WO2016208479A1

WO2016208479A1 - Method for producing cured film, and cured film

Info

Publication number: WO2016208479A1
Application number: PCT/JP2016/067877
Authority: WO
Inventors: 光司吉林
Original assignee: 富士フイルム株式会社
Priority date: 2015-06-22
Filing date: 2016-06-16
Publication date: 2016-12-29
Also published as: TW201706731A; TWI693484B; JPWO2016208479A1; KR20170141802A; KR102028938B1; JP6445156B2

Abstract

Provided are: a method for producing a cured film, whereby it becomes possible to produce a cured film having excellent reliability by a low-temperature process; and a cured film. A method for producing a cured film, comprising a step of irradiating a layer that is provided on a base material and is made from an active energy ray-curable composition with an electron beam having an accelerating voltage of 10 kV or more and less than 100 kV, wherein the operations throughout the process are carried out at a temperature of 100°C or lower.

Description

Method for producing cured film and cured film

The present invention relates to a method for producing a cured film using an electron beam, and a cured film.

In the method for producing a cured film, heat treatment is performed to sufficiently cure the curable composition. For example, the color filter is manufactured as follows. First, a curable composition (colored composition) containing a colorant is applied onto a substrate such as a glass substrate to form a colored composition layer. Next, the colored composition layer is exposed and developed to form a pattern. Next, the patterned colored composition layer is heat-treated (post-baked) to sufficiently cure the colored composition layer. In this way, the color filter is manufactured.
Also known is a method for producing a cured film by irradiating a curable composition with an electron beam (see Patent Documents 1 to 5).

Japanese Patent Laid-Open No. 10-268515 Japanese Patent Laid-Open No. 2004-12443 JP 2010-107928 A Japanese Unexamined Patent Publication No. 2009-244689 JP 2004-123802 A

Conventionally, a cured film has been manufactured on a base material made of a material having excellent heat resistance such as silicon.
In recent years, it has been required to produce a cured film on a substrate having poor heat resistance. In producing a cured film on a substrate having inferior heat resistance, it is desirable to produce a cured film by, for example, a low-temperature process of 100 ° C. or less to suppress thermal damage to the substrate. However, when a cured film is produced by a low-temperature process, problems such as abnormal appearance, large fluctuations in film thickness, large fluctuations in transmittance, etc. are likely to occur after performing a temperature cycle test or a constant temperature and humidity test. Compared with the cured film manufactured through the heat treatment at 1, the reliability of the cured film tended to be inferior.

Therefore, an object of the present invention is to provide a method for producing a cured film and a cured film, which can produce a cured film having excellent reliability by a low temperature process.

As a result of various studies by the present inventors, it has been found that a cured film having excellent reliability can be produced by a low-temperature process by irradiating an active energy ray-curable composition with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. The present invention has been completed. The present invention provides the following.
<1> A method for producing a cured film, comprising a step of irradiating an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV to a layer of an active energy ray-curable composition on a substrate, which is 100 ° C. throughout the entire process. The manufacturing method of the cured film performed at the following temperature.
<2> The method for producing a cured film according to <1>, wherein the active energy ray-curable composition contains an alkali-soluble resin.
<3> The method for producing a cured film according to <1> or <2>, wherein the base material is a thermoplastic resin base material composed of a thermoplastic resin having a glass transition temperature of 100 ° C. or lower.
<4> The method for producing a cured film according to <1> or <2>, wherein the substrate is a glass substrate having a thickness of 0.5 mm or less.
<5> The method for producing a cured film according to <1> or <2>, wherein the base material includes an organic semiconductor layer.
<6> The method for producing a cured film according to <1> or <2>, wherein the substrate has an organic semiconductor layer on the surface.
<7> The curing according to any one of <1> to <6>, further including a step of exposing the layer of the active energy ray-curable composition, wherein the step of irradiating the electron beam is performed after the step of exposing. A method for producing a membrane.
<8> Further, an electron beam includes a step of exposing the layer of the active energy ray-curable composition, and a step of developing the layer of the active energy ray-curable composition after the step of exposing to form a pattern. The method for producing a cured film according to any one of <1> to <6>, wherein the step of irradiating is performed after the step of forming the pattern.
<9> The method for producing a cured film according to <7> or <8>, wherein the exposing step is performed using ultraviolet rays.
<10> The active energy ray-curable composition comprises 0.01 to 5.0% by mass of a silane coupling agent in the solid content of the active energy ray-curable composition, according to <1> to <9> The manufacturing method of the cured film in any one.
<11> The method for producing a cured film according to <10>, wherein the active energy ray-curable composition contains a thermosetting resin.
<12> The method for producing a cured film according to any one of <1> to <11>, wherein the active energy ray-curable composition contains at least one selected from a chromatic colorant and a black colorant.
<13> The method for producing a cured film according to any one of <1> to <12>, wherein the cured film has an optical density of 1 or more with respect to any wavelength in a wavelength range of 260 to 440 nm.
<14> The method for producing a cured film according to <13>, wherein the cured film has a minimum optical density of 1 or more in a wavelength range of 260 to 440 nm.
<15> The method for producing a cured film according to <13>, wherein the cured film has an optical density of 1 or more with respect to a wavelength of 365 nm.
<16> The method for producing a cured film according to any one of <1> to <15>, wherein the active energy ray-curable composition contains a photopolymerization initiator and a radical polymerizable compound.
<17> The method for producing a cured film according to any one of <1> to <15>, wherein the active energy ray-curable composition contains an acid generator and a cationically polymerizable compound.
<18> The method for producing a cured film according to any one of <1> to <17>, wherein the cured film has a thickness of 0.1 to 45 μm.
<19> The cured film according to any one of <1> to <18>, wherein the active energy ray-curable composition is applied onto a substrate and then dried to form a layer of the active energy ray-curable composition. Manufacturing method.
<20> The method for producing a cured film according to any one of <1> to <19>, comprising a step of vacuum drying.
<21> The method for producing a cured film according to any one of <1> to <20>, further comprising a step of heat-treating the layer irradiated with the electron beam at a temperature of 100 ° C. or lower.
<22> The base material is a thermoplastic resin base material, and the heat treatment is performed at a temperature not higher than the glass transition temperature of the thermoplastic resin base material and not higher than 100 ° C. A method for producing a cured film.
<23> A cured film obtained by the method for producing a cured film according to any one of <1> to <22>.

According to the present invention, it is possible to provide a cured film manufacturing method and a cured film that can manufacture a cured film having excellent reliability by a low-temperature process.

It is a figure which shows the spectrum of the cured film before and after color mixing evaluation.

Hereinafter, the contents of the present invention will be described in detail.
In the notation of “group (atomic group)” in this specification, the notation that does not indicate substitution and non-substitution is meant to include not only those having no substituent but also those having 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).
As used herein, “light” means actinic rays or radiation. “Actinic light” or “radiation” means, for example, the emission line spectrum of a mercury lamp and far ultraviolet rays, extreme ultraviolet rays (EUV light) typified by excimer laser, X-rays, electron beams, and the like.
In this specification, “exposure” means not only exposure using far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays and EUV light, but also particle beams such as electron beams and ion beams, unless otherwise specified. Including drawing used.
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 the present specification, the “total solid content” refers to the total mass of components excluding the solvent from the total composition.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ") Allyl" represents both and / or allyl and methallyl, and "(meth) acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement.

<Method for producing cured film>
In the method for producing a cured film of the present invention, an electron having an acceleration voltage of 10 kV or more and less than 100 kV is applied to a layer of an active energy ray curable composition (hereinafter also referred to as an active energy ray curable composition layer) on a substrate. It is a manufacturing method of a cured film including the process of irradiating a line, and the manufacturing method of a cured film is performed at the temperature of 100 degrees C or less through all the processes.
According to the present invention, the active energy ray-curable composition layer is irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV at a low temperature of 100 ° C. or lower (hereinafter also referred to as a low-temperature process) throughout the entire process. Even if it goes, the cured film excellent in reliability can be manufactured.
In the present invention, “performed at a temperature of 100 ° C. or lower throughout all steps” means that all steps of curing the active energy ray-curable composition layer to form a cured film are performed at a temperature of 100 ° C. or lower. This means that each step of the manufacturing process of the cured film is performed at a temperature of 100 ° C. or less. That is, when the manufacturing process of the cured film further includes other steps in addition to the step of irradiating the electron beam, the other steps are also performed at a temperature of 100 ° C. or lower. For example, when it further has the process of forming an active energy ray curable composition layer on a base material, the process of forming an active energy ray curable composition layer is also performed at 100 degrees C or less. Moreover, when it has further the process to expose with respect to the active energy ray curable composition layer on a base material, the process to expose is also performed at 100 degrees C or less. Moreover, when it has the process of forming a pattern with respect to the active energy ray curable composition layer on a base material, the process of forming a pattern is also performed at the temperature of 100 degrees C or less. Moreover, when it has the process of performing post-processing, such as heat processing with respect to the active energy ray-curable composition layer after electron beam irradiation, post-processing is also performed at the temperature of 100 degrees C or less.
In addition, after forming the cured film, dicing (dividing into chips), bonding, or the like may be further performed. However, the process after the cured film is formed is not included in the “all processes” in the present invention. That is, the process after forming the cured film may be performed at a temperature exceeding 100 ° C. For example, when a thin film glass substrate is used as the substrate, cracking and warping may occur in the substrate if it is performed at a temperature exceeding 100 ° C. during formation of the cured film, but the temperature exceeds 100 ° C. after dicing. This is because cracking and warping are less likely to occur even when heated.
Hereinafter, each process is demonstrated in order about the manufacturing method of the cured film of this invention.

An active energy ray-curable composition layer is formed on a substrate using the active energy ray-curable composition. The active energy ray-curable composition will be described later.

As a base material, the base material comprised with glass, a silicon | silicone, resin etc. can be mentioned, for example. As glass, Corning's non-alkali glass Eagle series, 1737, such as glass used for optical equipment and display equipment, glass with an organic layer formed by dispersing or kneading a dye having a UV cut or infrared cut function (Including a form sandwiched with glass). Examples of the resin include polyethylene, polypropylene, vinyl chloride, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, acrylic, polyvinyl alcohol, vinylidene chloride, polycarbonate, polyamide, polyacetal, polybutylene. A terephthalate, a fluororesin, etc. are mentioned, Among these, it can be used combining 1 type (s) or 2 or more types. An organic light emitting layer, an organic semiconductor layer such as an organic photoelectric conversion layer, or the like may be formed on these base materials. Examples of the organic semiconductor include organic electro-renaissance (OLED), organic field effect transistor (OFET), and organic solar cell (OPV). Moreover, in this invention, an organic-semiconductor layer can also be used as a base material.
Although the film thickness of a base material changes with uses and materials, the thickness of a general base material is applicable.

According to the present invention, a cured film can be formed without damaging the substrate even for a substrate with poor heat resistance, and thus is particularly effective for a substrate with low heat resistance. Examples of the substrate having low heat resistance include a glass substrate having a thickness of 0.5 mm or less, a thermoplastic resin substrate, a substrate including an organic semiconductor layer (preferably a substrate having an organic semiconductor layer on the surface), and the like. Is mentioned.
Among the thermoplastic resin substrates, for example, in the case of a substrate composed of a thermoplastic resin having a glass transition temperature of 95 ° C. or lower, the effect of the present invention is remarkable. Particularly in a flexible substrate, a thermoplastic resin having a glass transition temperature of 90 ° C. or lower is more used. Particularly in recent years, those having a glass transition temperature of 70 ° C. or lower are particularly preferably used. The lower limit of the glass transition temperature of the thermoplastic resin is not particularly limited. For example, it may be normal temperature (23 ° C.) or higher. Moreover, the temperature below normal temperature can also be made into a lower limit. For example, the temperature can be 0 ° C. or higher, −50 ° C. or higher, −100 ° C. or higher, or −150 ° C. or higher.
In the present invention, when the thermoplastic resin has two or more glass transition temperatures, the lower temperature is set as the value of the glass transition temperature in the present invention.
The upper limit of the film thickness of the glass substrate is preferably 0.5 mm or less, and more preferably 0.3 mm or less. Although a minimum is not specifically limited, It can also be 0.1 mm or more.

As an application method of the active energy ray-curable composition to the substrate, various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method, spray coating and the like can be used. The application amount of the active energy ray-curable composition is preferably adjusted so that the film thickness after drying is 0.1 to 45 μm. For example, the upper limit is more preferably 44 μm or less, still more preferably 43 μm or less, and particularly preferably 40 m or less. For example, the lower limit is more preferably 0.2 μm or more.

In the present invention, the active energy ray-curable composition layer formed on the substrate may be dried. Drying includes room temperature drying, heat drying, vacuum drying, and the like, and vacuum drying is preferred because of drying speed and low temperature drying.
The vacuum drying is preferably performed under conditions of a degree of vacuum of 0.02 PaG or more and a temperature of 100 ° C. or less. The degree of vacuum is more preferably 0.05 PaG or more, and further preferably 0.09 PaG or more. The higher the degree of vacuum, the faster the drying speed and the shorter the drying time. The temperature condition is more preferably 70 ° C. or lower. The lower limit can be, for example, 23 ° C. or higher, and can be 30 ° C. or higher. The drying time is preferably 30 seconds to 1 hour, more preferably 1 minute to 30 minutes, and even more preferably 2 minutes to 20 minutes.
The heat drying is preferably performed at 100 ° C. or less, more preferably 80 ° C. or less, and further preferably 70 ° C. or less. A lower limit can be 23 degreeC or more, for example. The heating time is preferably 30 seconds to 1 hour, more preferably 1 minute to 30 minutes, and even more preferably 2 minutes to 20 minutes.
In addition, drying may be performed immediately before the process of irradiating the electron beam mentioned later, and may be performed after the process of irradiating an electron beam. Further, it may be performed before or after the development processing described later.

In the present invention, the active energy ray-curable composition layer formed on the substrate may be exposed. The exposure may be a whole surface exposure or a pattern exposure through a mask.
For example, pattern exposure can be performed by exposing the active energy ray-curable composition layer formed on the base material through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
The radiation (light) that can be used for exposure is preferably ultraviolet rays. Examples of ultraviolet rays include g-line, i-line, KrF, ArF and the like, and i-line is preferable. Irradiation dose (exposure dose), for example, preferably 30 ~ 5000mJ / cm ^2, more preferably 50 ~ 4000mJ / cm ^2, more preferably 80 ~ 3000mJ / cm ^2.

When the active energy ray-curable composition layer is exposed in a pattern, it is preferable to develop and remove the unexposed portion to form a pattern. The development removal of the unexposed portion can be performed using a developer. Thereby, the active energy ray-curable composition layer in the unexposed part is eluted in the developer, and only the photocured part remains.
As the developer, an alkali developer that does not damage the substrate is desirable.
The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as choline, pyrrole, piperidine and 1,8-diazabicyclo [5.4.0] -7-undecene.
Moreover, you may use an inorganic alkaline compound as an alkali agent used for a developing solution. As the inorganic alkaline compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.
An alkaline aqueous solution obtained by diluting these alkali agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.
Further, a surfactant may be used for the developer. Examples of the surfactant include surfactants described in the later-described active energy ray-curable composition, and nonionic surfactants are preferable. When the developer contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, and 0.01 to 1.0% by mass with respect to the total mass of the developer. More preferred.
When using a developer comprising such an alkaline aqueous solution, it is generally preferable to rinse (rinse) with pure water after development.
It is preferable to perform the drying described above after, for example, spin drying after washing.

Next, the active energy ray-curable composition layer on the substrate is irradiated with an electron beam. In the case where the active energy ray-curable composition layer is subjected only to the exposure and not subjected to the development, it is preferable to irradiate an electron beam after the exposure. Moreover, when patterning is performed on the active energy ray-curable composition layer (when exposure and development are performed), it is preferable to irradiate an electron beam after forming the pattern of the active energy ray-curable composition layer.

Acceleration voltage of electron beam is 10 kV or more and less than 100 kV. The lower limit is preferably 15 kV or more, more preferably 20 kV or more, and further preferably 30 kV or more. The upper limit is preferably 99 kV or less, more preferably 98 kV or less, and even more preferably 97 kV or less. When the acceleration voltage of the electron beam is in the above range, a cured film having excellent reliability can be produced. Furthermore, the appearance and spectral characteristics of the cured film obtained are also good.

The tube current of the electron beam is preferably 0.01 to 10 mA. If the tube current of the electron beam is in the above range, the electron beam density emitted from the filament is sufficiently maintained, and a cured film having excellent reliability can be produced. Furthermore, the appearance and spectral characteristics of the cured film obtained are also good. The tube current of the electron beam is preferably 0.01 mA or more, more preferably 0.1 mA or more, and further preferably 1 mA or more. The upper limit is preferably 10 mA or less, more preferably 9 mA or less, and even more preferably 8 mA or less. As long as the durability of the filament is maintained, the setting of the tube current is preferably large.

The electron beam is preferably irradiated in a range where the absorbed dose of the electron beam of the cured film is 10 kGy or more. When the absorbed dose of the electron beam is within the above range, a cured film having excellent reliability can be produced. The absorbed dose of the electron beam is more preferably 15 kGy or more, and further preferably 20 kGy or more.

In the step of irradiating with an electron beam, the treatment temperature (temperature in the apparatus) is 100 ° C. or lower, preferably 80 ° C. or lower, and more preferably 70 ° C. or lower. The lower limit can be, for example, 10 ° C. or higher, 15 ° C. or higher, or 20 ° C. or higher.
Moreover, it is preferable that the electron beam irradiation is performed in an atmosphere having an oxygen concentration of 3000 ppm by volume or less. The oxygen concentration is more preferably 1000 ppm by volume or less.
The clearance between the base material and the electron irradiation source is preferably 1 to 30 mm, more preferably 5 to 10 mm.

In the manufacturing method of the cured film of this invention, you may heat-process at the temperature of 100 degrees C or less with respect to the active energy ray curable composition layer which irradiated the electron beam. By heat treatment, drying of the cured film can be promoted, and the curability of the cured film can be stabilized.
The heat treatment temperature is preferably, for example, a temperature exceeding 23 ° C. to 100 ° C. or less. The upper limit is more preferably 80 ° C. or less, and further preferably 70 ° C. or less. Moreover, when a thermoplastic resin base material is used as the base material, the upper limit of the heat treatment temperature is a temperature of 100 ° C. or lower, preferably a temperature not higher than the glass transition of the thermoplastic resin base material. In addition, when the glass transition temperature of a thermoplastic resin base material exceeds 100 degreeC, the upper limit of heat processing temperature is 100 degreeC.
The heat treatment is performed by continuously heating the active energy ray-curable composition layer after electron beam irradiation using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so as to satisfy the above conditions. It can be performed in a batch or batch mode.
Further, vacuum drying may be performed instead of the heat treatment. Further, heat treatment and vacuum drying may be used in combination.

<Active energy ray-curable composition>
Next, the active energy ray-curable composition used in the method for producing a cured film of the present invention will be described.
In the present invention, any active energy ray-curable composition can be preferably used as long as it is a composition that cures upon irradiation with active energy rays. Here, active energy rays refer to those that can impart energy capable of generating starting species in the composition by irradiation, such as α rays, γ rays, X rays, ultraviolet rays, visible rays, An electron beam etc. are mentioned.

<< Resin >>
The active energy ray-curable composition preferably contains a resin. The resin is blended, for example, for the purpose of dispersing a pigment or the like in the composition and the purpose of a binder. A resin used mainly for dispersing pigments is also called a dispersant. However, such use of the resin is merely an example, and the resin can be used for other purposes.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is more preferably 1,000,000 or less, and further preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and even more preferably 5,000 or more.
Resins include (meth) acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyarylene ether phosphine oxide resin, polyimide Examples thereof include resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and siloxane resins. One of these resins may be used alone, or two or more thereof may be mixed and used.

In the active energy ray-curable composition, the content of the resin is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total solid content of the active energy ray-curable composition. The active energy ray-curable composition may contain only one type of resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<<< Alkali-soluble resin >>>
The active energy ray-curable composition preferably contains an alkali-soluble resin as a resin. By containing an alkali-soluble resin, developability and pattern formability are improved. The alkali-soluble resin can also be used as a dispersant or a binder.

The molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000.
The alkali-soluble resin may be a linear organic polymer, and at least one alkali solution is dissolved in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can select suitably from resin which has group which accelerates | stimulates.

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

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

As the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used. Examples thereof include alkali-soluble phenol resins such as maleic acid copolymers and novolac resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins 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 therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of the vinyl compound include hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. , Styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, poly Styrene macromonomer, polymethylmethacrylate 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. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

Moreover, in order to improve the crosslinking efficiency of the active energy ray-curable composition layer, an alkali-soluble resin having a polymerizable group may be used. 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 containing a polymerizable group in a side chain is useful. The alkali-soluble resin having a polymerizable group may be a thermosetting resin or a photocurable resin.
Examples of the alkali-soluble resin containing a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic acid oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscote R-264, and KS resist. 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA, thermosetting resin), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation) ), Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)

As alkali-soluble resins, benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / A multi-component copolymer composed of (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / A 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.

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

In formula (ED1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description of JP 2010-168539 A can be referred to.

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

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.

The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms that may contain a benzene ring. 20 alkyl groups are represented. 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 alkyl group of R ₃ has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and the alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

Specific examples of the alkali-soluble resin include the following.

The alkali-soluble resin can be referred to the description in paragraph Nos. 0558 to 0571 in JP 2012-208494 A (corresponding to paragraph numbers 0685 to 0700 in US 2012/0235099). Incorporated in the description.
Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 of JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraphs 0088 to 0098 of JP 2012-208474 A 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 No. -032770, paragraph number 003 It is also possible to use a binder resin according to ~ 0072. These contents are incorporated herein.

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

The content of the alkali-soluble resin is preferably 0.1 to 20% by mass with respect to the total solid content of the active energy ray-curable composition. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is more preferably 12% by mass or less, and further preferably 10% by mass or less. The active energy ray-curable composition may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<<< Dispersant >>>
The active energy ray-curable composition can contain a dispersant as a resin.
The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin contains a repeating unit having an acid group, the residue generated on the base can be further reduced when a pattern is formed by photolithography.
The repeating unit having an acid group can be constituted using a monomer having an acid group. Examples of the monomer having an acid group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, ω-carboxy- Polycaprolactone mono (meth) acrylate can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Among them, from the viewpoint of developing removability of the unexposed area, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, etc. An addition reaction product with an anhydride is preferred.
Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid.
Examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), and the like.
As the repeating unit having an acid group, the description in paragraph numbers 0067 to 0069 of JP-A-2008-165059 can be referred to, and the contents thereof are incorporated in the present specification.

The resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity for the solvent by the graft chain, it is excellent in pigment dispersibility and dispersion stability after aging. In addition, the composition has an affinity with a polymerizable compound or an alkali-soluble resin due to the presence of the graft chain, so that a residue can be hardly formed by alkali development.
In the present invention, the graft copolymer means a resin having a graft chain. The graft chain means from the base of the main chain of the polymer to the end of the group branched from the main chain.

In the present invention, the graft copolymer is preferably a resin having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000.
Further, the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, more preferably 50 to 2,000, and still more preferably 60 to 500.

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

As the macromonomer used when the graft copolymer is produced by radical polymerization, a known macromonomer can be used, which is a macromonomer AA-6 (polymethacrylic group whose terminal group is a methacryloyl group) manufactured by Toagosei Co., Ltd. Acid-6), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polyester whose terminal group is a methacryloyl group) Butyl acrylate), PLACEL FM5 manufactured by Daicel Corporation (2-hydroxyethyl methacrylate with 5 molar equivalents of ε-caprolactone), FA10L (2-hydroxyethyl acrylate with 10 molar equivalents of ε-caprolactone), And polyester-based mac described in JP-A-2-272009 And monomers.

In the present invention, a graft copolymer containing a repeating unit represented by any of the following formulas (1) to (4) can also be used as the resin. These graft copolymers can be particularly preferably used as a dispersant for a black pigment.

In the formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms.
In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

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

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited. Specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group, etc. Is mentioned. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 5 carbon atoms. 24 alkyl groups or alkoxy groups are preferable, and among them, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. . The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

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

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

The repeating unit represented by the formula (1) is more preferably a repeating unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability.
The repeating unit represented by the formula (2) is more preferably a repeating unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.

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

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

In addition, the graft copolymer described above preferably has a hydrophobic repeating unit in addition to the repeating units represented by the above formulas (1) to (4). However, in the present invention, the hydrophobic repeating unit is a repeating unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

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

logP is the common logarithm of the partition coefficient P (Partition Coefficient), and quantifies how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a typical numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

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

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

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

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, where R ³¹ Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), or combinations thereof.
L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) _n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

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

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

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

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

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

Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like. As examples of the compounds represented by formulas (i) to (iii), the compounds described in paragraph numbers 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification. .

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

In addition to the repeating units represented by the above formulas (1) to (4), the graft copolymer described above has a functional group (for example, an acid group, a basic group, a coordination group, etc.) that can form an interaction with a pigment. It is preferable to include a repeating unit having a coordinate group, a reactive group, and the like.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. Preferably, at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is used. Particularly preferred are carboxylic acid groups that have good adsorption power to colorants such as black pigments and that are highly dispersible.

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

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

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

When the graft copolymer has a functional group capable of forming an interaction with the pigment other than the graft chain, how these functional groups are introduced is not particularly limited. It preferably has one or more types of repeating units selected from repeating units derived from monomers represented by the following formulas (iv) to (vi).

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom number 1 to 6 alkyl groups (for example, methyl group, ethyl group, propyl group, etc.) are represented.
In formulas (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group. In general formula (iv), R ¹² and R ¹³ are each particularly preferably a hydrogen atom.

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

L ₁ in the formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups, and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR ³¹ ′ — Here, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.

L ₁ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₁ may include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) _n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with the pigment other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group. It is more preferable that

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

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

Specific examples of the graft copolymer include the following. Reference can also be made to the polymer compounds described in JP-A-2013-249417, paragraphs 0127 to 0129, the contents of which are incorporated herein.

The dispersant is also available as a commercial product. Specific examples of such a dispersant include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “DISPERBYK-101 (polyamideamine phosphate)” manufactured by BYK Chemie, and 107 (carvone). Acid ester), 110 (copolymer containing an acid group), 111 (phosphate dispersing agent), 130 (polyamide), 140, 142, 145, 161, 162, 163, 164, 165, 166, 170, 180 , 187, 190, 191, 2001, 2001, 2010, 2012, 2025 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), 9076 ”,“ EFKA4047, manufactured by EFKA Corporation ” 4050-4165 (polyurethane), EFKA4330-4340 (block copolymer) 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", manufactured by Ajinomoto Fine Techno Co., Ltd. “Azisper PB821, PB822, PB880, PB881”, “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon” manufactured by Enomoto Kasei Co., Ltd. KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725, “Demol RN, N” manufactured by Kao Corporation (Naphthalenesulfonic acid formalin Condensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”,“ homogenol L-18 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxyethylene) Nonylphenyl ether) ”,“ Acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, manufactured by Nippon Lubrizol Co., Ltd. 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (manufactured by Nikko Chemicals) Polio Siethylene monostearate), “Hinoact T-8000E” manufactured by Kawaken Fine Chemical Co., Ltd., “Organosiloxane Polymer KP341” manufactured by Shin-Etsu Chemical Co., Ltd., “EFKA-46, EFKA-47” manufactured by Morishita Sangyo Co., Ltd. , EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "(Sannopco) "ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA Corporation, and Sanyo Chemical ( "Ionet" manufactured by And the like (trade name) S-20 ", and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.

<< Radically polymerizable compound >>
The active energy ray-curable composition can contain a radically polymerizable compound. The radical polymerizable compound is preferably a polymerizable compound having an ethylenically unsaturated bond. The radical polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more, and still more preferably three or more. For example, the upper limit is preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The radical polymerizable compound may be in any chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred.
The molecular weight of the radical polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500.
The radical polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

As the radical polymerizable compound, a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure is also preferable. As examples thereof, for example, paragraph number 0227 of JP 2013-29760 A and paragraph numbers 0254 to 0257 of JP 2008-292970 A can be referred to, and the contents thereof are incorporated in the present specification.

Radical polymerizable compounds include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) , A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, commercially available from Sartomer) SR454, SR49 9) is preferred. These oligomer types can also be used. NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used.
Preferred embodiments of the radical polymerizable compound are shown below.

The radical polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. As the radically polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A radically polymerizable compound having an acid group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

The preferable acid value of the radical polymerizable compound is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

As a radically polymerizable compound, a compound having a caprolactone structure is also a preferred embodiment.
The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone be able to. Among these, a compound having a caprolactone structure represented by the following formula (Z-1) is preferable.

In the formula (Z-1), all six Rs are groups represented by the following formula (Z-2), or 1 to 5 of the six Rs are represented by the following formula (Z-2) And the remainder is a group represented by the following formula (Z-3).

In formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.

In formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

Radical polymerizable compounds having a caprolactone structure are commercially available from, for example, Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3)), Number of groups represented by formula (Z-2) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, group represented by formula (Z-2)) Number = 3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, R ¹ is all hydrogen atoms) Compound), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms).

As the radical polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can also be used.

In formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —. Each represents independently an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
In the formula (Z-4) or the formula (Z-5), — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — represents an oxygen atom side. A form in which the terminal of X is bonded to X is preferred.

The compounds represented by formula (Z-4) or formula (Z-5) may be used singly or in combination of two or more. In particular, in Formula (Z-5), all six X are acryloyl groups, and in Formula (Z-5), a compound in which all six X are acryloyl groups, Among these, an embodiment in which at least one of the compounds is a mixture with a hydrogen atom is preferable. According to this aspect, developability can be further improved.

In the radical polymerizable compound, the content of the compound represented by the formula (Z-4) or the formula (Z-5) is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the formula (Z-4) or (Z-5) is a conventionally known process, which is a ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol. Can be synthesized by a step of bonding a ring-opened skeleton and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opened skeleton. Each step is a well-known step, and those skilled in the art can easily synthesize the compounds represented by the formulas (Z-4) and (Z-5).

Among the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.

Examples of commercially available radical polymerizable compounds represented by formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

The content of the radical polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the active energy ray-curable 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 further preferably 20% 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 total amount exists in said range.

<< Cationically polymerizable compound >>
The active energy ray-curable composition can contain a cationically polymerizable compound. Examples of the cationic polymerizable compound include compounds having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable.
The cationically polymerizable compound is preferably a compound having two or more cyclic ether groups in one molecule.
The cationically polymerizable compound may be a low molecular compound (for example, a molecular weight of less than 2,000, or even a molecular weight of less than 1,000), or a macromolecule (for example, a molecular weight of 2,000 or more, in the case of a polymer). And a weight average molecular weight of 2,000 or more). The weight average molecular weight of the cationic polymerizable compound is preferably 200 to 100,000, and more preferably 500 to 50,000.

Specific examples of the compound having two or more epoxy groups in the molecule include aliphatic epoxy compounds. In addition, the description of paragraph numbers 0021 to 0031 of WO2012 / 093591 can be referred to, and the contents thereof are incorporated in the present specification.
These are available as commercial products. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321 , EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX -920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301 DLC-402 (manufactured by Nagase ChemteX), Celoxide 2021P, 2081, 3000, EHPE3150, Porido GT400, Serubinasu B0134, B0177 ((Ltd.) Daicel), and the like.
These can be used alone or in combination of two or more.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.

In addition, the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.

The content of the cationic polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the active energy ray-curable 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 further preferably 20% by mass or less. One cationic polymerizable compound may be used alone, or two or more cationic polymerizable compounds may be used in combination. When using 2 or more types together, it is preferable that a total amount exists in said range.

<< photopolymerization initiator >>
The active energy ray-curable composition can contain a photopolymerization initiator. When the active energy ray-curable composition contains a radical polymerizable compound, it is preferable to contain 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, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, Examples include the compounds described in Japanese Patent No. 4221976.

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, triallylimidazole dimers, onium compounds A compound selected from the group consisting of benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds is preferred.

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, α-aminoketone compounds More preferred is at least one compound selected from the group consisting of oxime compounds, triallylimidazole dimers, and benzophenone compounds.
As specific examples of the photopolymerization initiator, for example, paragraph numbers 0265 to 0268 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.

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

More preferred examples of the photopolymerization initiator include oxime compounds.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of oxime compounds that can be preferably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2 -One, and 2-ethoxycarbonyloxyimino-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. Examples also include compounds described in 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, and JP-A 2006-342166.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can be used.

Further, as oxime compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of the carbazole ring, and those described in US Pat. Compounds, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Publication WO2009 / 131189, triazine skeleton and oxime skeleton In the same molecule, a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, and the like. Also good.
Preferably, for example, paragraph numbers 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.

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-T-2014-500852, and JP 2013-164471 A. (C-3) described in the above. These contents are incorporated herein.

In the present invention, a compound represented by the following formula (1) or formula (2) can also be used as a photopolymerization initiator.

In the formula (1), R ¹ and R ² are each independently a chain alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, Alternatively, it represents an arylalkyl group having 7 to 30 carbon atoms, and when R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond Or a carbonyl group.

In the formula (2), R ^1, R ^2, R ³ and R ⁴ have the same meanings as R ^1, R ^2, R ³ and R ⁴ in the formula (1), R ⁵ is -R ^6, -OR ⁶ , —SR ⁶ , —COR ⁶ , —CONR ⁶ R ⁶ , —NR ⁶ COR ⁶ , —OCOR ⁶ , —COOR ⁶ , —SCOR ⁶ , —OCSR ⁶ , —COSR ⁶ , —CSOR ⁶ , —CN, halogen R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

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

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.
The oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. More preferably, it is 1,000.
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 the photoinitiator used for this invention 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. The active energy ray-curable composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Acid generator >>
The active energy ray-curable composition can contain an acid generator. In particular, when the active energy ray-curable composition contains a cationic polymerizable compound, it is preferable to contain an acid generator.
The acid generator is preferably a compound that generates an acid upon irradiation with active energy rays (radiation). Examples of the acid generator include a photocationic polymerization initiator, a photodecoloring agent for dyes, a photochromic agent, or light (400 to 200 nm ultraviolet rays, far ultraviolet rays, particularly preferably g-rays) used in a microresist. , H-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X-ray, molecular beam, ion beam, etc. It is preferable to select an acid generator having a high sensitivity.

Acid generators that generate acids upon decomposition upon irradiation with radiation, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, ortho-nitrobenzyl Examples thereof include sulfonate compounds such as sulfonate. Examples of the acid generator, specific compounds, and preferred examples include compounds described in paragraph numbers 0066 to 0122 of JP-A-2008-13646, and these can be applied to the present invention. it can.

Preferred examples of the acid generator that can be used in the present invention include compounds represented by the following formulas (b1), (b2), and (b3).

In formula (b1), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represents an organic group. X ⁻ represents a non-nucleophilic anion, preferably a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ or the following And the like, and BF ₄ ⁻ , PF ₆ ⁻ and SbF ₆ ⁻ are preferable.

Examples of commercially available acid generators include WPAG-469 (manufactured by Wako Pure Chemical Industries, Ltd.).

The content of the acid generator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20%, based on the total solid content of the active energy ray-curable composition. % By mass. The active energy ray-curable composition may contain only one type of acid generator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Silane coupling agent >>
The active energy ray-curable composition may contain a silane coupling agent for the purpose of improving the adhesion to the substrate. In particular, when the active energy ray-curable composition contains a thermosetting resin, it is preferable to further contain a silane coupling agent. Even when a cured film is produced by a low temperature process of 100 ° C. or lower using an active energy ray-curable composition containing a thermosetting resin, by further containing a silane coupling agent, Can be sufficiently secured.

In the present invention, the silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. A hydrolyzable group such as an alkoxy group is preferably bonded to a silicon atom. 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, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In the present invention, the silane coupling agent preferably contains no fluorine atom or silicon atom (except for a silicon atom to which a hydrolyzable group is bonded) in order to improve the adhesion of the cured film. Does not include atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, straight-chain alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms. Is desirable.

The silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
Formula (Z) * -Si (R ^z1 ) _3-m (R ^z2 ) _m
R ^z1 represents an alkyl group, R ^z2 represents a hydrolyzable group, and m represents an integer of 1 to 3. The number of carbon atoms of the alkyl group represented by R ^z1 is preferably 1 to 5, and more preferably 1 to 3. The definition of the hydrolyzable group represented by R ^z2 is as described above.

The silane coupling agent preferably has a curable functional group. The curable functional group includes (meth) acryloyloxy group, epoxy group, oxetanyl group, isocyanate group, hydroxyl group, amino group, carboxyl group, thiol group, alkoxysilyl group, methylol group, vinyl group, (meth) acrylamide. It is preferably at least one selected from the group consisting of a group, a styryl group, and a maleimide group, and is at least one selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group It is more preferable. The curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.

The molecular weight of the silane coupling agent is not particularly limited, and is preferably from 100 to 1,000 from the viewpoint of handleability, preferably from 270 or more, and more preferably from 270 to 1,000, from the viewpoint of more excellent effects of the present invention.

One preferred embodiment of the silane coupling agent is a silane coupling agent X represented by the formula (W).
Formula ^{(W) R z3 -Lz-Si} (R z1) 3-m (R z2) m
R ^z1 represents an alkyl group, R ^z2 represents a hydrolyzable group, R ^z3 represents a curable functional group, Lz represents a single bond or a divalent linking group, and m is an integer of 1 to 3. Represents.
The definition of the alkyl group represented by R ^z1 is as described above. The definition of the hydrolyzable group represented by R ^z2 is as described above. The definition of the curable functional group represented by R ^z3 is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, —SO ₂ NR ¹² —, —O—, —S—, —SO. _2- or a combination thereof.
The alkylene group preferably has 1 to 20 carbon atoms. The alkylene group may be linear or branched. The alkylene group and the arylene group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.
Lz is at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms and an arylene group having 6 to 12 carbon atoms, or these groups and —NR ¹² —, —CONR ¹² —, —CO—. , —CO ₂ —, —SO ₂ NR ¹² —, —O—, —S—, and a group consisting of a combination with at least one group selected from the group consisting of —SO ₂ — are preferred. A group consisting of ˜10 alkylene groups, —CO ₂ —, —O—, —CO—, —CONR ¹² —, or a combination of these groups is more preferred. Here, R ¹² represents a hydrogen atom or a methyl group.
m represents 1 to 3, preferably 2 to 3, and more preferably 3.

As the silane coupling agent X, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyltrimethoxysilane ( Shin-Etsu Chemical Co., Ltd. trade name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBE-602), γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical) Industrial brand name KBM-903), γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBM-503) Glycidoxyoctyltrimethoxysilane (trade name KBM-480 manufactured by Shin-Etsu Chemical Co., Ltd.) 3).

The silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a curable functional group in the molecule and a hydrolyzable group bonded to the silicon atom is also preferable.
The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different. Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group that can be substituted with an aryl group, silyl Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like. These substituents further include an amino group, a halogen atom, a sulfonamide group, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, and the like.
Note that at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by the formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group. The amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline. Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide. Group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxy group, ammonium group, alkylammonium group, carboxyl group or a salt thereof, sulfo group and the like.
Moreover, it is preferable that the nitrogen atom is couple | bonded with the curable functional group through arbitrary organic coupling groups. Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
The silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to have two or more curable functional groups in one molecule. From the viewpoints of sensitivity and stability, the molecule preferably has 2 to 20 curable functional groups, more preferably 4 to 15 and even more preferably 6 to 10.

Examples of the silane coupling agent Y include compounds represented by the following formula (Y).
Formula (Y) (R ^y3 ) _n -LN-Si (R ^y1 ) _3-m (R ^y2 ) _m
R ^y1 represents an alkyl group, R ^y2 represents a hydrolyzable group, R ^y3 represents a curable functional group,
LN represents a (n + 1) -valent linking group having a nitrogen atom,
m represents an integer of 1 to 3, and n represents an integer of 1 or more.
R ^y1 , R ^y2 , R ^y3 and m in the formula (Y) have the same ^meanings as R ^z1 , R ^z2 , R ^z3 and m in the formula (W), respectively, and preferred ranges are also the same.
N in the formula (Y) represents an integer of 1 or more. For example, the upper limit is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, the lower limit is preferably 2 or more, more preferably 4 or more, and still more preferably 6 or more. Also, n can be 1.
LN in the formula (Y) represents a group having a nitrogen atom.
The group having a nitrogen atom is at least one selected from the following formulas (LN-1) to (LN-4), or the following formulas (LN-1) to (LN-4), and —CO—, —CO _{2 -, - O -, -} S- and -SO ₂ - groups, which consist of a combination of at least one selected from the like. The alkylene group may be linear or branched. The alkylene group and the arylene group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.

In the formula, * represents a connecting hand.

Specific examples of the silane coupling agent Y include the following compounds. In the formula, Et represents an ethyl group. Further, compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 can be mentioned, the contents of which are incorporated herein.

The content of the silane coupling agent is preferably 0.01 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the active energy ray-curable composition. The lower limit is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount exists in said range.

<< Chromatic colorant >>
The active energy ray-curable composition can contain a chromatic colorant. In the present invention, the chromatic colorant means a colorant other than the white colorant and the black colorant. The chromatic colorant is preferably a colorant having an absorption maximum in a wavelength range of 400 nm or more and less than 650 nm.

In the present invention, the chromatic colorant may be a pigment or a dye. A pigment is preferable.
The average particle size (r) of the pigment preferably satisfies 20 nm ≦ r ≦ 300 nm, more preferably 25 nm ≦ r ≦ 250 nm, and further preferably 30 nm ≦ r ≦ 200 nm. The “average particle size” here means the average particle size of secondary particles in which primary particles of the pigment are aggregated.
Further, the particle size distribution of the secondary particles of the pigment that can be used (hereinafter also simply referred to as “particle size distribution”) is such that the secondary particles falling into (average particle size ± 100) nm are 70% by mass or more of the total. It is preferable that it is 80% by mass or more. The particle size distribution of the secondary particles can be measured using the scattering intensity distribution.
In addition, the average particle diameter of primary particles is observed with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and 100 particle sizes are measured at a portion where the particles are not aggregated, and an average value is calculated. Can be determined by

The pigment is preferably an organic pigment, and examples thereof include the following. However, the present invention is not limited to these.
Color Index (CI)

Pigment Yellow

1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (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, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (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, etc. (above, blue pigment),
These organic pigments can be used alone or in various combinations.

The dye is not particularly limited, and a known dye can be used. Chemical structures include pyrazole azo, anilino azo, triaryl methane, anthraquinone, azomethine, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole Azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

Moreover, as a dye, an acid dye and / or a derivative thereof may be preferably used.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

Specific examples of the acid dye are shown below, but are not limited thereto. Examples thereof include the following dyes and derivatives of these dyes.
Acid alizarin violet N,
Acid blue 1,7,9,15,18,23,25,27,29,40-45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1,
Acid Chrome violet K,
Acid Fuchsin; Acid green 1,3,5,9,16,25,27,50,

Acid orange

6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95,

Acid red

1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252 257, 260, 266, 274,
Acid violet 6B, 7, 9, 17, 19,
Acid yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184 243,
Food Yellow 3

Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.
Among them, as the dye, triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo A colorant selected from anilinoazo, pyrazolotriazole azo, pyridoneazo, anthrapyridone, and pyromethene is preferred.
Further, pigments and dyes may be used in combination.

When the active energy ray-curable composition contains a chromatic colorant, the content of the chromatic colorant is preferably 1 to 80% by mass with respect to the total solid content of the active energy ray curable composition. The lower limit is more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 75% by mass or less, and still more preferably 70% by mass or less.

<< Black colorant >>
The active energy ray-curable composition can contain a black colorant. As the black colorant, either an organic black colorant or an inorganic black colorant may be used. Moreover, both can also be used together. A composition containing a black colorant has low curability upon exposure and has been conventionally heat-treated at a high temperature. However, a cured film having excellent reliability can be produced by a low-temperature process, and the effect of the present invention is particularly remarkable.

(Organic black colorant)
Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. Examples of the bisbenzofuranone compounds include those described in JP-T 2010-534726, JP-A 2012-515233, JP-A 2012-515234, etc., for example, “IRGAPHOR Black” manufactured by BASF Is available as Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, and the like, and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd. The azo compound is not particularly limited, and preferred examples include a compound represented by the following formula (A-1).

(Inorganic black colorant)
Examples of the inorganic black colorant include carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, and graphite. These can realize a high optical density in a small amount. Especially, it is preferable to contain at least 1 sort (s) of carbon black and titanium black, and titanium black is especially preferable.

Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water-repellent substance as disclosed in JP-A-2007-302836 is also possible. Is possible.
The titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small.
Specifically, the average primary particle size is preferably in the range of 10 nm to 45 nm. In the present invention, the particle diameter, that is, the particle diameter is a diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.

The specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is used in order that the water repellency after the surface treatment of titanium black with a water repellent becomes a predetermined performance. It is preferably 5 to 150 m ² / g, more preferably 20 to 120 m ² / g.
Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).

In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed. A dispersed material containing Si and Ti as components can be obtained. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia. Examples of titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo). Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: manufactured by Evonik).
A dispersant may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the above-mentioned column of the dispersant.
The dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. Specific examples include those described in the column of organic solvent described later.
Titanium black in which Si / Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the method described in paragraph No. 0005 and paragraph Nos. 0016 to 0021 of Japanese Patent Application Laid-Open No. 2008-266045. .

In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
Further, in this dispersion, in addition to titanium black, for the purpose of adjusting dispersibility, colorability, etc., complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline A black pigment composed of black or the like may be used alone or in combination of two or more.
In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
In addition, in this dispersion, for the purpose of adjusting the light shielding property, other colorants (such as organic pigments and dyes) may be used in combination with titanium black as long as the effects of the present invention are not impaired. Good.
Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
Furthermore, if the particle size of the silica particles is smaller than the film thickness when the light shielding film is formed, the light shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include, for example, the silica described in paragraph No. 0039 of JP2013-249417A, the contents of which are incorporated herein.

When the active energy ray-curable composition contains a black colorant, the content of the black colorant is preferably 1 to 80% by mass with respect to the total solid content of the active energy ray-curable composition. The lower limit is more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 75% by mass or less, and still more preferably 70% by mass or less.
The total content of the black colorant and the chromatic colorant is preferably 1 to 80% by mass with respect to the total solid content of the active energy ray-curable composition. The lower limit is more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 75% by mass or less, and still more preferably 70% by mass or less.

<< Infrared absorber >>
The active energy ray curable composition may contain an infrared absorber.
In the present invention, the infrared absorber means a compound having maximum absorption in the infrared region (preferably, a wavelength region of 800 to 1300 nm).

Examples of infrared absorbers include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylene compounds, dithiol metal complex systems. Compounds, croconium compounds and the like.

As the pyrrolopyrrole compound, compounds described in JP-A-2009-263614, paragraphs 0049 to 0058 may be used, the contents of which are incorporated herein. As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraph numbers 0010 to 0081 of JP 2010-1111750 A may be used. Embedded in the book. In addition, as for the cyanine compound, for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Kojiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. .
Further, as infrared absorbers, compounds disclosed in paragraphs 0004 to 0016 of JP 07-164729 A, compounds disclosed in paragraphs 0027 to 0062 of JP 2002-146254 A, JP Near infrared absorbing particles composed of crystallites of oxides containing Cu and / or P disclosed in paragraph Nos. 0034 to 0067 of Japanese Patent No. 164583 and having a number average aggregate particle diameter of 5 to 200 nm may be used. Is incorporated herein by reference. Further, FD-25 (manufactured by Yamada Chemical Co., Ltd.), IRA842 (manufactured by Exiton), etc. can be used.

When the active energy ray-curable composition contains an infrared absorber, the content of the infrared absorber is preferably 1 to 80% by mass with respect to the total solid content of the active energy ray-curable composition. The lower limit is more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 75% by mass or less, and still more preferably 70% by mass or less.
The total content of the infrared absorber, the black colorant, and the chromatic colorant is preferably 1 to 80% by mass with respect to the total solid content of the active energy ray-curable composition. The lower limit is more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 75% by mass or less, and still more preferably 70% by mass or less.

<< Pigment derivative >>
The active energy ray-curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferable.

<< Organic solvent >>
The active energy ray curable composition may contain an organic solvent.
The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied.

Examples of organic solvents include esters such as 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, Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate etc. (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )) 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy -Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutane Ethyl acetate, etc. For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like, and ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbons, Example For example, toluene, xylene and the like are preferable.

These organic solvents are also preferably used as a mixture of two or more kinds from the viewpoints of solubility of polymerizable compounds, alkali-soluble resins and the like, and improvement of the coated surface. In this case, particularly preferably, the above methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

The content of the organic solvent in the active energy ray-curable composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass from the viewpoint of coating properties, and is 5 to 60% by mass. More preferred is 10 to 50% by mass.
The active energy ray-curable composition may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
The active energy ray-curable composition is desirably added with a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition.
Polymerization inhibitors include hydroquinone, para-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When the active energy ray-curable 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 active energy ray-curable composition.
The active energy ray-curable 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.

<< Surfactant >>
Various surfactants may be added to the active energy ray-curable composition from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

For example, by containing a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. That is, when forming a cured film using a colored composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. As a result, the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

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 this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S-393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656 PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.
A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples include compounds described in JP-A 2010-164965, paragraph numbers 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102 and RS-718K manufactured by DIC. . The fluorine-containing polymer having an ethylenically unsaturated group in the side chain is a compound different from the above-described radical polymerizable compound.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, poly Oxyethylene 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 from BASF, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R ), Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like. Alternatively, Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. may be used.

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

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

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.

When the active energy ray-curable composition contains a surfactant, the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the active energy ray-curable composition. It is preferably 0.005 to 1.0% by mass.
The active energy ray-curable composition may contain only one type of surfactant or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Other additives >>
The active energy ray-curable composition can contain various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like, if necessary. Examples of these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
The active energy ray-curable composition contains 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. be able to.

<Example of active energy ray-curable composition>
In the production method of the present invention, the active energy ray-curable composition has an optical density of 1 or more with respect to any wavelength in the wavelength range of 260 to 440 nm when a cured film having a thickness of 0.5 μm is formed. In the case of a composition that is preferably 2 or more, more preferably 3 or more, it is effective.
In the active energy ray-curable composition, when a cured film having a thickness of 0.5 μm is formed, the minimum value of the optical density in the wavelength range of 260 to 440 nm is preferably 1 or more, and 2 or more. More preferred is 3 or more.
The active energy ray-curable composition preferably has an optical density of 1 or more at a wavelength of 365 nm, more preferably 2 or more, and further preferably 3 or more when a cured film having a thickness of 0.5 μm is formed. preferable.

The optical density is a value expressed by the logarithm of the degree of absorption and is defined by the following formula. In the present invention, the optical density of the cured film is a value obtained by entering light having a wavelength of 365 nm and measuring the transmittance with a spectroscope (UV4100 (trade name)) manufactured by Hitachi High-Technologies Corporation.
OD (λ) = Log ₁₀ [T (λ) / I (λ)]
λ represents a wavelength, OD (λ) represents an optical density at the wavelength λ, T (λ) represents a transmitted light amount at the wavelength λ, and I (λ) represents an incident light amount at the wavelength λ.

In order to set the minimum value of the optical density in the above wavelength region of the cured film to 1 or more, a colorant that absorbs light in the wavelength region of 260 to 440 nm is contained, or the content of the colorant in the total solid content is appropriately set. This can be achieved by adjusting.

Examples of the active energy ray-curable composition having the optical density include an active energy ray-curable composition containing a black colorant (preferably an inorganic black colorant).

Further, as another example of the active energy ray-curable composition having the optical density, a minimum absorbance A in a wavelength range of 400 nm or more and less than 580 nm and a minimum absorbance B in a wavelength range of 580 nm or more and 750 nm or less The ratio A / B is 0.3 to 3, and the ratio C / D between the minimum absorbance C in the wavelength range from 400 nm to 750 nm and the maximum absorbance D in the wavelength range from 1000 nm to 1300 nm is 5 or more. An active energy ray-curable composition that becomes: By using the composition having the spectral characteristics, the maximum value of the transmittance in the wavelength range of 400 to 700 nm is 20% or less, and the minimum value in a specific range of the wavelength 850 to 1300 nm is 80% or more. A cured film having can be suitably formed.

The absorbance Aλ at a certain wavelength λ is defined by the following equation (1).
Aλ = −log (Tλ) (1)
Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance at the wavelength λ.
In the present invention, the absorbance value may be a value measured in a solution state, or may be a value in a film state formed using the composition. When measuring the absorbance in a film state, the composition is applied on a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined film thickness, and is used at 100 ° C. using a hot plate. It is preferable to use a membrane prepared by drying for 120 seconds. The film thickness is measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) on the substrate having the film.

The absorbance can be measured using a conventionally known spectrophotometer. Absorbance measurement conditions are not particularly limited, but in a condition where the minimum absorbance A in the wavelength range of 400 nm to less than 580 nm is adjusted to 0.1 to 3.0, in the wavelength range of 580 nm to 750 nm. It is preferable to measure the minimum absorbance B, the minimum absorbance C in the wavelength range from 400 nm to 750 nm, and the maximum absorbance D in the wavelength range from 1000 nm to 1300 nm. By measuring the absorbance under such conditions, the measurement error can be further reduced. There is no particular limitation on the method for adjusting the minimum absorbance A in the wavelength range of 400 nm or more and less than 580 nm to be 0.1 to 3.0. For example, when measuring absorbance in the state of a composition (solution), a method of adjusting the optical path length of the sample cell can be mentioned. Moreover, when measuring a light absorbency in the state of a film | membrane, the method etc. which adjust a film thickness are mentioned.

Measuring methods for the spectral characteristics and film thickness of the film are shown below.
The composition was applied onto a glass substrate by a method such as spin coating so that the film thickness after drying was the predetermined film thickness described above, and dried at 100 ° C. for 120 seconds using a hot plate. The film thickness of the film was measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) for the dried substrate having the film. The substrate having this film after drying was measured for transmittance in the wavelength range of 300 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

Examples of the active energy ray-curable composition having the spectral characteristics include a composition containing a colorant that blocks visible light. The colorant that blocks visible light is preferably a material that absorbs light in the wavelength range from purple to red. It is preferable that the color material that blocks visible light satisfies at least one of the following requirements (A) and (B).
(A): Two or more chromatic colorants are included, and black is formed by a combination of two or more chromatic colorants.
(B): Contains an organic black colorant.

Examples of the chromatic colorant and the organic black colorant include those described above.
In the present invention, the colorant that blocks visible light has, for example, an A / B that is a ratio of the minimum absorbance A in the wavelength range of 450 to 650 nm and the minimum absorbance B in the wavelength range of 900 to 1300 nm. It is preferable that it is 4.5 or more. The above characteristics may be satisfied by one kind of material, or may be satisfied by a combination of a plurality of materials.

In the case of the embodiment (A), it is preferable to contain two or more colorants selected from a red colorant, a yellow colorant, a blue colorant, and a purple colorant. Moreover, it is preferable to contain at least 1 sort (s) chosen from a red colorant, a yellow colorant, and a purple colorant, and a blue colorant. Of these, any of the following embodiments (1) to (3) is preferable.
(1) An embodiment containing a red colorant, a yellow colorant, a blue colorant, and a purple colorant.
(2) An embodiment containing a red colorant, a yellow colorant, and a blue colorant.
(3) An embodiment containing a yellow colorant, a blue colorant, and a purple colorant.

When the chromatic colorant contains a red colorant, a yellow colorant, a blue colorant, and a purple colorant, the mass ratio of the red colorant is 0.1 in the mass ratio to the total amount of the chromatic colorant. The mass ratio of yellow colorant is 0.1 to 0.4, the mass ratio of blue colorant is 0.1 to 0.6, and the mass ratio of purple colorant is 0.00. It is preferably 01 to 0.3. More preferably, the mass ratio of the red colorant is 0.2 to 0.5, the mass ratio of the yellow colorant is 0.1 to 0.3, and the mass ratio of the blue colorant is 0.2 to 0. And the mass ratio of the purple colorant is 0.05 to 0.25.
Further, when the chromatic colorant contains a red colorant, a yellow colorant, and a blue colorant, the mass ratio of the red colorant is 0.2 to 0.00 in the mass ratio with respect to the total amount of the chromatic colorant. Preferably, the mass ratio of the yellow colorant is 0.1 to 0.4, and the mass ratio of the blue colorant is 0.1 to 0.6. More preferably, the mass ratio of the red colorant is 0.3 to 0.6, the mass ratio of the yellow colorant is 0.1 to 0.3, and the mass ratio of the blue colorant is 0.2 to 0. .5.
Further, when the chromatic colorant contains a yellow colorant, a blue colorant, and a purple colorant, the mass ratio of the yellow colorant is 0.1 to 0.00 in the mass ratio with respect to the total amount of the chromatic colorant. Preferably, the mass ratio of the blue colorant is 0.1 to 0.6, and the mass ratio of the purple colorant is 0.2 to 0.7. More preferably, the mass ratio of the yellow colorant is 0.1 to 0.3, the mass ratio of the blue colorant is 0.2 to 0.5, and the mass ratio of the purple colorant is 0.3 to 0. .6.

Further, the active energy ray-curable composition having the above spectral characteristics may further contain an infrared absorber (preferably an infrared absorber having an absorption maximum in the wavelength range of 800 to 900 nm). Thereby, a cured film having a spectral characteristic in which the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less and the minimum value of the transmittance in the wavelength range of 1000 to 1300 nm is 80% or more can be suitably formed. .
In this embodiment, the infrared absorber is preferably contained in an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the colorant that blocks visible light. In addition, the content of the infrared absorber is preferably 1 to 60% by mass, more preferably 10 to 40% by mass, based on the total solid content of the composition. The content of the colorant that blocks visible light is preferably 10 to 60% by mass, more preferably 30 to 50% by mass, based on the total solid content of the composition. The total amount of the infrared absorber and the colorant that blocks visible light is preferably 1 to 80% by mass, more preferably 20 to 70% by mass, based on the total solid content of the composition. More preferably, it is 30 to 70% by mass.

<Method for preparing active energy ray-curable composition>
The active energy ray-curable composition can be prepared by mixing the aforementioned components.
In preparing the active energy ray-curable composition, each component may be blended at once, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
In the preparation of the active energy ray-curable 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 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 and / or ultrahigh) And a filter using a material such as a molecular weight polyolefin resin). Among these materials, polypropylene (including 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. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth composition in a subsequent process. Further, it is also preferable to use a fiber-like filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like, specifically, SBP type series (SBP008 etc.) and TPR type series manufactured by Loki Techno Co., Ltd. (Such as TPR002 and TPR005) and SHPX type series (such as SHPX003) filter cartridges can be used.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, 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.
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

<Curing film>
The cured film of the present invention is obtained by the above-described method for producing a cured film of the present invention.
The cured film of the present invention preferably has an optical density of 1 or more, more preferably 2 or more, and further preferably 3 or more with respect to any wavelength in the wavelength range of 260 to 440 nm.
Further, the minimum value of the optical density in the wavelength range of 260 to 440 nm is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more.
The optical density at a wavelength of 365 nm is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more.
According to the present invention, even a cured film having a high optical density in the wavelength region can be produced by a low temperature process. For this reason, the higher the optical density, the more remarkable the effect of the present invention.
The optical density is preferably a value when the thickness of the cured film is 0.5 μm or more.

The thickness of the cured film of the present invention is preferably 0.1 to 45 μm. For example, the upper limit is more preferably 44 μm or less, still more preferably 43 μm or less, and even more preferably 40 m or less. For example, the lower limit is more preferably 0.2 μm or more. When the thickness of the cured film is in the above range, the reliability of the cured film and the adhesion with the substrate are good.

The cured film of the present invention can be preferably used for a color filter, an infrared transmission filter, an infrared cut filter, a light shielding film, a transparent film, a band-pass filter, and the like. Moreover, a printed matter can also be formed using an active energy ray curable composition as printing ink.
In the present invention, the color filter means a filter that transmits light having a specific wavelength among light having a wavelength in the visible light range and shields light having a specific wavelength. The infrared transmission filter means a filter that blocks light having a wavelength in the visible light range and transmits light (infrared light) having a specific infrared wavelength. The infrared cut filter refers to a filter that transmits light having a wavelength in the visible light range (visible light) and shields at least a part of light having a wavelength in the infrared region (infrared light). In addition, the light shielding film means a film that shields at least light having a wavelength in the visible range. A transparent film means a film that transmits at least light having a wavelength in the visible light range.

Color filters, infrared transmission filters, and infrared cut filters are solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), image display devices such as liquid crystal display devices, and organic electroluminescence (organic). EL) can be preferably used for an element or the like.

The light shielding film can be formed and used on various members in an image display device or a sensor module (for example, an infrared cut filter, an outer peripheral portion of a solid-state imaging device, an outer peripheral portion of a wafer level lens, a rear surface of a solid-state imaging device, etc.). Moreover, it is good also as an infrared cut filter with a light shielding film by forming a light shielding film in at least one part on the surface of an infrared cut filter.

The transparent film can be used, for example, as a protective film such as an image display device, a solid-state image sensor, or an organic EL element. It can also be used for optical devices.

The solid-state imaging device is not particularly limited as long as it has the cured film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

The support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.). A light-shielding film having an opening only in the light-receiving portion, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion, and a color filter on the device protective film It is the structure which has.
Further, a configuration having a light collecting means (for example, a micro lens, 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 collecting means on the color filter, etc. It may be.

Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The image display device may have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, JP 2003-45676 A, supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. The spectrum of white light emitted from the organic EL device preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.

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.

<Test Example 1>
[Production of Titanium Black A-1]
120 g of titanium oxide having a BET specific surface area of 110 m ² / g (“TTO-51N”, trade name: manufactured by Ishihara Sangyo) and 25 g of silica particles having a BET surface area of 300 m ² / g (“AEROSIL (registered trademark) 300”, manufactured by Evonik) , And 100 g of a dispersant (“DISPERBYK-190”, manufactured by BYKChemie), weighed 71 g of ion-exchanged water and used MURASTAR KK-400W manufactured by KURABO to achieve a revolution speed of 1360 rpm and a rotation speed of 1047 rpm. For 30 minutes to obtain a uniform aqueous mixture. This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is added at 100 mL / min for 5 hours at the same temperature. The nitriding reduction treatment was carried out by flowing. After the completion, the recovered powder was pulverized in a mortar to obtain a powdery titanium black (A-1) containing titanium atoms and containing Si atoms and having a specific surface area of 85 m ² / g [a dispersion containing titanium black particles and Si atoms].

[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.
The obtained dispersion a was subjected to a dispersion treatment using the Ultra Apex Mill UAM015 manufactured by Kotobuki Industry Co., Ltd. under the following conditions, and a nylon filter having a pore diameter of 0.45 μm (manufactured by Nippon Pole Co., Ltd., DFA4201NXEY). ) To obtain a titanium black dispersion (hereinafter referred to as TB dispersion 1).

(Composition 1)
-Titanium black (A-1) obtained as described above-25 parts by mass-30% by mass solution of propylene glycol monomethyl ether acetate in resin 1-25 parts by mass-Propylene glycol monomethyl ether acetate (PGMEA) ... 50 parts by mass / resin 1: The following structure. The synthesis was performed with reference to the description in JP2013-249417A. In the formula of resin 1, x was 43% by mass, y was 49% by mass, and z was 8% by mass. The weight average molecular weight of Resin 1 was 30,000, the acid value was 60 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.

(Distribution condition)
・ Bead diameter: 0.05mm in diameter
・ Bead filling rate: 75% by volume
・ Mill peripheral speed: 8 m / sec ・ Mixed liquid amount for dispersion treatment: 500 g
・ Circulating flow rate (pump supply amount): 13 kg / hour ・ Processing liquid temperature: 25-30 ° C.
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Number of passes: 90 passes

(Preparation of active energy ray-curable composition)
After mixing the following composition, it filtered using the nylon filter (Nihon Pole Co., Ltd. product, DFA4201NXEY) with the hole diameter of 0.45 micrometer, and prepared the active energy ray hardening composition.

TB dispersion 1 ... 63.9 parts by mass Alkali-soluble resin 1 (solid content 30%, solvent: propylene glycol monomethyl ether acetate) ... 10.24 parts by mass Photopolymerization initiator (IRGACURE-OXE02 (manufactured by BASF) )) ... 1.81 parts by mass Radical polymerizable compound (KAYARAD DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.)) ... 6.29 parts by mass Surfactant 1 ... 0.02 parts by mass Solvent (cyclohexanone): 4.66 parts by mass Fluorosurfactant (Megafac RS-72-K, fluorinated polymer having ethylenically unsaturated groups in the side chain (manufactured by DIC Corporation, solid content 30) %, Solvent: propylene glycol monomethyl ether acetate)): 10.65 parts by mass Silane coupling agent (KBM-4803 (manufactured by Shin-Etsu Chemical Co., Ltd.)) : 0.36 parts by weight

Alkali-soluble resin 1: the following structure. The compound was synthesized according to the production methods described in JP-A 2010-106268, paragraph numbers 0338 to 0340. In the following formula, x was 90% by mass and z was 10% by mass. The alkali-soluble resin 1 had a weight average molecular weight of 40,000, an acid value of 100 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.

Surfactant 1: The following mixture (Mw = 14,000)

[Production of cured film]
A glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)) treated with hexamethyldisilazane (HMDS) was used as the substrate. The HMDS treatment was performed at 100 ° C. for 60 seconds using ACT8 (trade name) manufactured by Tokyo Electron Limited.
The active energy ray-curable composition prepared above was applied by spin coating to a glass substrate that had been subjected to HMDS treatment, and then heat-treated (prebaked) for 100 seconds using a 65 ° C. hot plate. The coating thickness of the active energy ray-curable composition was adjusted so that the thickness after pre-baking was 4.0 μm.
Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc., NA / σ = 0.63 / 0.65, Focus offset = 0 μm), a transfer pattern (10 μm × 10 μm island, pitch is The film was exposed at a dose of 8,000 J / m ² through a mask having a thickness of 20 μm.
Then, using AD-1200 (manufactured by Mikasa Co., Ltd.), 0.3 wt% of a surfactant NCW-101 (nonionic surfactant) manufactured by Wako Pure Chemical Industries, Ltd. and tetramethylammonium hydroxide ( (Development with TMAH) 0.01% by mass with paddle for 40 seconds.
Next, a rinsing process was performed using pure water, and then drying was performed at a high speed of 200 rpm for 30 seconds.
Next, electron beam irradiation was performed under the following conditions to produce a cured film.
Electron beam irradiation conditions Device: manufactured by Hamamatsu Photonics, Inc. Electron beam irradiation device Acceleration voltage: 5.0 kV to 200 kV, tube current value: 4.0 mA
Absorbed dose 145kGy
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveying speed (scanning speed during processing) 100mm / sec (2mm / sec for 200mm diameter substrate)
Processing temperature: 23 ° C or 50 ° C

(Measurement of optical density (OD value) of cured film)
Light having a wavelength of 260 to 440 nm is incident on the obtained cured film (film thickness: 4 μm), and the transmittance is measured using a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies, and optical in the wavelength range of 260 to 440 nm is measured. The minimum concentration was measured.

(Evaluation of adhesion of cured film)
The obtained cured film was immersed in a cyclohexanone solution for 10 minutes, and then the adhesion was evaluated according to the following criteria.
A: No pattern peeling B: Pattern peeling occurred

(Appearance evaluation of cured film)
The appearance of the obtained cured film was evaluated.
A: Good B: White turbidity occurs on the surface, but there is no problem.
C: Many cloudiness occurs on the surface, which is not practical.

(Evaluation of cured film reliability)
-Temperature cycle test tolerance The temperature cycle test of the cured film was done on condition of the following.
Device: LTS-150-A / W (manufactured by Hutech)
Test conditions: Each sample was left in an atmosphere of −45 ° C. and 85 ° C. for 15 minutes, and this was regarded as one cycle for 50 cycles. The resistance to temperature cycle test was evaluated according to the following criteria.
A: No pattern peeling
B: White turbidity occurred on the surface, but there was no problem, and there was no pattern peeling. C: Many white turbidity occurred on the surface, which was not practical. Consistent peeling of patterns and resistance to constant temperature and humidity test The constant temperature and humidity test of the cured film was conducted under the following conditions.
After being left in an environment of 85 ° C. and relative humidity of 85% for 100 hours, the resistance to constant temperature and humidity test was evaluated according to the following criteria.
A: There is no pattern peeling.
B: White turbidity occurred on the surface, but there is no problem, and there is no pattern peeling.
C: Many cloudiness occurs on the surface, which is not practical. Pattern peeling is also mixed.

As shown in the above table, Test No. irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. Nos. 101 to 108 were able to produce cured films with excellent reliability. The obtained cured film also had good adhesion and appearance.
On the other hand, test No. whose acceleration voltage is less than 10 kV. C11, test No. whose acceleration voltage is 100 kV or more. C12 and 13 were inferior in the reliability of the obtained cured film.

<Test Example 2>
(Preparation of active energy ray-curable composition)
After mixing the following composition, it filtered using the nylon filter (Nihon Pole Co., Ltd. product, DFA4201NXEY) with the hole diameter of 0.45 micrometer, and prepared the active energy ray hardening composition.
(composition)
Thermosetting resin (Cyclomer P (ACA) 230AA, (manufactured by Daicel Corporation)) 10.96% by mass
Propylene glycol monomethyl ether acetate: 89.03 mass%
Surfactant 1 ... 0.01% by mass
Silane coupling agent (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.): ratio shown in Table 2 (mass% based on solid content in the composition)
The same surfactant 1 as the surfactant 1 of the active energy ray-curable composition of Test Example 1 was used.

[Production of cured film]
The active energy ray-curable composition prepared above was applied by spin coating to a glass substrate that had been subjected to HMDS treatment, and then heat-treated (prebaked) for 100 seconds using a 65 ° C. hot plate. The coating thickness of the active energy ray-curable composition was adjusted so that the thickness after pre-baking was 0.3 μm.
Next, electron beam irradiation was performed under the following conditions to produce a cured film.
Electron beam irradiation conditions Device: manufactured by Hamamatsu Photonics, Inc. Electron beam irradiation device Acceleration voltage: 70 kV, tube current value: 4.0 mA
Absorbed dose 145kGy
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveying speed (scanning speed during processing) 100mm / sec (2mm / sec for 200mm diameter substrate)
Processing temperature: 23 ° C

(Measurement of optical density (OD value))
In the same manner as in Test Example 1, the OD value of the obtained cured film (film thickness: 0.3 μm) was measured.

(Evaluation of adhesion (cross cut))
The adhesion of the cured film prepared above was evaluated by a cross-cut test (according to JIS K5600, but with a lattice pattern consisting of 100 film pieces). In the cross-cut test, incisions having a depth until reaching the base material were cut into the cured film at 11 points in the vertical and horizontal directions.
The number of the film pieces peeled in 100 film pieces was evaluated according to the following evaluation criteria, and the obtained results are shown in Table 2 below.
A: 0 B: 1 or more and less than 100 C: 100

(Appearance evaluation of cured film)
In the same manner as in Test Example 1, the appearance of the cured film was evaluated.

(Evaluation of cured film reliability)
-Temperature cycle test tolerance It carried out similarly to Test Example 1, and evaluated the temperature cycle test tolerance of the cured film.
-Resistance to constant temperature and humidity test In the same manner as in Test Example 1, the resistance to constant temperature and humidity test of the cured film was evaluated.

As shown in the above table, Test No. irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. Nos. 201 to 206 were able to produce cured films having excellent reliability.

<Test Example 3>
(Preparation of active energy ray-curable composition)
After mixing the following composition, it filtered using the nylon filter (Nihon Pole Co., Ltd. product, DFA4201NXEY) with the hole diameter of 0.45 micrometer, and prepared the active energy ray hardening composition.
(composition)
Resin (Acrycure RD-F8, manufactured by Nippon Shokubai Co., Ltd.) ... 19.08 parts by mass Radical polymerizable compound (Aronix TO-2349, manufactured by Toagosei Co., Ltd.) ... 47.7 parts by mass Photopolymerization started Agent (IRGACURE-184, manufactured by BASF) ... 4.10 parts by mass Photopolymerization initiator (Lucirin-TPO, manufactured by BASF) ... 0.57 parts by mass Silane coupling agent (KBM-602, Shin-Etsu Chemical) 0.05 mass parts Surfactant (NCW-101, Wako Pure Chemical Industries, Ltd.) 0.01 mass parts Propylene glycol monomethyl ether acetate 28.62 mass parts

[Production of cured film]
After applying the active energy ray-curable composition prepared above to a glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)) under the following conditions, 65 Heat treatment (pre-baking) was performed for 100 seconds using a hot plate at 0 ° C.
Application: Spray coating method Atomization pressure: 450Pa
Flow rate: 3.0 cm ³ / min Distance between nozzle and substrate: 30 mm
Application scan speed: 200 mm / sec (2 mm / sec for 200 mm diameter substrate)
Scan pitch: 5.0mm
Coating film thickness: 10.0 μm-50.0 μm (film thickness after pre-baking, film thickness is defined by the number of scans)
Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc., NA / σ = 0.63 / 0.65, Focus offset = 0 μm), a transfer pattern (500 μm × 500 μm island, pitch is The film was exposed through a mask having a thickness of 1000 μm) at an exposure amount of 8000 J / m ² .
Subsequently, using AD-1200 (manufactured by Mikasa Co., Ltd.), development was performed with an alkaline developer (tetramethylammonium hydroxide (TMAH) 0.3 mass% aqueous solution) in a paddle for 60 seconds.
Next, a rinsing process was performed using pure water, and then drying was performed at a high speed of 200 rpm for 30 seconds.
Next, electron beam irradiation was performed under the following conditions to produce a cured film.
Electron beam irradiation conditions Device: manufactured by Hamamatsu Photonics Co., Ltd. Electron beam irradiation device Acceleration voltage: 95 kV, tube current value: 4.0 mA
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveying speed (scanning speed during processing) 100mm / sec (2mm / sec for 200mm diameter substrate)
Processing temperature: 23 ° C

(Measurement of optical density (OD value))
In the same manner as in Test Example 1, the OD value of the obtained cured film (film thickness described in Table 3) was measured.

<Test Example 4>
As the substrate, the glass substrate used in Test Example 1 and subjected to HMDS treatment was used.
A red resist (SR2000, manufactured by Fuji Film Electronics Materials Co., Ltd.) was applied by spin coating, and then heat-treated (prebaked) for 150 seconds using a 65 ° C. hot plate. The coating thickness of the active energy ray-curable composition was adjusted so that the thickness after pre-baking was 2 μm.
Next, an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc., NA / σ = 0.63 / 0.65, Focus offset = 0 μm) was used, and a transfer pattern (pattern size: 100 μm × 100 μm) was used. It exposed with the exposure amount of 800 mJ / cm < ² > through the mask which has.
Subsequently, using AD-1200 (manufactured by Mikasa Co., Ltd.), development was performed with an alkaline developer (tetramethylammonium hydroxide (TMAH) 0.3 mass% aqueous solution) in a paddle for 60 seconds.
Next, a rinsing process was performed using pure water, and then drying was performed at a high speed of 200 rpm for 30 seconds.
Next, the hardening process was performed on either of the following conditions, and the cured film (red coloring pattern) was manufactured.
(EB curing 1)
Apparatus: Electron beam irradiation apparatus manufactured by Hamamatsu Photonics Co., Ltd. Acceleration voltage: 70 kV, tube current value: 4.0 mA
Absorbed dose: 145 kGy
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveying speed (scanning speed during processing) 100mm / sec (2mm / sec for 200mm diameter substrate)
Processing temperature: 23 ° C
(EB curing 2)
Apparatus: Electron beam irradiation apparatus manufactured by Hamamatsu Photonics Inc. Acceleration voltage: 120 kV, tube current value: 4.0 mA
Absorbed dose: 145 kGy
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveying speed (scanning speed during processing) 100mm / sec (2mm / sec for 200mm diameter substrate)
Processing temperature: 23 ° C
(UV curing)
Exposure amount (ultraviolet light): 3,000 mJ / cm ²
Temperature: 35 ° C

(Spectral evaluation)
The spectrum of the film before the curing process and the spectrum of the film after the curing process under the conditions of EB curing 1 were measured using a spectroscope (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.). I couldn't.

(Reliability of cured film)
The cured film cured under the conditions of EB curing 1 was subjected to temperature cycle test resistance and constant temperature and humidity test resistance in the same manner as in Test Example 1, and when the reliability of the cured film was evaluated, there was no pattern peeling. Excellent reliability.

(Evaluation of color mixture)
The spectrum of the film before the curing treatment was measured using a spectroscope (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.) to measure the maximum transmittance T0 in the wavelength range of 600 to 700 nm.
Next, on the red coloring pattern produced by performing each curing treatment, a blue resist for color mixture evaluation (SB2000, manufactured by Fuji Film Electronics Materials Co., Ltd.) is spin-coated so that the film thickness after drying becomes 2 μm, Heat treatment (prebaking) was performed at 65 ° C. for 150 seconds.
Next, through a mask having a transfer pattern (pattern size: 100 μm × 100 μm), an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc., NA / σ = 0.63 / 0.65, Focus offset = 0 μm) and was exposed at an exposure amount of 800 mJ / cm ² .
Subsequently, using AD-1200 (manufactured by Mikasa Co., Ltd.), development was performed with an alkaline developer (tetramethylammonium hydroxide (TMAH) 0.3 mass% aqueous solution) in a paddle for 60 seconds.
Next, a rinsing process was performed using pure water, followed by drying at a high speed of 200 rpm for 30 seconds to form a blue colored pattern.
Next, with respect to the cured film (red colored pattern) after forming the blue coloring pattern, the maximum transmittance T1 in the wavelength range of 600 to 700 nm is measured using a spectroscope (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.). The transmittance change (ΔT = T0−T1) was calculated.
Further, FIG. 1 shows the spectrum of the red coloring pattern curing process, the EB curing 1 and the spectrum after color mixing of the red coloring pattern after the curing process under the UV curing conditions.

From the above results, the test No. 1 was cured under the conditions of EB curing 1. 401 was able to effectively suppress color mixing of other colors.

<Test Example 5>
The substrate shown in the following table was subjected to electron beam irradiation or heat treatment at 220 ° C. for 5 minutes (hot plate) or 1 hour (oven), and the damage of the substrate was evaluated according to the following criteria.
Electron beam irradiation was performed under the following conditions.
Electron beam irradiation conditions Device: manufactured by Hamamatsu Photonics Co., Ltd. Electron beam irradiation device Acceleration voltage: 95 kV, tube current value: 4.0 mA
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveying speed (scanning speed during processing) 100mm / sec (2mm / sec for 200mm diameter substrate)
Processing temperature: 23 ° C
Five substrates were used for each processing condition. The numerical value in parentheses in the table is the defect rate.
A: The substrate after the treatment is not warped, chipped, cracked or discolored.
B: A part of the substrate was cracked or chipped.
C: 1 to 3 substrates were cracked or warped.
D: There were cracks or warpage in four or more substrates.
Examples of the method for curing the composition include a 220 ° C. hot plate / oven and electron beam irradiation. The damage of the base material by these curing methods was evaluated (use of 5 base materials).

As is clear from the above results, even if the substrate was warped, chipped, or cracked by heat treatment, it was not warped, chipped or cracked by electron beam irradiation.

<Test Example 6>
[Preparation of pigment dispersion B-1]
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-1 was prepared.
A mixed pigment (CI pigment red 254: CI pigment yellow 139 = 4: 1 (mass) consisting of a red pigment (CI pigment red 254) and a yellow pigment (CI pigment yellow 139) Ratio)) ... 11.8 parts by mass-Resin 1 (dispersant) (BYK Chemie, DISPERBYK-111)-9.1 parts by mass-Propylene glycol methyl ether acetate-79.1 parts by mass

[Preparation of pigment dispersion B-2]
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-2 was prepared.
A mixed pigment (CI pigment blue 15: 6: CI pigment violet 23 = 9) consisting of a blue pigment (CI pigment blue 15: 6) and a purple pigment (CI pigment violet 23) : 4 (mass ratio)) ... 12.6 parts by mass Resin 1 (dispersant) (BYPER Chemie, DISPERBYK-111) ... 2.0 parts by mass resin 2 (dispersant) ... 3 3 parts by mass, cyclohexanone 31.2 parts by mass, propylene glycol methyl ether acetate 50 parts by mass

Resin 2: The following structure (ratio in repeating units is molar ratio, Mw = 14,000)
Resin 2 is also an alkali-soluble resin.

(Preparation of active energy ray-curable composition)
After mixing the following composition, it filtered using the nylon filter (Nihon Pole Co., Ltd. product, DFA4201NXEY) with the hole diameter of 0.45 micrometer, and prepared the active energy ray hardening composition.
(composition)
-Pigment dispersion B-1 ... 46.5 parts by mass-Pigment dispersion B-2 ... 37.1 parts by mass-Alkali-soluble resin 1 ... 1.1 parts by mass-Radical polymerizable compound 1- 1.8 mass parts Silane coupling agent 1 0.6 mass parts Photoinitiator 1 0.9 mass parts Surfactant 1: 4.2 mass parts Polymerization inhibitor (para-methoxyphenol): 0.001 part by mass / PGMEA: 7.8 parts by mass

Alkali-soluble resin 1: the following structure (ratio in repeating units is molar ratio, Mw = 11,000)

Radical polymerizable compound 1: structure shown below (a mixture in which the molar ratio of the left compound to the right compound is 7: 3)

・ Silane coupling agent 1: Structure shown below

Photopolymerization initiator 1: structure shown below

The same surfactant 1 as the surfactant 1 of the active energy ray-curable composition of Test Example 1 was used.

[Production of cured film]
After applying the active energy ray-curable composition prepared above to a glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)), a 65 ° C. hot plate was applied. Heat treatment (pre-baking) was performed for 120 seconds using it. The coating thickness of the active energy ray-curable composition was adjusted so that the thickness after pre-baking was 2 μm.
Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc., NA / σ = 0.63 / 0.65, Focus offset = 0 μm), a transfer pattern (pattern size: 100 μm × 100 μm) was used. It exposed with the exposure amount of 500 mJ / cm < ² > through the mask which has.
Subsequently, using AD-1200 (manufactured by Mikasa Co., Ltd.), development was performed with an alkaline developer (tetramethylammonium hydroxide (TMAH) 0.3 mass% aqueous solution) in a paddle for 60 seconds.
Next, a rinsing process was performed using pure water, and then drying was performed at a high speed of 200 rpm for 30 seconds.
Subsequently, after performing a curing process under any of the following conditions, an additional baking process was performed at 240 ° C. for 5 minutes using a hot plate.
(EB curing)
Apparatus: Electron beam irradiation apparatus manufactured by Hamamatsu Photonics Co., Ltd. Acceleration voltage: 70 kV, tube current value: 4.0 mA
Absorbed dose: 145 kGy
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveying speed (scanning speed during processing) 100mm / sec (2mm / sec for 200mm diameter substrate)
Processing temperature: 23 ° C
(UV curing)
Exposure amount (ultraviolet light): 3,000 mJ / cm ²
Temperature: 35 ° C
(Heat curing)
1 hour at 220 ° C in oven

(Measurement of optical density (OD value))
In the same manner as in Test Example 1, the OD value of the obtained cured film (film thickness: 2 μm) was measured.

(appearance)
The appearance of the film before the curing process, after the curing process, and after the additional baking was evaluated.
A: No problem B: Wrinkles on the surface

As shown in the above table, Test No. irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. No. 601 is a No. 601 after heat curing. A cured film equivalent to 603 and excellent in reliability could be produced. Further, the film after additional baking was free from wrinkles and had a good appearance.
On the other hand, UV curing was performed, test No. 602 was inferior in reliability. Furthermore, wrinkles occurred in the film after the additional baking. This is presumed that wrinkles were generated on the surface due to the difference in film shrinkage between the surface and the inner surface due to the treatment at a high temperature because the curing of only the surface of the exposure pattern was promoted and the polymerization inside the pattern was insufficient. .

<Test Example 7>
(Preparation of active energy ray-curable composition)
After mixing the following composition, it filtered using the nylon filter (Nihon Pole Co., Ltd. product, DFA4201NXEY) with the hole diameter of 0.45 micrometer, and prepared the active energy ray hardening composition.
(composition)
・ Cationically polymerizable compound (EHPE 3150, manufactured by Daicel Chemical Industries, Ltd.): 4.0% by mass
Acid generator (WPAG-469, Wako Pure Chemical Industries, 20% propylene glycol monomethyl ether acetate solution) ... 1.0% by mass
・ Surfactant 1 ... 0.1% by mass
Propylene glycol monomethyl ether acetate (PGMEA) ... 94.9% by mass
The same surfactant 1 as the surfactant 1 of the active energy ray-curable composition of Test Example 1 was used.

[Production of cured film]
After applying the active energy ray-curable composition prepared above to a glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)) by spin coating, 65 Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 0 ° C. The coating thickness of the active energy ray-curable composition was adjusted so that the thickness after pre-baking was 0.1 μm.
Next, electron beam irradiation (manufactured by Hamamatsu Photonics) was performed under the following conditions to produce a cured film.
(EB condition 1)
Acceleration voltage: 70 kV, tube current value: 4.0 mA
Absorbed dose: 145 kGy
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveyance speed (scanning speed during processing) 100 mm / sec x 1 scan Processing temperature: 23 ° C
(EB condition 2)
Acceleration voltage: 50 kV, tube current value: 2.6 mA
Absorbed dose: 15 kGy
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveyance speed (scanning speed during processing) 100 mm / sec x 1 scan Processing temperature: 23 ° C
(EB condition 3)
Acceleration voltage: 50 kV, tube current value: 2.6 mA
Absorbed dose: 30 kGy
Clearance between substrate and electron irradiation source: 10mm
Oxygen concentration ≤ 1000 ppm by volume
Conveyance speed (scanning speed during processing) 100 mm / second x 2 scans Processing temperature: 23 ° C

(Solvent resistance)
The obtained cured film was immersed in PGMEA or cyclohexanone for 5 minutes, and then the solvent resistance of the cured film was evaluated according to the following criteria.
A: Abnormal film surface and no film thickness variation B: Abnormal film surface or film thickness variation

As shown in the above table, Test No. irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. Nos. 701 to 703 were able to produce cured films with excellent reliability.

Claims

A method for producing a cured film comprising a step of irradiating an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV to a layer of an active energy ray-curable composition on a substrate, and at a temperature of 100 ° C. or lower throughout the whole process. A method for producing a cured film.
The method for producing a cured film according to claim 1, wherein the active energy ray-curable composition contains an alkali-soluble resin.
The method for producing a cured film according to claim 1 or 2, wherein the base material is a thermoplastic base material made of a thermoplastic resin having a glass transition temperature of 100 ° C or lower.
The method for producing a cured film according to claim 1 or 2, wherein the substrate is a glass substrate having a thickness of 0.5 mm or less.
The method for producing a cured film according to claim 1 or 2, wherein the substrate includes an organic semiconductor layer.
The method for producing a cured film according to claim 1 or 2, wherein the base material has an organic semiconductor layer on a surface thereof.
And a step of exposing the layer of the active energy ray-curable composition.
The method for producing a cured film according to any one of claims 1 to 6, wherein the step of irradiating the electron beam is performed after the step of exposing.
Furthermore, the step of exposing the layer of the active energy ray-curable composition, and the step of developing the layer of the active energy ray-curable composition to form a pattern after the exposing step,
The method for producing a cured film according to any one of claims 1 to 6, wherein the step of irradiating the electron beam is performed after the step of forming the pattern.
The method for producing a cured film according to claim 7 or 8, wherein the exposing step is performed using ultraviolet rays.
The active energy ray-curable composition contains 0.01 to 5.0 mass% of a silane coupling agent in the solid content of the active energy ray-curable composition. The manufacturing method of the cured film as described in claim | item.
The method for producing a cured film according to claim 10, wherein the active energy ray curable composition contains a thermosetting resin.
The method for producing a cured film according to any one of claims 1 to 11, wherein the active energy ray-curable composition contains at least one selected from a chromatic colorant and a black colorant.
The method for producing a cured film according to any one of claims 1 to 12, wherein the cured film has an optical density of 1 or more with respect to any wavelength in a wavelength range of 260 to 440 nm.
The method for producing a cured film according to claim 13, wherein the cured film has a minimum optical density of 1 or more in a wavelength range of 260 to 440 nm.
The method for producing a cured film according to claim 13, wherein the cured film has an optical density of 1 or more with respect to a wavelength of 365 nm.
The method for producing a cured film according to any one of claims 1 to 15, wherein the active energy ray-curable composition contains a photopolymerization initiator and a radically polymerizable compound.
The method for producing a cured film according to any one of claims 1 to 15, wherein the active energy ray-curable composition contains an acid generator and a cationically polymerizable compound.
The method for producing a cured film according to any one of claims 1 to 17, wherein the thickness of the cured film is 0.1 to 45 µm.
The cured film according to any one of claims 1 to 18, wherein the active energy ray-curable composition is applied onto the substrate and then dried to form a layer of the active energy ray-curable composition. Manufacturing method.
The method for producing a cured film according to any one of claims 1 to 19, further comprising a step of vacuum drying.
The method for producing a cured film according to any one of claims 1 to 20, further comprising a step of heat-treating the layer irradiated with the electron beam at a temperature of 100 ° C or lower.
The said base material is a thermoplastic resin base material, The said heat-processing process is the temperature below the glass transition temperature of the said thermoplastic resin base material, and is performed at the temperature of 100 degrees C or less. A method for producing a cured film.
A cured film obtained by the method for producing a cured film according to any one of claims 1 to 22.