crystal is a chemical non-stoichiometric crystalline compound composed of at least two elements. Further, the adduct may be a mixed substitution crystal in which two substances form a joint crystal, and atoms of the second component are located at regular lattice positions of the first component.

The metal azo pigment may be a physical mixture or a chemical composite compound. Preferably, it is a physical mixture. Preferable examples of the physical mixture include the following 1) and 2).
1) Adduct 1 of a metal azo compound composed of the anion and Zn ²⁺ and a compound represented by the formula (II), a metal azo compound composed of the anion and Cu ²⁺ , A physical mixture of adduct 2 with the compound represented by II).
2) In the physical mixture of 1), a metal azo compound composed of the above anion and a divalent or trivalent metal ion other than Zn ²⁺ and Cu ²⁺ , and a compound represented by the formula (II) A physical mixture comprising adduct 3 with

Regarding the above-mentioned metal azo pigments, the descriptions in paragraph numbers 0011 to 0062 and 0139 to 0190 of JP-A-2017-171914 can be referred to, and the contents thereof are incorporated in the present specification.

The content of the colorant is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more based on the total solid content of the negative photosensitive composition. There is no restriction | limiting in particular about an upper limit, It is preferable that it is 45 mass% or less, and it is more preferable that it is 40 mass% or less.

<< Transparent particles >>
The negative photosensitive composition in the present invention can contain transparent particles. A negative photosensitive composition containing transparent particles can be preferably used for forming white (colorless) pixels of a color filter.

The transparent particles are at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, Nb, In, P and S. And oxide particles containing at least one element selected from Ti, Zr, Sn, Al, and Si are preferable. Specifically, titanium dioxide, zirconium dioxide, silicon dioxide, zinc oxide, aluminum oxide, tungsten oxide (including composite oxides containing tungsten such as cesium tungsten oxide), niobium oxide, copper oxide, germanium oxide, indium oxide, Examples thereof include particles of tin oxide and magnesium oxide. Among these, particles of titanium dioxide, tin oxide, indium oxide and zirconium dioxide are preferable, and particles of titanium dioxide and zirconium dioxide are more preferable. Examples of the titanium oxide include rutile type titanium oxide, anatase type titanium oxide, and amorphous type titanium oxide, and rutile type titanium oxide is preferable. In addition, the oxide is preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include inorganic compounds and organic compounds. An inorganic compound and an organic compound may be used in combination. Specific examples of the surface treatment agent include polyol, aluminum oxide, aluminum hydroxide, amorphous silica, hydrous silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agent, titanate coupling agent. Etc.

The shape of the transparent particles is not particularly limited. For example, isotropic shapes (for example, spherical shape, polyhedral shape, etc.), anisotropic shapes (for example, needle shape, rod shape, plate shape, etc.), irregular shapes, and the like can be mentioned.

The weight average diameter of the primary particles of the transparent particles is preferably 150 nm or less, more preferably 100 nm or less, and still more preferably 80 nm or less. There is no particular lower limit, and it is preferably 1 nm or more. The measuring method of the weight average diameter of the transparent particles is in accordance with JIS K 0062: 1992.
The refractive index of the transparent particles at a wavelength of 500 nm is preferably 1.64 or more, more preferably 1.8 to 3.0, and still more preferably 1.8 to 2.8. The method for measuring the refractive index of the transparent particles is in accordance with JIS K 0062: 1992.

Transparent particles may be commercially available. For example, titanium dioxide includes TTO series (TTO-51 (A), TTO-51 (C), TTO-55 (C), etc.), TTO-S, V series (TTO-S-1, TTO-S-). 2, TTO-V-3, etc. (above, trade name, manufactured by Ishihara Sangyo Co., Ltd.), MT series (MT-01, MT-05, etc.) (trade name, manufactured by Teika Co., Ltd.), and the like. Examples of commercially available products of zirconium oxide, silicon dioxide, zinc oxide, aluminum oxide, cesium tungsten oxide, niobium oxide, tin oxide, magnesium oxide, and indium oxide include products described in Examples described later.

The content of the transparent particles is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more with respect to the total solid content of the negative photosensitive composition. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.

<< Resin >>
The negative photosensitive composition preferably contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and the use of a binder. In addition, a resin that is mainly used for dispersing particles such as pigment is also referred to as a dispersant. However, such use of the resin is an example, and the resin can be used for purposes other than such use.

In the negative photosensitive composition, the resin content is preferably 1 to 95% by mass with respect to the total solid content of the negative photosensitive composition. The lower limit is more preferably 5% by mass or more, and further preferably 10% by mass or more. The upper limit is more preferably 90% by mass or less, and still more preferably 85% by mass or less.

(Dispersant)
The negative photosensitive composition in the present invention preferably contains a dispersant as a resin. In particular, when a particle such as a pigment is included, a dispersant is preferably included. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).

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 acid groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 5 to 105 mgKOH / g.
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 exceeds 50 mol% 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.

Examples of the dispersant include a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth). Acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.

Polymer dispersants can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures. The polymer dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface can be cited as preferred structures. In addition, a dispersant described in paragraph numbers 0028 to 0124 of JP2011-070156A and a dispersant described in JP2007-277514A are also preferably used. These contents are incorporated herein.

As the resin (dispersant), a graft copolymer may be used. Details of the graft copolymer can be referred to the descriptions in paragraphs 0025 to 0094 of JP2012-255128A, the contents of which are incorporated herein. Specific examples of the graft copolymer include the following resins and resins described in paragraph numbers 0072 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein.

Also, as the resin (dispersant), an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can 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. Specific examples of the oligoimine dispersant include resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A, for example.

A commercially available product can also be used as the dispersant. For example, the product described in paragraph No. 0129 of JP2012-137564A can be used as a dispersant. The resin described in the column of the dispersant can be used for purposes other than the dispersant. For example, it can be used as a binder.

The content of the dispersing agent is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is preferably 150 parts by mass or less, and more preferably 100 parts by mass or less.

(Alkali-soluble resin)
The negative photosensitive composition in this invention can contain 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 alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali dissolution. Examples of the group that promotes alkali dissolution (hereinafter also referred to as an acid group) include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group, and a carboxyl group is preferable. Only one type of acid group may be included in the alkali-soluble resin, or two or more types may be used.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 100,000. The number average molecular weight (Mn) of the alkali-soluble resin is preferably 1,000 to 20,000.

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. Further, from the viewpoint of developing property control, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable.

The alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain. For example, a copolymer having a repeating unit derived from a monomer such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinyl benzoic acid, partially esterified maleic acid, Examples thereof include alkali-soluble phenol resins such as novolac resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable with (meth) acrylic acid 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, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Is mentioned. Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. Examples of other monomers include N-substituted maleimide monomers described in JP-A-10-300922, such as N-phenylmaleimide and N-cyclohexylmaleimide. Only one kind of these other monomers copolymerizable with (meth) acrylic acid may be used, or two or more kinds may be used.

Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate. A multi-component copolymer composed of / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate and another monomer, described in JP-A-7-140654, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-Hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used. Further, as a commercially available product, for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can be used.

An alkali-soluble resin having a polymerizable group can also be used as the alkali-soluble resin. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in the side chain is useful. Commercially available alkali-soluble resins having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscort R-264. KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation), Examples include ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) and DP-1305 (manufactured by Fuji Fine Chemicals Co., Ltd.).

The alkali-soluble resin includes at least one compound selected from the compound represented by the following formula (ED1) and the compound represented by the formula (1) in JP 2010-168539 A (hereinafter referred to as “ether dimer”). It is also preferable to include a polymer obtained by polymerizing a monomer component including “.

In 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.

As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A 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.

Examples of the polymer obtained by polymerizing a monomer component containing an ether dimer include polymers having the following structure.

The alkali-soluble resin may contain a repeating 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 has 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the above formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. The carbon number of the alkyl group of R ₃ is preferably 1-10. The 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.

The description of paragraphs 0558 to 0571 in JP 2012-208494 A (paragraph numbers 0685 to 0700 in the corresponding US Patent Application Publication No. 2012/0235099) can be referred to for the alkali-soluble resin. Embedded in the book. Further, the copolymer (B) described in paragraphs 0029 to 0063 of JP2012-32767A and the alkali-soluble resin used in the examples, paragraphs 0088 to 0098 of JP2012-208474A, The binder resin described in the description and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A and the binder resin used in the examples, JP2013-024934A Binder resin described in paragraph Nos. 0132 to 0143 of the gazette and the binder resin used in the examples, paragraph numbers 0092 to 0098 of the gazette of JP2011-242752 and the binder resin used in the examples, and JP2012 -032770, paragraph number 0030 0072 can also be used a binder resin according to. 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, still more preferably 200 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less.

The content of the alkali-soluble resin is preferably 1 to 95% by mass with respect to the total solid content of the negative photosensitive composition. The lower limit is more preferably 2% by mass or more, and further preferably 3% by mass or more. The upper limit is more preferably 93% by mass or less, and still more preferably 90% by mass or less. The negative photosensitive composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are included, the total is preferably within the above range.

(Other resins)
The negative photosensitive composition in the present invention may contain a resin (also referred to as other resin) other than the resin described above in the column of the dispersant and the alkali-soluble resin. Examples of other resins include (meth) acrylic resin, (meth) acrylamide resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene ether. Examples thereof include phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Examples of the polyimide resin include resins described in JP-A-2014-201695, and the contents thereof are incorporated herein. As for other resins, one kind of these resins may be used alone, or two or more kinds may be mixed and used.

<< Compound having epoxy group >>
The negative photosensitive composition can also contain a compound having an epoxy group (hereinafter also referred to as an epoxy compound). The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The lower limit is more preferably 2 or more. For example, the upper limit may be 10 or less, and may be 5 or less.

The epoxy compound preferably has an epoxy equivalent (= molecular weight of epoxy compound / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g / equivalent. Further preferred.

The epoxy compound may be a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, still more preferably 5000 or less, and even more preferably 3000 or less.

The epoxy compounds 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. Compounds can also be used. These contents are incorporated herein. As commercially available products, for example, as bisphenol A type epoxy resins, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050 , EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation) and the like. Examples of the bisphenol F type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE-602S. (Nippon Kayaku Co., Ltd.) and the like. As phenol novolac type epoxy resins, jER152, jER154, jER157S70, jER157S65 (Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation), etc. Is mentioned. Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.

When the negative photosensitive composition contains an epoxy compound, the content of the epoxy compound is preferably 0.1 to 40% by mass relative to the total solid content of the negative photosensitive composition. 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. One epoxy compound may be used alone, or two or more epoxy compounds may be used in combination. When using 2 or more types together, it is preferable that a sum total becomes the said range.

<< Solvent >>
The negative photosensitive composition 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 negative photosensitive composition are satisfied.

Examples of organic solvents include the following organic solvents. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyalkyl acetate (Eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid) Til, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.) Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and Ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, Acetoacetate Le, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of ethers 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 Examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Preferable examples of aromatic hydrocarbons include toluene and xylene. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be better reduced for environmental reasons (for example, 50 mass ppm or less with respect to the total amount of organic solvent, 10 Or less than 1 ppm by mass).

Organic solvents may be used alone or in combination of two or more. 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, methyl 3-methoxypropionate , 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. Further, it is preferable to use an organic solvent having a low metal content. For example, the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less. If necessary, an organic solvent having a metal content of mass ppt (parts per trill) level may be used. Such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, 2015) November 13).

The content of the solvent is preferably such that the total solid content of the negative photosensitive composition is 5 to 80% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

<< Curing accelerator >>
The negative photosensitive composition may contain a curing accelerator for the purpose of improving the hardness of the pattern and lowering the curing temperature. Examples of the curing accelerator include thiol compounds.

Examples of the thiol compound include polyfunctional thiol compounds having two or more mercapto groups in the molecule. The polyfunctional thiol compound 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 more preferably a compound having a structure represented by the following formula (T1).
Formula (T1)

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

In the above formula (T1), L is preferably an aliphatic group having 2 to 12 carbon atoms. In the above formula (T1), it is more preferable that 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 preferable. One thiol compound may be used, or two or more thiol compounds may be used in combination.

Curing accelerators include methylol compounds (for example, compounds exemplified as a crosslinking agent in paragraph No. 0246 of JP-A-2015-34963), amines, phosphonium salts, amidine salts, amide compounds (for example, JP-A-2013-41165, curing agent described in paragraph No. 0186), base generator (for example, ionic compound described in JP-A-2014-55114), isocyanate compound (for example, JP-A-2012-150180) A compound described in paragraph No. 0071 of the publication), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP2011-255304A), an onium salt compound (for example, JP2015-34963A). Illustrated as an acid generator in paragraph 0216 Compounds, compounds described in JP-A-2009-180949) or the like can be used.

When the negative photosensitive composition contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass relative to the total solid content of the negative photosensitive composition. It is more preferably 8 to 6.4% by mass.

<< Pigment derivative >>
When the negative photosensitive composition in the present invention contains a pigment, the negative photosensitive composition preferably further contains a pigment derivative. Examples of the pigment derivative include a compound having a structure in which a part of the chromophore is substituted with an acidic group, a basic group, or a phthalimidomethyl group. The chromophores constituting the pigment derivative include quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, and perinone skeleton. Perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, selenium skeleton, metal complex skeleton, etc., quinoline skeleton, benzimidazolone skeleton, diketopyrrolo A pyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferable, and an azo skeleton and a benzimidazolone skeleton are more preferable. As an acidic group which a pigment derivative has, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable. Specific examples of the pigment derivative include compounds described in Examples described later. Further, compounds described in paragraph numbers 0162 to 0183 of JP2011-252065A can also be mentioned, the contents of which are incorporated herein.

In the case where the negative photosensitive composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<< Surfactant >>
The negative photosensitive composition can contain a surfactant. Various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used as surfactants, further improving coatability. A fluorosurfactant is preferable because it can be used. The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within the above range is effective in terms of uniformity of coating film thickness and liquid-saving properties.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (and above, DIC Corporation). ), Florard FC430, FC431, FC171 (Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 and compounds described in paragraph numbers of 0117 to 0132 of JP-A No. 2011-132503 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 molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heat is applied can be suitably used. . Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21, and these may be used.

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) (meta). ) 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. In the following formula,% indicating the ratio of repeating units is mol%.

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

As the fluorosurfactant, a fluorine-containing polymer having a group having an ethylenically unsaturated bond in the side chain can also be used. Specific examples thereof include the compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965A. Examples of commercially available products include Megafac RS-101, RS-102, RS-718-K, and RS-72-K manufactured by DIC Corporation.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BA F), Solsperse 20000 (Nippon Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.), Pionein D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

Examples of cationic surfactants include 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.

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.

The content of the surfactant is preferably from 0.001 to 0.2% by mass, more preferably from 0.0015 to 0.1% by mass, based on the total solid content of the negative photosensitive composition. More preferred is 0.05% by mass. Only one type of surfactant may be used, or two or more types may be combined. When two or more types are included, the total amount is preferably within the above range.

<< Silane coupling agent >>
The negative photosensitive composition can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group.

The silane coupling agent is composed of at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. A silane compound having Specific examples of the silane coupling agent include, for example, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyltri Methoxysilane (Shin-Etsu Chemical Co., KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., KBE-602), γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical) Industrial company KBM-903), γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., KBM-503), 3- And glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403). For details of the silane coupling agent, the description of paragraph numbers 0155 to 0158 in JP2013-254047A can be referred to, the contents of which are incorporated herein.

When the negative photosensitive composition contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass with respect to the total solid content of the negative photosensitive composition. 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable. The negative photosensitive composition may contain only one kind of silane coupling agent, or may contain two or more kinds. When two or more silane coupling agents are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
The negative photosensitive composition can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) and the like.
When the negative photosensitive composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the negative photosensitive composition. The negative photosensitive composition 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.

<< UV absorber >>
The negative photosensitive composition may contain an ultraviolet absorber. The ultraviolet absorber is preferably a conjugated diene compound. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.). Further, as the ultraviolet absorber, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a triazine compound, or the like can be used. Specific examples thereof include compounds described in JP2013-68814A. Moreover, as a benzotriazole compound, you may use the MYUA series (Chemical Industry Daily, February 1, 2016) made from Miyoshi oil and fat.

When the negative photosensitive composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, based on the total solid content of the negative photosensitive composition, Is more preferably from 5 to 5% by weight, particularly preferably from 0.1 to 3% by weight. Moreover, only 1 type may be used for an ultraviolet absorber and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Other additives >>
Various additives, for example, fillers, adhesion promoters, antioxidants, anti-aggregation agents, and the like can be blended with the negative photosensitive composition as necessary. Examples of these additives include additives described in JP-A-2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein. As the antioxidant, for example, phenol compounds, phosphorus compounds (for example, compounds described in paragraph No. 0042 of JP2011-90147A), thioether compounds, and 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). Only one type of antioxidant may be used, or two or more types may be used. The negative photosensitive composition can contain a sensitizer and a light stabilizer described in paragraph No. 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph No. 0081 of the publication.

Depending on the raw material used, the negative photosensitive composition may contain a metal element, but from the viewpoint of suppressing the occurrence of defects, the inclusion of a Group 2 element (calcium, magnesium, etc.) in the negative photosensitive composition The amount is preferably 50 ppm by mass or less, more preferably 0.01 to 10 ppm by mass. Further, the total amount of the inorganic metal salt in the negative photosensitive composition is preferably 100 ppm by mass or less, more preferably 0.5 to 50 ppm by mass.

<Method for preparing negative photosensitive composition>
A negative photosensitive composition can be prepared by mixing each component mentioned above. In preparing the negative photosensitive composition, the components constituting the negative photosensitive composition may be blended together, or the components may be blended sequentially after being dissolved or dispersed in an organic solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. Moreover, when a negative photosensitive composition contains a pigment, it is preferable to include the process of dispersing a pigment. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion. Also, “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion Technology and Industrial Application Centered on Suspension (Solid / Liquid Dispersion System)” The process and the disperser described in “Issuance, October 10, 1978” can be preferably used. In the process of dispersing the pigment, the pigment may be refined by a salt milling process. As materials, equipment, processing conditions, etc. used in the salt milling process, for example, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used.

In preparing the negative photosensitive composition, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) And a filter using a material such as polyolefin resin). Among these materials, polypropylene (including high density and ultra high molecular weight high density polypropylene) and nylon are preferable.

The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm.

Also, it is preferable to use a filter using a fiber-like filter medium as the filter. Examples of the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber. Specific examples of filters using fiber-shaped filter media include filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Loki Techno. .

When using filters, different filters may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more.
For example, you may combine the 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, select 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.
Moreover, filtration with a 1st filter may be performed only with a dispersion liquid, and may filter with a 2nd filter, after mixing another component. As the second filter, a filter formed of the same material as the first filter can be used.

The water content of the negative photosensitive composition is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

<Color filter manufacturing method>
The color filter manufacturing method of the present invention includes the above-described pattern manufacturing method of the present invention. The type of pixel in the color filter varies depending on the application, and examples thereof include colored pixels such as red, green, blue, magenta, yellow, and cyan, white (colorless) pixels, and black pixels. The color filter may further include an infrared cut filter and a red transmission filter. The color filter may be a color filter composed of single color pixels, but is preferably a color filter having a plurality of color pixels. In a color filter having a plurality of color pixels, it is preferable that pixels of different colors are adjacent to each other.

In a color filter having pixels of a plurality of colors, it is required to be precise with respect to the pattern size in each color pixel. Variations in the pattern size of each pixel may cause product defects. According to the pattern manufacturing method of the present invention, the allowable range (margin) of exposure energy can be widened, so that a pattern as designed can be easily formed even if the exposure energy varies during exposure. For this reason, the pattern manufacturing method of the present invention is particularly effective when manufacturing a color filter having a plurality of color pixels.

The color filter manufacturing method of the present invention is more effective when manufacturing a color filter having a small pixel size. The width of the pixel is not particularly limited, and is preferably, for example, 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, still more preferably 1 μm or less, and 0.8 μm. It is particularly preferred that There is no lower limit in particular, and it is practical that it is 100 nm or more. Speaking of the pixels of the Bayer pattern, it is preferably 5 μm square or less, more preferably 3 μm square or less, further preferably 2 μm square or less, and even more preferably 1 μm square or less in plan view. Preferably, it is particularly preferably 0.8 μm or less. There is no particular lower limit, and it is practical that it is 100 nm square or more. In addition, it is preferable that the pixels are adjacent to each other because the effects of the present invention are more conspicuous.

The thickness of the pixel is preferably, for example, 0.3 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.75 μm or more. The upper limit is preferably 2 μm or less, more preferably 1.5 μm or less, and particularly preferably 1 μm or less.

<Method for Manufacturing Solid-State Imaging Device and Image Display Device>
A solid-state imaging device, an image display device, and the like can be manufactured using the pattern manufacturing method of the present invention.

The configuration of the solid-state imaging device is not particularly limited as long as the configuration functions as a solid-state imaging device, and examples thereof include the following configurations.

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) on a support; A light-shielding film in which only the light-receiving part of the photodiode is opened on the photodiode and the transfer electrode, a device protection 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 part, and a device A color filter is provided on the protective film. Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective film and below 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 film forming each 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 pixel. Examples of the solid-state imaging device having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A. Further, examples of the CMOS image sensor include a back-illuminated image sensor that can be inverted after being formed with a light receiving portion and bonded to a wiring layer.

Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of the image display device and details of each image display device, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junaki Ibuki, Industrial Book ( Stock), issued in 1989) ”. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Preparation of negative photosensitive composition>
Photosensitive compositions 1 and 2 were produced by mixing the raw materials so that the composition ratio (parts by mass) shown in the following table was obtained.

The raw materials described in the above table are as follows.
(Green pigment dispersion)
C. I. Pigment green 58 in an amount of 7.55 parts by mass; I. 1.89 parts by weight of Pigment Yellow 185, 0.94 parts by weight of Pigment Derivative A, 3.7 parts by weight of Dispersant D-1, and 65.7 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) Were mixed and dispersed for 3 hours using a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)) to prepare a Green pigment dispersion.
Pigment derivative A: compound having the structure shown below

Dispersant D-1: Resin having the following structure (The numerical value attached to the main chain is a molar ratio. The numerical value attached to the side chain indicates the number of repetitions. Acid value = 50 mgKOH / g, Mw = 24000)

(Blue pigment dispersion)
C. I. Pigment Blue 15: 6 and 10.2 parts by mass; I. 1.27 parts by mass of Pigment Violet 23, 24.42 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), 14.62 parts by mass of cyclohexanone, 1.03 parts by mass of propylene glycol monomethyl ether, a dispersant D-2 was mixed with 2.54 parts by mass, and mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism manufactured by Nippon BEE Co., Ltd.) to disperse Blue pigment. A liquid was prepared.
Dispersant D-2: Resin having the following structure (weight average molecular weight = 14000, the numbers attached to the main chain are molar ratios)

(resin)
P-1: ACA230AA (manufactured by Daicel Corporation, Mw = 14000, acid value = 37 mgKOH / g)
P-2: ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)

(Radically polymerizable compound)
M-1: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-2: Aronix TO-2349 (manufactured by Toagosei Co., Ltd.)
M-3: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)

(Surfactant)
S-1: Pionein D-6315 (manufactured by Takemoto Yushi Co., Ltd., nonionic surfactant)
S-2: The following mixture (Mw = 14000,% indicating the ratio of repeating units is mol%)

(Photopolymerization initiator)
I-1, I-2: Compounds having the following structures

Polymerization inhibitor: p-methoxyphenol Epoxy compound: EHPE3150 (manufactured by Daicel Corporation)

(solvent)
Butyl acetate PGMEA: Propylene glycol monomethyl ether acetate

Test Example 1 Pattern Manufacturing Method A 200 mm (8 inch) silicon wafer was heat-treated at 200 ° C. for 1 minute on a hot plate. Next, CT-4000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied on the silicon wafer so as to have a film thickness of 0.1 μm after post-baking. Furthermore, it heated for 5 minutes with a 220 degreeC hotplate (post-baking), the undercoat layer was formed, and the silicon wafer substrate with an undercoat layer was obtained. Each photosensitive composition 1 and 2 was apply | coated on the undercoat layer of the silicon wafer with an undercoat layer so that a film thickness might be set to 0.6 micrometer after post-baking, and the photosensitive composition layer was formed. And this photosensitive composition layer was heat-processed (prebaked) for 120 second using a 100 degreeC hotplate.
Next, using an i-line stepper exposure apparatus FPA5510iZs (manufactured by Canon Inc.), exposure was performed under the following exposure conditions through a mask having a pattern.
Next, the exposed photosensitive composition layer was spray-developed under the following development conditions, and then subjected to heat treatment (post-bake) for 300 seconds using a 220 ° C. hot plate to produce a pattern.

[Exposure conditions]
Exposure wavelength: 365 nm (i-line)
Exposure illuminance: 10,000 W / m ²
Exposure atmosphere: Air (O ₂ concentration 21% by volume)
Lighting conditions: NA / σ = 0.57 / 0.40
Reduction projection magnification: 1/4 reduction Focus: Best focus (focus offset 0.0 μm). Note that, from the depth of focus (DOF) characteristic, the best focus setting value of CD (Critical Dimension) and pattern shape was set as the best focus.
Mask: Mask consisting of the following masks 1 to 7 (target line width 1.0 μm Bayer pattern, mask bias 0.0 μm)
Exposure energy: from 50 mJ / cm ² by increasing the exposure energy to 5 mJ / cm ² intervals were examined optimum exposure energy (Eopt). The optimal exposure energy is a condition of exposure energy that can form a pattern according to the design dimension of the mask.
[Mask type]
Mask 1: Laminated body of Cr and CrO ₂ (Cr / CrO ₂ = 730Å / 300Å, optical density (OD value) = 2.7 at a wavelength of 365 nm)
Mask 2: Laminated body of Cr and CrO ₂ (Cr / CrO ₂ = 1050Å / 300Å, optical density (OD value) at wavelength 365 nm = 3.5)
Mask 3: Laminated body of Cr and CrO ₂ (Cr / CrO ₂ = 1130Å / 300Å, optical density (OD value) at wavelength 365 nm = 3.7)
Mask 4: Laminated body of Cr and CrO ₂ (Cr / CrO ₂ = 1300Å / 300Å, optical density (OD value) = 4.0 at a wavelength of 365 nm)
Mask 5: Laminated body of Cr and CrO ₂ (Cr / CrO ₂ = 1550Å / 300Å, optical density (OD value) at a wavelength of 365 nm = 5.0)
Mask 6: Laminated body of Cr and CrO ₂ (Cr / CrO ₂ = 1800Å / 300Å, optical density (OD value) at wavelength 365 nm = 6.0)
Mask 7: Laminated body of Cr and CrO ₂ (Cr / CrO ₂ = 2050/300 mm, optical density (OD value) at wavelength 365 nm = 7.0)

The optical density (OD value) of the mask was measured under the following conditions.
Apparatus: V-7200 (manufactured by JASCO Corporation)
Reference: Glass substrate on which Cr and CrO ₂ are not deposited Measurement mode: Wavelength scan Measurement wavelength region: 230 nm to 700 nm
Deuterium (D2) lamp: ON
Halogen (WI) lamp: ON

[Development conditions] Spray development The silicon wafer having the photosensitive composition layer after exposure was transported to a development unit of a developing machine (ACT8, manufactured by Tokyo Electron Ltd.) and placed on a spin chuck. While rotating the silicon wafer, a developer (CD-1040, manufactured by Fuji Film Electronics Materials) at 23 ° C. is applied to the photosensitive composition layer from above the rotation center for 10 seconds with two fluids of N _2. It was applied in the form of a spray (N ₂ flow rate 5 to 10 L / min, developer flow rate = 150 mL / min, nozzle height = 20 mm from the silicon wafer). Next, the rotating device was stopped and development was carried out by resting for 60 seconds. After performing a series of these treatments twice in total, the rotating device is operated to rotate the silicon wafer at a rotational speed of 2000 rpm, and the pure water is supplied in a shower form from the straight nozzle above the rotation center to perform the rinsing treatment. (30 seconds) and then spin dried for 20 seconds.

<Test Example 2>
In the pattern production method of Test Example 1, a pattern was produced in the same manner as in Test Example 1 except that the photosensitive composition 1 was used, and the development conditions were changed as follows to perform paddle development.
[Development Conditions] Paddle Development A silicon wafer having a photosensitive composition layer after exposure was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemtronics Co., Ltd.). While rotating the silicon wafer by operating the rotating device, the developer (CD-1040, manufactured by Fuji Film Electronics Materials) at 23 ° C. is applied from the straight nozzle to the photosensitive composition layer from above the rotation center. It was discharged and applied for 2 seconds. Next, the rotating device was stopped and left for 60 seconds for development (paddle development). After performing a series of these treatments twice in total, the rotating device is operated to rotate the silicon wafer at a rotational speed of 2000 rpm, and the pure water is supplied in a shower form from the straight nozzle above the rotation center to perform the rinsing treatment. (30 seconds) and then spin dried for 20 seconds.

<Evaluation of depth of focus (DOF) margin>
Depth of focus (DOF) at best exposure (Eopt) is shifted from the best focus, and the range of focus depth within which the line width variation of the resulting pattern falls within the mask design dimension ± 5% (= 0.95 to 1.05 μm) Asked.

<Evaluation of residue and pattern shape>
The line width measurement electron microscope S9260A (manufactured by Hitachi High-Technologies Corporation) was used to observe the image with a magnification of 20000 times, and the residue and pattern shape between the patterns were observed and measured according to the following criteria.
(Evaluation of residue)
A: There is no residue between patterns.
B: A trace amount of residue exists between patterns.
C: A little residue exists between patterns.
D: There are many residues between patterns.
(Evaluation of pattern shape)
A: The roughness of the edge of the pattern is good.
B: The roughness of the edge of the pattern is good but inferior to A.
C: The roughness of the pattern edge is good but inferior to B.
D: The roughness of the edge of the pattern is bad.

When a mask with an OD value of 2.7 was used, the pattern edge vicinity was defined as the line width of the pattern, but there were many residues and it was not at a practical level.
When spray development was used as the development method, the exposure energy margin, DOF margin, and pattern shape were better than when paddle development was used.

In the above table, exposure energy 1 is exposure energy (mJ / cm ² ) when the line width of the pattern expresses a value of mask design dimension × 95% (= 0.95 μm), and exposure energy 2 The exposure energy (mJ / cm ² ) when the line width of the pattern expresses a value of the mask design dimension × 105% (= 1.05 μm). The larger the difference between the exposure energy 1 and the exposure energy 2, the wider the exposure energy margin.

As shown in the above table, the test example using a mask having an optical density (OD value) of 3.6 or more was excellent with a wide exposure energy margin and a DOF margin. Moreover, there was little residue between patterns and the pattern shape was also excellent.
Further, in Test Example 1 group using spray development as a developing method, generation of residue could be suppressed more easily than in Test Example 2 group using paddle development, and a pattern having excellent rectangularity was easily obtained.

<Test Example 3>
In the pattern manufacturing method of Test Example 1, the same procedure as in Test Example 1 was conducted except that the photosensitive composition 1 was used and the exposure illuminance at the time of exposure and the oxygen concentration at the time of exposure were changed to the conditions described in the following table, respectively. Patterns were manufactured and the resolution was evaluated. The resolution was evaluated by obtaining the exposure energy (optimum exposure energy (Eopt)) that can form a pattern according to the design dimensions of the mask and the Δ exposure energy obtained from the following equation. The design dimension of the mask was 1.0 μm.
Δexposure energy = | exposure energy (mJ / cm ² ) when the line width of the pattern expresses a value of the mask design dimension × 105% (= 1.05 μm) −the line width of the pattern is the mask design dimension × 95 % (= 0.95 μm) exposure energy (mJ / cm ² ) |
A: Δexposure energy is 200 mJ / cm ² or more, and Eopt is in the range of 50 to 500 mJ / cm ² .
B: Δexposure energy is 100 mJ / cm ² or more and less than 200 mJ / cm ² and Eopt is in the range of 50 to 500 mJ / cm ² .
C: Δexposure energy is 50 mJ / cm ² or more and less than 100 mJ / cm ² and Eopt is in the range of 50 to 500 mJ / cm ² .
D: delta exposure energy is less than 50 mJ / cm ^2, and Eopt is in the range of 50 ~ 500mJ / cm ^2.
E: Eopt is less than 50 mJ / cm ² or more than 500 mJ / cm ² .
F: The target dimension cannot be formed.

As shown in the above table, in the test example using a mask having an optical density (OD value) of 3.6 or more, the exposure energy margin was wide. Also, the resolution was excellent. On the other hand, in the test example using the mask having an optical density (OD value) of 2.7, it was judged that the residue was so large that it was not at a practical level.

<Test Example 4>
(Manufacture of color filters)
Green, blue and red pixels are formed between the light-shielding films on the image sensor substrate on which a light-shielding film (tungsten light-shielding film) having a width of 0.1 μm and a height of 0.4 μm is formed, thereby improving processing accuracy. confirmed. The rule of the pixel was 1.0 μm square, and the dimension of the inter-pixel light shielding film was 0.1 μm.
A composition for forming pixels of each color was applied on the substrate on which the light-shielding film was formed so as to have a film thickness of 0.6 μm after post-baking to form a photosensitive composition layer. And this photosensitive composition layer was heat-processed (prebaked) for 120 second using a 100 degreeC hotplate.
Next, exposure was performed under the following conditions. In addition, at the time of exposure of the composition for pixel formation of each color, the position of the base material was detected using an alignment wavelength of 900 nm. As a detection target, a tungsten mark placed on the lower layer of the pixel or a silicon uneven mark stamped on the base material was used.
Next, spray development was performed under the same conditions as in Test Example 1, and then heat treatment (post-baking) was performed for 300 seconds using a 220 ° C. hot plate to produce a pattern. At this time, in order to suppress thermal shrinkage, a sealed hot plate having a low oxygen concentration (oxygen concentration: 100 ppm) was used.
A color filter in which pixels of each color were embedded between the light shielding films could be manufactured.

[Used composition for pixel formation]
Composition for green pixel formation: photosensitive composition 1 described above
Composition for forming blue pixel: photosensitive composition 2 described above
Composition for forming red pixel: SR2000S (manufactured by FUJIFILM Electronics Materials)

[Exposure conditions]
Exposure wavelength: 365 nm (i-line)
Exposure illuminance: 250,000 W / m ²
Exposure atmosphere: Air (O ₂ concentration 35% by volume)
Lighting conditions: NA / σ = 0.57 / 0.50
Reduction projection magnification: 1/4 reduction Focus: Best focus Mask: Mask composed of the above-described mask 5 (target line width 1.0 μm Bayer pattern, mask bias 0.0 μm, mask optical density (OD value) at 365 nm) = 5 .0)
Exposure energy: 250 mJ / cm ² in the case of a composition for a green pixel forming, 320 mJ / cm ² in the case of a composition for a blue pixel forming, 350 mJ / cm ² in the case of a composition for the red pixel formed

(Formation of microlenses)
On the color filter obtained by the above method, the composition of Test 101 of JP-A-2016-74797 was applied and dried, followed by heat sintering (220 ° C. × 5 minutes). A lens material layer was formed (film thickness 1.0 μm). For this lens material layer, a mask was formed on the lens material layer under the following conditions.

[Mask formation conditions]
Photosensitive photoresist: GKR-5113 (trade name; manufactured by FUJIFILM Electronics Materials)
Formed film thickness: 0.7 μm
Pattern size: 1.0 μm square, positive remaining portion 0.8 μm, space portion 0.2 μm.
Exposure energy: 46 mJ / m ² (NA / σ: 0.63 / 0.65)
Pre-bake / post-exposure heating / post-bake: 120 ° C. × 90 seconds / 110 ° C. × 90 seconds / 155 ° C. × 60 seconds

Next, etching was performed under the following conditions to form a microlens on the color filter. The microlens pattern has an array in which there is no gap between lenses in either the pitch direction or the diagonal direction.

[Etching conditions]
Dry etching equipment: U-621 (manufactured by Hitachi High-Technologies Corporation)
Gas flow rate: CF ₄ / C ₄ F ₆ = 350 (mL / min) / 50 (mL / min)
Bias: High frequency (RF) power: 1000W
Antenna bias: 400W
Wafer bias: 400W
Electrode height: 68mm
Pressure: 2.0Pa
Etching time: 500 seconds Substrate temperature: 20 ° C

In this embodiment, the image forming property of the color filter is improved, and the occurrence of flare, color mixing, etc. is suppressed. Therefore, the image quality of the imaging device can be improved.
The present invention is not only a color filter composed of red, green, and blue, but also a white pixel that is transparent to visible light and controls condensing by controlling the refractive index, and blocks visible light so that it can transmit near-infrared light. The present invention can also be suitably applied to an imaging apparatus having infrared transmission filter pixels to be controlled.

<Test Example 5>
[Production of Titanium Black (A-1)]
100 g of titanium oxide MT-150A (trade name: manufactured by Teika Co., Ltd.) having an average particle size of 15 nm, 25 g of silica particles AROPERL (registered trademark) 300/30 (manufactured by Evonik) having a BET surface area of 300 m ² / g, and dispersion 100 g of the agent Disperbyk190 (trade name: manufactured by Big Chemie), add 71 g of ion-exchange water, and use MURASTAR KK-400W manufactured by KURABO for 20 minutes at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm. Gave a homogeneous aqueous mixture. This aqueous solution was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the atmosphere was replaced with nitrogen, and nitriding reduction treatment was performed by flowing ammonia gas at 100 mL / min for 5 hours at the same temperature. After the completion, the collected powder was pulverized in a mortar to obtain titanium black A-1 [dispersed material containing titanium black particles and Si atoms] containing Si atoms and having a powdery specific surface area of 73 m ² / g.

[Preparation of Titanium Black Dispersion (TB Dispersion 1)]
The component shown in the following composition 1 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion a.

(Composition 1)
Titanium black (A-1): 25 parts by mass 30% by mass solution of propylene glycol monomethyl ether acetate in specific resin 1: 25 parts by mass Propylene glycol monomethyl ether acetate (PGMEA): 50 parts by mass

Specific resin 1: Resin having the following structure (The numerical value attached to the main chain is% by mass, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight = 30000, acid value = 60 mgKOH / g, graft chain The number of atoms (excluding hydrogen atoms) is 117). The specific resin 1 was synthesized with reference to the description in JP2013-249417A.

The obtained dispersion a is subjected to a dispersion treatment using the Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. under the following conditions to obtain a titanium black dispersion (hereinafter referred to as TB dispersion 1). Obtained.

(Distribution condition)
・ Bead diameter: 0.05mm in diameter
・ Bead filling rate: 75% by volume
・ Mill peripheral speed: 8m / sec
・ Amount of liquid mixture to be dispersed: 500 g
・ Circulation flow rate (pump supply amount): 13 kg / hour
・ Processing liquid temperature: 25-30 ℃
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Number of passes: 90 passes

[Preparation of black photosensitive composition]
A black photosensitive composition was obtained by mixing the following composition. When a film having a thickness of 1.5 μm was formed using this black photosensitive composition, the resulting film had an optical density of 2.7 at a wavelength of 365 nm. The optical density was measured by the same method as the optical density of the mask.
-TB dispersion 1 ... 58.93 parts by mass-Alkali-soluble resin (Acryl RD-F8, manufactured by Nippon Shokubai Co., Ltd., solid content 40%, solvent: propylene glycol monomethyl ether) ... 10.545 mass Parts Photopolymerization initiator (compound with the following structure): 1.38 parts by mass

Polymerizable compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., hexafunctional polymerizable compound (amount of ethylenically unsaturated group: 10.4 mmol / g), and pentafunctional polymerizable compound (ethylenically unsaturated group) Of 9.5 mmol / g)) ... 6.82 parts by mass Surfactant (Megafac F-780, manufactured by DIC Corporation) ... 0.02 parts by massPropylene glycol monomethyl ether Acetate ... 5.48 parts by massCyclohexanone ... 16.76 parts by mass

(Production of evaluation board)
Substrate type: Black photosensitive composition layer was applied on a glass wafer with an antireflection film of 8 inches (20.32 cm) so that the film thickness was 1.5 μm after post-baking. Formed. And this black photosensitive composition layer was heat-processed (prebaked) for 120 second using a 90 degreeC hotplate.
Next, using an i-line stepper exposure apparatus FPA5510iZs (manufactured by Canon Inc.), exposure was performed under the following exposure conditions through a mask having a pattern.
Subsequently, spray development was performed on the photosensitive composition layer after the exposure under the same conditions as in Test Example 1. Thereafter, heat treatment (post-baking) was performed for 10 minutes using a 150 ° C. hot plate to produce a pattern. At this time, in order to suppress thermal shrinkage, a sealed hot plate having a low oxygen concentration (oxygen concentration: 100 ppm) was used.

[Exposure conditions]
Exposure wavelength: 365nm
Exposure illuminance: 30000 W / m ²
Exposure atmosphere: air (O ₂ concentration 21 volume%) atmosphere or atmosphere with O ₂ concentration 40 volume% Illumination conditions: NA / σ = 0.57 / 0.40
Reduced projection magnification: 1/4 reduction Focus: -0.9 μm to +0.9 μm, pattern was produced with a pitch of 0.3 μm, the best focus was determined to be a focus offset +0.3 μm, and cross-sectional observation was +0.3 μm evaluated.
Mask: Masks 1 to 5 described above (target line width 10 μm line pattern, mask bias 0.0 μm)
Exposure energy: 500 mJ / cm ²

(Measurement of undercut width)
The obtained pattern was subjected to cross-sectional observation (observation magnification 20,000 times), and the undercut width was measured. A scanning microscope (S4800, manufactured by Hitachi High-Technologies Corporation) was used as a measuring device. The undercut width was measured by measuring the width of a region (width of an arrow line in FIG. 2) that is separated from the substrate at the bottom of the pattern from the top of the pattern eaves in the cross-sectional observation of the pattern. The undercut width is preferably 0.5 μm or less, and more preferably 0.3 μm or less.

As shown in the above table, the use of a mask having an optical density of 3.6 or more can effectively suppress the occurrence of undercut. Moreover, the undercut could be more effectively suppressed by increasing the oxygen concentration during exposure.

<Test Example 6>
(Production of photosensitive composition 101, photosensitive composition 201, photosensitive composition 301, photosensitive composition 401, photosensitive composition 501, and photosensitive composition 601)
Each photosensitive composition was manufactured by mixing each raw material so that the composition ratio (part by mass) described in the following table was obtained.

(Production of photosensitive compositions 102 to 105)
Photosensitive compositions 102 to 105 were produced in the same manner as the photosensitive composition 101 except that the same amount of the green pigment dispersions 102 to 105 was used instead of the green pigment dispersion 101.

(Production of photosensitive compositions 202 to 205)
Photosensitive compositions 202 to 205 were produced in the same manner as the photosensitive composition 201 except that the same amount of the green pigment dispersions 202 to 205 was used instead of the green pigment dispersion 201.

(Production of photosensitive compositions 302 to 305)
Photosensitive compositions 302 to 305 were produced in the same manner as the photosensitive composition 301 except that the same amount of the yellow pigment dispersion liquids 102 to 105 was used instead of the yellow pigment dispersion liquid 101.

(Production of photosensitive compositions 402 to 405)
Photosensitive compositions 402 to 405 were produced in the same manner as the photosensitive composition 401 except that the same amount of the yellow pigment dispersions 102 to 105 was used instead of the yellow pigment dispersion 101.

(Production of photosensitive compositions 502 to 505)
Photosensitive compositions 502 to 505 were produced in the same manner as the photosensitive composition 501, except that the same amount of the yellow pigment dispersions 102 to 105 was used instead of the yellow pigment dispersion 101.

(Production of photosensitive compositions 602 to 605)
Photosensitive compositions 602 to 605 were produced in the same manner as the photosensitive composition 601, except that the same amount of the yellow pigment dispersion liquids 102 to 105 was used instead of the yellow pigment dispersion liquid 101.

Each of the obtained photosensitive compositions was evaluated in the same manner as in Test Examples 1 to 3, and good results were obtained in all cases.

The raw materials used for each photosensitive composition are as follows.

(Green pigment dispersion 101)
C. I. CI Pigment Green 58, 8.5 parts by mass; I. Pigment Yellow 150 (4.6 parts by mass), Pigment Derivative A (1.3 parts by mass), Dispersant D-1 (5.1 parts by mass), and Propylene glycol monomethyl ether acetate (PGMEA) (80. parts by mass). 4 parts by mass is mixed, and mixed and dispersed for 3 hours using a bead mill (high pressure disperser with pressure reducing mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) to prepare Green pigment dispersion 101 did.

(Green pigment dispersion 102)
C. I. Green pigment dispersion liquid 102 was prepared in the same manner as Green pigment dispersion liquid 101, except that the pigment of Sample 3 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Green pigment dispersion 103)
C. I. Green pigment dispersion 103 was prepared in the same manner as Green pigment dispersion 101 except that the pigment of Sample 10 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Green pigment dispersion 104)
C. I. Green pigment dispersion 104 was prepared in the same manner as Green pigment dispersion 101 except that the pigment of Sample 15 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Green pigment dispersion 105)
C. I. Green pigment dispersion 105 was prepared in the same manner as Green pigment dispersion 101 except that the pigment of Sample 29 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Green pigment dispersion 201)
C. I. CI pigment green 36 is 8.5 parts by mass; I. Pigment Yellow 150 (4.6 parts by mass), Pigment Derivative A (1.3 parts by mass), Dispersant D-1 (5.1 parts by mass), and Propylene glycol monomethyl ether acetate (PGMEA) (80. parts by mass). 4 parts by mass is mixed, and mixed and dispersed for 3 hours using a bead mill (high pressure disperser with pressure reducing mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) to prepare Green pigment dispersion 201 did.

(Green pigment dispersion 202)
C. I. Green pigment dispersion 202 was prepared in the same manner as Green pigment dispersion 201 except that the pigment of Sample 3 of JP-A-2017-171914 was used instead of Pigment Yellow 150.

(Green pigment dispersion 203)
C. I. Green pigment dispersion 203 was prepared in the same manner as Green pigment dispersion 201 except that the pigment of Sample 10 of JP-A-2017-171914 was used instead of Pigment Yellow 150.

(Green pigment dispersion 204)
C. I. Green pigment dispersion 204 was prepared in the same manner as Green pigment dispersion 201 except that the pigment of Sample 15 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Green pigment dispersion 205)
C. I. Green pigment dispersion 205 was prepared in the same manner as Green pigment dispersion 201 except that the pigment of Sample 29 of JP-A-2017-171914 was used instead of Pigment Yellow 150.

(Yellow pigment dispersion 101)
C. I. 11.3 parts by mass of Pigment Yellow 150, 1.6 parts by mass of the pigment derivative A described above, 3.9 parts by mass of the dispersant D-1 described above, and 83. parts of propylene glycol monomethyl ether acetate (PGMEA). 2 parts by mass is mixed, and mixed and dispersed for 3 hours using a bead mill (high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)) to prepare Yellow pigment dispersion 101. did.

(Yellow pigment dispersion 102)
C. I. A Yellow pigment dispersion liquid 102 was prepared in the same manner as the Yellow pigment dispersion liquid 101, except that the pigment of Sample 3 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Yellow pigment dispersion 103)
C. I. A Yellow pigment dispersion 103 was prepared in the same manner as the Yellow pigment dispersion 101 except that the pigment of Sample 10 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Yellow pigment dispersion 104)
C. I. A Yellow pigment dispersion 104 was prepared in the same manner as the Yellow pigment dispersion 101 except that the pigment of Sample 15 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Yellow pigment dispersion 105)
C. I. A Yellow pigment dispersion 105 was prepared in the same manner as the Yellow pigment dispersion 101 except that the pigment of Sample 29 of JP-A No. 2017-171914 was used instead of Pigment Yellow 150.

(Red pigment dispersion 101)
C. I. 11.6 parts by weight of Pigment Red 254, 1.4 parts by weight of the pigment derivative A described above, 4.5 parts by weight of the dispersant D-3 shown below, and 82 parts of propylene glycol monomethyl ether acetate (PGMEA) And mixing and dispersing for 3 hours using a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by BB Co., Ltd. Japan)) to prepare a Red pigment dispersion 101. Prepared.
Dispersant D-3: Resin having the following structure (the numerical value attached to the main chain is a molar ratio. The numerical value attached to the side chain represents the number of repetitions. Mw = 24000)

(Red pigment dispersion 201)
C. I. Pigment Red 264, 11.6 parts by mass, Pigment derivative A, 1.4 parts by mass, Dispersant D-3, 4.5 parts by mass, and Propylene glycol monomethyl ether acetate (PGMEA), 82. 5 parts by mass is mixed, and mixed and dispersed for 3 hours using a bead mill (high pressure disperser with pressure reducing mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) to prepare Red pigment dispersion 201. did.

(Red pigment dispersion 301)
C. I. 11.6 parts by weight of Pigment Red 177, 1.4 parts by weight of the pigment derivative A described above, 4.5 parts by weight of the dispersant D-3 described above, and 82 .mu.m of propylene glycol monomethyl ether acetate (PGMEA). 5 parts by mass is mixed and mixed and dispersed for 3 hours using a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism manufactured by Nippon BEE Co., Ltd.) to prepare a Red pigment dispersion 301. did.

(resin)
P-2: The above-described resin P-2

(Radically polymerizable compound)
M-1, M-3: The above-mentioned radical polymerizable compounds M-1, M-3
M-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(Surfactant)
S-2: The above-described surfactant S-2
S-3: KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd., siloxane surfactant)

(Photopolymerization initiator)
I-3: IRGACURE OXE02 (manufactured by BASF, oxime initiator)

(UV absorber)
U-1: UV-503 (Daito Chemical Co., Ltd.)

Polymerization inhibitor: p-methoxyphenol Epoxy compound: EHPE3150 (manufactured by Daicel Corporation)
PGMEA: Propylene glycol monomethyl ether acetate

1: Condenser lens 2: Projection lens 4: Work piece 5: Reticle

Claims (14)

1. Applying a negative photosensitive composition on a support to form a negative photosensitive composition layer;
   Exposing the negative photosensitive composition layer through a mask having a pattern;
   Removing the negative photosensitive composition layer in the unexposed area and developing;
   A method for producing a pattern including:
   The said mask is a manufacturing method of the pattern whose optical density with respect to the light of the wavelength used for the said exposure is 3.6 or more.
2. 2. The pattern manufacturing method according to claim 1, wherein the mask has an optical density of 3.6 or more with respect to light having a wavelength of 365 nm.
3. 3. The pattern manufacturing method according to claim 1, wherein the mask includes at least one selected from chromium and a chromium compound.
4. The method for producing a pattern according to any one of claims 1 to 3, wherein the negative photosensitive composition comprises a photopolymerization initiator and a radical polymerizable compound.
5. 5. The method for producing a pattern according to claim 1, wherein the negative photosensitive composition contains a colorant.
6. 6. The method for producing a pattern according to claim 1, wherein the negative photosensitive composition contains transparent particles.
7. 7. The method for producing a pattern according to claim 1, wherein the negative photosensitive composition is a negative photosensitive composition for forming a pixel of a color filter.
8. The pattern manufacturing method according to any one of claims 1 to 7, wherein an exposure illuminance is 5000 to 50000 W / m ² during the exposure.
9. The pattern manufacturing method according to any one of claims 1 to 8, wherein an oxygen concentration is 21% or more during the exposure.
10. 10. The method for producing a pattern according to claim 1, wherein in the development, a developer is spray-coated on the negative photosensitive composition layer.
11. A method for producing a color filter, comprising the method for producing a pattern according to any one of claims 1 to 10.
12. A method for manufacturing a color filter having a plurality of color pixels, wherein at least one of the plurality of color pixels is formed using the pattern manufacturing method according to any one of claims 1 to 10. The manufacturing method of a color filter.
13. A method for producing a solid-state imaging device, comprising the method for producing a pattern according to any one of claims 1 to 10.
14. An image display device manufacturing method including the pattern manufacturing method according to any one of claims 1 to 10.

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