KR20170141802A - And a curing film - Google Patents

Abstract

A method for producing a cured film and a cured film which can produce a cured film excellent in reliability by a low temperature process. A process for producing a cured film comprising a step of irradiating a layer of an active energy ray-curable composition on a substrate with an electron beam having an acceleration voltage of not less than 10 kV and less than 100 kV.

Description

And a curing 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 in order to sufficiently cure the curable composition. For example, the color filter is manufactured as follows. First, a curable composition (coloring composition) containing a colorant is applied to a substrate such as a glass substrate to form a coloring composition layer. Then, the colored composition layer is exposed and developed to form a pattern. Then, the patterned colored composition layer is heat-treated (post-baked) to sufficiently cure the colored composition layer. Thus, a color filter is manufactured.

There is also known a method for producing a cured film by irradiating the curable composition with electron beams (see Patent Documents 1 to 5).

Patent Document 1: JP-A-10-268515 Patent Document 2: JP-A No. 2004-12843 Patent Document 3: JP-A-2010-107928 Patent Document 4: JP-A-2009-244689 Patent Document 5: JP-A No. 2004-123802

Conventionally, the cured film has been produced on a substrate composed of a material such as silicon excellent in heat resistance.

In recent years, it has been required to produce a cured film on a substrate having poor heat resistance. In the production of a cured film on a substrate having poor heat resistance, it is preferable to manufacture a cured film by a low-temperature process at a temperature of, for example, 100 캜 or less to suppress thermal damage to the substrate. However, in the case where a cured film is produced by a low-temperature process, after the temperature cycle test or the constant-temperature and constant-humidity test, appearance problems are liable to occur, the film thickness fluctuation is large, The reliability of the cured film tends to be lower than that of the cured film produced through the heat treatment at a high temperature.

It is therefore an object of the present invention to provide a cured film production method and a cured film which can produce a cured film excellent in 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 electron beam having an acceleration voltage of 10 kV or more and less than 100 kV to an active energy ray curable composition, It came to the following. The present invention provides the following.

<1> A method for producing a cured film, comprising the step of irradiating a layer of an active energy ray-curable composition on a substrate with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV, &Lt; / RTI &gt;

&Lt; 2 > The method for producing a cured film according to < 1 >, wherein the active energy ray curable composition comprises an alkali soluble resin.

<3> The method for producing a cured film according to <1> or <2>, wherein the substrate is a thermoplastic resin substrate made 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 substrate comprises 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 its surface.

&Lt; 7 > The method for producing a cured film according to any one of < 1 > to < 6 >, further comprising a step of exposing a layer of the active energy ray curable composition, wherein the step of irradiating the electron beam is performed after the step of exposing.

The method of manufacturing an active energy ray curable composition according to any one of claims 1 to 7, further comprising the steps of: exposing a layer of an active energy ray curable composition; and developing a layer of an active energy ray- The method for producing a cured film according to any one of < 1 > to < 6 >

<9> The method for producing a cured film according to <7> or <8>, wherein the step of exposing is performed using ultraviolet light.

<10> The method for producing a cured film according to any one of <1> to <9>, wherein the active energy ray curable composition contains 0.01 to 5.0% by mass of a silane coupling agent in a solid content of the active energy ray curable composition.

<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 the group consisting of 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 at any wavelength in the 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 in a 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 at 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 process 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 cationic polymerizable compound.

<18> The method for producing a cured film according to any one of <1> to <17>, wherein the film thickness of the cured film is 0.1 to 45 μm.

<19> A process for producing a cured film according to any one of <1> to <18>, wherein an active energy ray-curable composition is applied on a substrate and then dried to form a layer of an active energy ray-curable composition.

<20> A method for producing a cured film according to any one of <1> to <19>, which comprises a step of performing 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 electron beams at a temperature of 100 ° C. or lower.

<22> The method for producing a cured film according to <21>, wherein the base material is a thermoplastic resin base material, and the step of 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.

<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 becomes possible to provide a method of manufacturing a cured film and a cured film which can produce a cured film having excellent reliability by a low-temperature process.

1 is a view showing a spectrum of a cured film before and after a color mixture evaluation.

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

In the notation of "group (atomic group)" in the present specification, the notation in which substitution and non-substitution are not described means that the substituent includes both a group having a substituent and a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, the term "light" means an actinic ray or radiation. The term " actinic ray "or" radiation " means deep ultraviolet rays (EUV light), X rays, electron rays, and the like represented by, for example, a luminescence spectrum of a mercury lamp and an excimer laser.

In the present specification, "exposure" includes not only exposure using deep ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers but also imaging using particle beams such as electron beams and ion beams .

In the present specification, the numerical range indicated by using "~ " means a range including numerical values written before and after" ~ "as a lower limit value and an upper limit value.

As used herein, the term "total solids" refers to the total mass of components excluding the solvent from the total composition of the composition.

In the present specification, the term "(meth) acrylate" refers to both or either of acrylate and methacrylate, "(meth) acryl" refers to both acrylate and methacrylate, The term "(meth) allyl" represents either or both of allyl and methallyl, and "(meth) acryloyl" represents either or both acryloyl and methacryloyl.

In the present specification, the term " process "is included in this term, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values in Gel Permeation Chromatography (GPC) measurement.

&Lt; Process for producing a cured film &

The method for producing a cured film of the present invention includes 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 (hereinafter also referred to as an active energy ray curable composition layer) And the production method of the cured film is performed at a temperature of 100 DEG C or lower through the entire process.

According to the present invention, even when 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 and is performed at a low temperature of 100 캜 or below (hereinafter also referred to as a low temperature process) An excellent cured film can be produced.

In the present invention, "performed at a temperature of 100 占 폚 or less through the whole process" means that the entire process of curing the active energy ray curable composition layer to form a cured film is performed at a temperature of 100 占 폚 or less, Each step of the membrane fabrication process is performed at a temperature of 100 DEG C or less. That is, in the case where the manufacturing process of the cured film includes another process in addition to the process of irradiating the electron beam, the other process is also performed at a temperature of 100 ° C or lower. For example, when the active energy ray-curable composition layer is further formed on the substrate, the step of forming the active energy ray-curable composition layer is also carried out at 100 DEG C or less. When the active energy ray-curable composition layer on the substrate is further provided with an exposure step, the exposure step is also carried out at 100 DEG C or less. When the active energy ray-curable composition layer on the substrate has a step of forming a pattern, the step of forming the pattern is also performed at a temperature of 100 DEG C or less. When the active energy ray-curable composition layer after irradiation with electron beam is further subjected to a post-treatment such as heat treatment, the post-treatment is also carried out at a temperature of 100 DEG C or lower.

Further, after the cured film is formed, dicing (dividing into chips) and bonding may be additionally performed. However, the step after the cured film formation is not included in the "whole process" That is, the step after forming the cured film may be performed at a temperature exceeding 100 캜. For example, when a thin film glass substrate is used as the substrate, cracking or warping may occur in the substrate when the curing film is formed at a temperature exceeding 100 캜. However, even if heated to a temperature exceeding 100 캜 after dicing , And cracks and warps are less likely to occur.

Hereinafter, each of the steps of the method for producing a cured film of the present invention will be described in order.

An active energy ray curable composition is used to form an active energy ray curable composition layer on a substrate. The active energy ray-curable composition will be described later.

As the substrate, for example, a substrate composed of glass, silicon, resin or the like can be given. Examples of the glass include glass used for optical devices and display devices such as the Eagle series of Corning's alkali-free glass, 1737, glass having an organic layer formed by dispersing or kneading a dye having a UV blocking function or an infrared ray blocking function ). Examples of the resin include polyolefins such as polyethylene, polypropylene, vinyl chloride, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, acrylic, polyvinyl alcohol, Vinylidene chloride, polycarbonate, polyamide, polyacetal, polystyrene terephthalate, and fluororesin. One or more of these may be used in combination. On these substrates, an organic light emitting layer, an organic semiconductor layer such as an organic photoelectric conversion layer, or the like may be formed. Examples of organic semiconductors include organic electroluminescence (OLED), organic field effect transistor (OFET), and organic solar cell (OPV). In the present invention, the organic semiconductor layer may be used as a substrate.

Though the thickness of the substrate varies depending on the use and the material, a thickness of a general substrate can be applied.

According to the present invention, a cured film can be formed without damaging the substrate even for a substrate having poor heat resistance, so that it is particularly effective for a substrate having 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 (preferably a substrate having an organic semiconductor layer on its surface) containing an organic semiconductor layer, and the like.

Among the thermoplastic resin base materials, for example, in the case of a base made of a thermoplastic resin having a glass transition temperature of 95 캜 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 占 폚 or lower is more widely used. Especially recently, those having a glass transition temperature of lower than 70 캜 are particularly preferably used. The lower limit of the glass transition temperature of the thermoplastic resin is not particularly limited. For example, at room temperature (23 캜) or higher. The lower limit of the temperature may be lower than the normal temperature. For example, 0 ° C or higher, or -50 ° C or higher, or -100 ° C or higher, or -150 ° C or higher.

In the present invention, when the thermoplastic resin has a glass transition temperature of 2 or more, the lower temperature is the glass transition temperature of the present invention.

The upper limit of the film thickness of the glass base material is preferably 0.5 mm or less, more preferably 0.3 mm or less. The lower limit is not particularly limited, but may be 0.1 mm or more.

Various methods such as slit coating, inkjet coating, spin coating, salting coating, roll coating, screen printing, and spray coating can be used as a method of applying the active energy ray-curable composition to a substrate. The application amount of the active energy ray curable composition is preferably adjusted so that the film thickness after drying becomes 0.1 to 45 占 퐉. The upper limit is more preferably 44 μm or less, more preferably 43 μm or less, and particularly preferably 40 m or less. The lower limit is more preferably 0.2 m or more, for example.

In the present invention, the active energy ray curable composition layer formed on the substrate may be dried. Drying may be drying at room temperature, drying by heating, or vacuum drying. Vacuum drying is preferred because of drying speed and drying at a low temperature.

The vacuum drying is preferably performed under the conditions of a vacuum degree of 0.02 PaG or more and a temperature of 100 占 폚 or less. The degree of vacuum is more preferably 0.05 Pa or more, and more preferably 0.09 Pa 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 deg. C or less. The lower limit may be, for example, 23 占 폚 or higher, and may be 30 占 폚 or higher. The drying time is preferably from 30 seconds to 1 hour, more preferably from 1 minute to 30 minutes, even more preferably from 2 minutes to 20 minutes.

The heat drying is preferably carried out at 100 ° C or lower, more preferably 80 ° C or lower, and further preferably 70 ° C or lower. The lower limit may be, for example, 23 占 폚 or higher. The heating time is preferably 30 seconds to 1 hour, more preferably 1 minute to 30 minutes, still more preferably 2 minutes to 20 minutes.

The drying may be performed immediately before the step of irradiating an electron beam to be described later, or may be carried out after the step of irradiating the electron beam. And may be performed before or after the developing process described below.

In the present invention, the active energy ray curable composition layer formed on the substrate may be exposed. The exposure may be an entire surface exposure or a pattern exposure through a mask.

For example, the active energy ray-curable composition layer formed on a substrate can be pattern-exposed by exposure through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, the exposed portion can be cured.

As the radiation (light) usable for exposure, ultraviolet rays are preferable. Examples of the ultraviolet ray include g line, i line, KrF, ArF and the like, and i line is preferable. Irradiation dose (exposure dose) of, for example 30 ~ 5000mJ / cm ² are preferred, and 50 ~ 4000mJ / cm ² is more preferably, 80 ~ 3000mJ / cm ² is more preferred.

When the active energy ray curable composition layer is exposed in a pattern shape, it is preferable to form the pattern by developing and removing the unexposed portion. The development of the unexposed portion can be removed by using a developing solution. As a result, the active energy ray-curable composition layer of the unexposed portion is eluted into the developer, leaving only the photo-cured portion.

As the developer, an alkali developing solution which does not damage the substrate is preferable.

The temperature of the developing solution is preferably 20 to 30 占 폚, for example. The development time is preferably 20 to 180 seconds.

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like.

In addition, an inorganic alkaline compound may be used as an alkaline agent for use in 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 to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as a developer.

As the developing solution, a surfactant may be used. Examples of the surfactant include surfactants described in the later-described active energy ray-curable composition, and nonionic surfactants are preferred. When the developer contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.0% by mass based on the total mass of the developer.

When such a developer composed of an alkaline aqueous solution is used, it is generally preferable to rinse with pure water after development.

After the cleaning, it is preferable to perform the above-mentioned drying after, for example, spin drying.

Next, the active energy ray curable composition layer on the substrate is irradiated with an electron beam. When the above-described activation energy ray-curable composition layer is subjected to only the above-described exposure and when the above-described development is not carried out, it is preferable to irradiate the electron beam after exposure. Further, in the case of performing pattern formation (in the case of performing exposure and development) with respect to the active energy ray curable composition layer, it is preferable to irradiate electron rays after pattern formation of the active energy ray curable composition layer.

The acceleration voltage of the 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 more preferably 30 kV or more. The upper limit is preferably 99 kV or less, more preferably 98 kV or less, and more preferably 97 kV or less. When the acceleration voltage of the electron beam is within the above range, a cured film excellent in reliability can be produced. Further, the appearance and spectral characteristics of the resulting cured film are also good.

The tube current of the electron beam is preferably 0.01 to 10 mA. When the tube current of the electron beam is within the above range, the electron beam density emitted from the filament is sufficiently maintained, and a cured film excellent in reliability can be produced. Further, the appearance and spectral characteristics of the resulting cured film 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 more 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. If the durability of the filament is maintained, it is preferable that the setting of the tube current is large.

The electron beam is preferably irradiated within a range in which 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 excellent in reliability can be produced. The absorbed dose of the electron beam is more preferably 15 kGy or more, and more preferably 20 kGy or more.

In the step of irradiating the electron beam, the treatment temperature (temperature in the apparatus) is 100 占 폚 or lower, preferably 80 占 폚 or lower, and more preferably 70 占 폚 or lower. The lower limit may be, for example, 10 占 폚 or higher, 15 占 폚 or higher, or 20 占 폚 or higher.

The irradiation of the electron beam is preferably performed under an atmosphere having an oxygen concentration of 3,000 ppm or less. The oxygen concentration is more preferably 1000 ppm by volume or less.

The clearance between the substrate and the electron irradiation source is preferably 1 to 30 mm, more preferably 5 to 10 mm.

In the method for producing a cured film of the present invention, the active energy ray curable composition layer irradiated with an electron beam may be subjected to heat treatment at a temperature of 100 ° C or lower. The curing of the cured film can be stabilized by promoting the drying of the cured film by the heat treatment.

The heat treatment temperature is preferably, for example, a temperature higher than 23 deg. C to 100 deg. The upper limit is more preferably 80 DEG C or lower, and further preferably 70 DEG C or lower. When the thermoplastic resin base material is used as the base material, the upper limit of the heat treatment temperature is a temperature of 100 占 폚 or lower, and a temperature not higher than the glass transition temperature of the thermoplastic resin base is preferable. When the glass transition temperature of the thermoplastic resin base exceeds 100 캜, the upper limit of the heat treatment temperature is 100 캜.

In the heat treatment, the active energy ray-curable composition layer after irradiation with electron beams is continuously or batch-wise heated by a heating means such as a hot plate, a convection oven (hot-air circulation type drier) .

Instead of the heat treatment, vacuum drying may be performed. Heat treatment and vacuum drying may also be used in combination.

&Lt; 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, the active energy ray-curable composition can be preferably used as long as it is a composition which is cured by irradiation with active energy rays. Herein, the active energy ray is an energy ray that can impart energy that can generate openings in the composition by the irradiation, and includes, for example,? Rays,? Rays, X rays, ultraviolet rays, visible rays, And the like.

<< Resin >>

The active energy ray curable composition preferably includes a resin. Resins are used, for example, for dispersing a pigment or the like in a composition or for use as a binder. The resin mainly used for dispersing the pigment or the like is also referred to as a dispersant. However, such use of the resin is merely an example, and the resin may 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 more preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and more preferably 5,000 or more.

Examples of the resin include (meth) acrylic resin, epoxy resin, n-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyparaphenylene resin, Polybutylene terephthalate resin, phenanthrene resin, phenanthrene resin, phenanthrene resin, phenanthrene resin, phenanthrene resin, phenanthrene resin, phenanthrene resin, These resins may be used singly or in combination of two or more kinds.

In the active energy ray curable composition, the content of the resin is preferably 10 to 80 mass%, more preferably 20 to 60 mass%, of 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 two or more kinds of resins. When two or more kinds are included, it is preferable that the total amount is 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 forming property are improved. The alkali-soluble resin may also be used as a dispersant or a binder.

The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5000 to 100,000. The number average molecular weight (Mn) is preferably from 1,000 to 20,000.

The alkali-soluble resin may be a linear organic polymer or a resin having a group capable of promoting at least one alkali dissolution in a molecule (preferably, an acrylic copolymer, a styrene-based copolymer as a main chain).

The alkali-soluble resin is preferably a polyhydroxystyrene-based resin, a polysiloxane-based resin, an acrylic resin, an acrylamide-based resin or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance, , An acrylamide resin, and an acrylic / acrylamide copolymer resin.

Examples of the group capable of promoting alkali dissolution (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. However, the group capable of being soluble in an organic solvent and capable of being developed by a weakly alkaline aqueous solution , And (meth) acrylic acid is particularly preferable. These acid groups may be one kind or two or more kinds.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally.

As the alkali-soluble resin, a polymer having a carboxylic acid in its 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, a partially esterified maleic acid copolymer, Soluble resin such as an alkali-soluble phenol resin such as a phenol resin, an acid-soluble phenol resin such as a phenol resin, and an acidic cellulose derivative having a carboxyl group in the side chain; and a resin obtained by adding an acid anhydride to a polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and other monomer copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl , And cyclohexyl (meth) acrylate. Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone Tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. As another monomer, N-substituted maleimide monomers described in JP-A-10-300922, for example, N-phenylmaleimide and N-cyclohexylmaleimide can be given. These monomers copolymerizable with (meth) acrylic acid may be used singly or in combination of two or more.

Further, 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 (meth) allyl group and (meth) acryloyl group. The alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin containing a polymerizable group in a side chain. 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.), Viscot R- KS Resist 106 (all manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series (for example, ACA230AA, thermosetting resin), FLACCEL CF200 series (all available from Daicel), Ebecryl 3800 Ltd.) and Acricheure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / benzyl (meth) acrylate / (Meth) acrylic acid / other monomers can be preferably used. (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylate copolymer as described in JP-A-7-140654, a copolymer of 2-hydroxyethyl Acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl Methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like can also be preferably used.

As a commercially available product, for example, FF-426 (manufactured by Fujikura Chemical Co., Ltd.) may be used.

The alkali-soluble resin is a polymer obtained by polymerizing a monomer component comprising a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as " .

[Chemical Formula 1]

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

(2)

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), reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2010-168539.

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-propyl, isopropyl, , Isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl and the like; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; And an alkyl group substituted with an aryl group such as benzyl. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like, or a substituent of a primary or secondary carbon which is difficult to be desorbed by heat, is preferable from the viewpoint of heat resistance.

As a specific example of the ether dimer, reference can be made, for example, to Japanese Patent Laid-Open Publication No. 2013-29760, paragraph number 0317, which is incorporated herein by reference. The ether dimer may be one kind or two or more kinds.

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

(3)

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkylene group having 1 to 20 carbon atoms Alkyl group. n represents an integer of 1 to 15;

In the formula (X), the number of carbon atoms of the alkylene group of R ₂ is preferably 2 to 3. 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 include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (isopropyl) group.

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

[Chemical Formula 4]

The alkali-soluble resin may refer to the description of Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraphs 0685 to 0700) .

Further, the copolymer (B) described in paragraphs [0029] to [0063] of JP-A No. 2012-32767 and the alkali-soluble resin used in the examples, the binder resin described in paragraphs 0088 to 0098 of Japanese Patent Application Publication No. 2012-208474 The binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Laid-Open Patent Publication No. 2012-137531 and the binder resin used in the examples, and the binder resins used in the examples described in paragraphs 0132 to 0143 of JP-A- The binder resin described and the binder resin used in the examples, the binder resins used in the examples and the paragraphs Nos. 0092 to 0098 of Japanese Laid-Open Patent Publication No. 2011-242752 and the binder resins used in the examples, The binder resin described may also be used. The contents of which are incorporated herein by reference.

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 more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, still more preferably 200 mgKOH / g or less, still more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less.

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

<<< Dispersant >>>

The active energy ray curable composition may contain a dispersing agent as a resin.

The resin used as the dispersing agent preferably contains a repeating unit having an acid group. By including the repeating unit having an acid group in the resin, it is possible to further reduce the residues generated in the base (ground) when the pattern is formed by photolithography.

The repeating unit having an acid group can be formed 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. Addition reaction products of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride or cyclohexanedicarboxylic anhydride, Caprolactone mono (meth) acrylate, and the like. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as a precursor of the carboxyl group. Among them, from the viewpoint of developing removability of the unexposed portion, it is preferable to use a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic monocarboxylic acid such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, Additional reactants with anhydrides are preferred.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamide-2-methylpropanesulfonic acid and the like.

Examples of the vinyl monomer having a phosphoric acid group include mono (2-acryloyloxyethyl ester) phosphate and mono (1-methyl-2-acryloyloxyethyl ester) phosphate.

As the repeating unit having an acid group, reference can be made to the description of paragraphs 0067 to 0069 of Japanese Laid-Open Patent Publication No. 2008-165059, which is incorporated herein by reference.

The resin used as a dispersant is also preferably a graft copolymer. Since graft copolymers have affinity for a solvent by a graft chain, the graft copolymer is excellent in the dispersibility of the pigment and the dispersion stability after aging. In addition, the composition has affinity with a polymerizable compound, an alkali-soluble resin and the like due to the presence of a graft chain, so that it is possible to make it difficult to generate a residue by an alkali phenomenon.

In the present invention, the graft copolymer means a resin having a graft chain. The graft chain indicates from the origin of the main chain of the polymer to the end of the group branched from the main chain.

In the present invention, as the graft copolymer, a resin having a graft chain in the range of 40 to 10,000 atoms excluding hydrogen atoms is preferable.

The number of atoms excluding the hydrogen atom per one 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 a (meth) acrylic resin, a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, and a polyether resin. Among them, a (meth) acrylic resin is preferable.

The graft chain of the graft copolymer is preferably a graft chain having a poly (meth) acrylate, a polyester or a polyether in order to improve the interactivity of the graft region and the solvent and thereby improve the dispersibility, More preferably a graft chain having an ester or polyether.

The graft copolymer preferably contains, in terms of mass, the repeating unit having a graft chain in a range of 2 to 90 mass%, preferably 5 to 30 mass%, based on the total mass of the graft copolymer More preferable. When the content of the repeating unit having a graft chain is within this range, the dispersibility of the colorant is good.

Known macromonomers can be used as the macromonomers used when the graft copolymer is produced by radical polymerization. Macromonomer AA-6 (polymethacryloylmethyl group whose terminal group is methacryloyl group) manufactured by DOKOSEI CO., LTD. , AN-6S (a copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (poly (meth) acrylate having a terminal group of methacryloyl group), AS-6 (polystyrene in which the terminal group is methacryloyl group) Butyl acrylate), Flaccel FM5 (manufactured by Daicel Chemical Industries, Ltd.) (5-molar equivalent of 2-hydroxyethyl methacrylate), FA10L (10 molar equivalents of? -Caprolactone of 2-hydroxyethyl acrylate And the polyester-based macromonomers described in JP-A-2-272009.

In the present invention, a graft copolymer containing repeating units represented by any one of the following formulas (1) to (4) may be used as the resin. These graft copolymers can be particularly preferably used as dispersants for black pigments.

[Chemical Formula 5]

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 preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and independently of each other, a hydrogen atom or a methyl group More preferably 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 linking groups represented by the following (Y-1) to (Y-21). In the structures shown below, A and B each represent a bonding site with the left terminal group and the right terminal group in the formulas (1) to (4).

[Chemical Formula 6]

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, but specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, . Among them, as an organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , from the viewpoint of improving the dispersibility, it is preferable to have a steric repulsion effect, and each independently an alkyl group or an alkoxy group having 5 to 24 carbon atoms Among them, branched alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups having 5 to 24 carbon atoms, and alkoxy groups having 5 to 24 carbon atoms are 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 formulas (1) and (2) are preferably an integer 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 linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, plural R ³ may be the same or different.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a straight chain 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, more preferably a straight chain alkyl group having 1 to 20 carbon atoms, More preferably a straight-chain alkyl group having 1 to 6 carbon atoms. When q is 2 to 500 in the formula (4), a plurality of X ⁵ and R ⁴ existing in the graft copolymer may be the same or different.

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

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

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

(7)

Formula (1A) of the, X ^1, Y ^1, Z ¹ and n is ^1, X, Y ^1, Z ¹ and n and the consent of the formula (1), are also the same preferable range.

In the formula ^{(2A), X 2, Y} 2, Z 2 and m is ^2, X, Y ^2, Z ² and m and consent of the formula (2) are also the same preferable range.

In the formula (3A) or ^{(3B), X 3, Y} 3, Z 3 , and p is ^3, and X, Y ^3, Z ^3, and p and consent of the formula (3) it is also the same preferable range.

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

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

The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "computed logP" calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of the compound and estimates the logP value of the compound by dividing the chemical structure into partial structures (fragments) and summing the assigned logP contributions for the fragments. The details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v 4.82 is used.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., P. 295, Pergamon Press, 1990 C. Hansch & A. J. Leo. &Lt; / RTI &gt; SUBSTITUTE FORMULATIONS IN CHEMISTRY AND BIOLOGY. John Wiley &amp; Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306,1993.

log P means a common logarithm of the partition coefficient P, and is a physical property value indicating how an organic compound is distributed in an equilibrium of a two-phase system of oil (generally, 1-octanol) and water as a quantitative value, Is expressed by the following equation.

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 value of logP is increased to 0 with 0, the oil solubility is increased and when the minus value is increased, the water solubility is increased. There is a negative correlation with the water solubility of the organic compound, And is widely used as a parameter for evaluating the hydrophilicity of water.

The graft copolymer is preferably a hydrophobic repeating unit having at least one repeating unit selected from repeating units derived from a monomer represented by the following formulas (i) to (iii).

[Chemical Formula 8]

In the formulas (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine or bromine) (For example, a methyl group, an ethyl group, a 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. It is particularly preferable that R ² and R ³ are hydrogen atoms.

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

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, a substituted alkenylene group), a divalent aromatic group (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, wherein R ³¹ represents a hydrogen atom or a substituted or unsubstituted arylene group), a divalent heterocyclic group, An aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), or a combination thereof.

L is preferably a divalent linking group containing a single bond, an alkylene group or 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 repeating oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by - (OCH ₂ CH ₂ ) _n -, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

Z is preferably an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (e.g., an arylene group, a substituted arylene group), a heterocyclic group, -S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-) .

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the cyclic hydrocarbon groups include a bicyclohexyl group, a perhydronaphthalene group, a biphenyl group, and a 4-cyclohexylphenyl group. As the bridged cyclic hydrocarbon ring, there may be mentioned, for example, phenane, bonene, nopine, novone, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] , Etc.), tricyclic [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane ring, such as homocyclododecane, homocyclododecane, Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, and perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like can be given . Examples of the bridged cyclic hydrocarbon ring include condensed cyclic hydrocarbon rings such as perhydro- naphthalene (decalin), perhydroanthracene, perhydro-phenanthrene, perhydro-acenaphthene, perhydrofluorene, perhydroindene, And a condensed ring in which a plurality of 5- to 8-membered cycloalkene rings such as a benzene ring are condensed. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. Provided that the aliphatic group does not have an acid group as a substituent.

The number of carbon atoms in the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 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. Provided that the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^32, where R ³² be an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Provided that the heterocyclic group does not have an acid group as a substituent.

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

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, L is a single bond or an alkylene group or an oxyalkylene structure, X is an oxygen An atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. The monomer represented by the formula (ii) is preferably a compound wherein 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 formula (iii) is preferably a compound wherein R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group.

Examples of representative compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrene, and the like. As an example of the compounds represented by the formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of Japanese Laid-Open Patent Publication No. 2013-249417, the contents of which are incorporated herein by reference.

In the graft copolymer, the hydrophobic repeating unit is contained preferably in a range of 10 to 90 mass%, more preferably 20 to 80 mass%, based on the total mass of the graft copolymer in mass conversion desirable. When the content is in the above range, sufficient pattern formation is obtained.

The above-mentioned graft copolymer may contain, in addition to the repeating units represented by the above-mentioned formulas (1) to (4), a functional group capable of forming an interaction with a pigment or the like (e.g., an acid group, a basic group, a coordinating group, ) As a repeating unit.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Particularly preferred is a colorant such as a black pigment And a carboxylic acid group having a high dispersibility.

The graft copolymer may have one or more repeating units having an acid group.

The graft copolymer may or may not contain a repeating unit having an acid group, but if contained, the content of the repeating unit having an acid group is preferably 5 to 80% by mass, in terms of mass, based on the total mass of the graft copolymer , And more preferably from 10 to 60 mass%.

Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, an amide group and the like. Particularly preferably, the basic group has a good adsorption ability to a colorant, It is a tertiary amino group with high dispersibility. The graft copolymer may have one or more of these basic groups.

The graft copolymer may or may not contain a repeating unit having a basic group. When contained, the content of the repeating unit having a basic group is preferably 0.01 to 50% by mass, based on the total mass of the graft copolymer, By mass, and more preferably from 0.01 to 30% by mass from the viewpoint of inhibiting developability.

Examples of the coordinating group and the reactive functional group include an acetyl acetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, an acid chloride, and the like. Particularly preferred is an acetyl acetoxy group having good adsorptivity to a colorant and high dispersibility. The graft copolymer may contain 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 functional group having a reactivity, but if contained, the content of these repeating units is, on a mass basis, the total weight of the graft copolymer , Preferably from 10 to 80 mass%, and more preferably from 20 to 60 mass% from the viewpoint of suppressing development inhibition.

In the case where the graft copolymer has a functional group capable of forming an interaction with the pigment other than the graft chain, there is no particular limitation on how these functional groups are introduced. The graft copolymer may be represented by the following formulas (iv) to (vi) Is preferably one having at least one repeating unit selected from repeating units derived from a monomer represented by the following formula

[Chemical Formula 9]

R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), or a carbon atom (For example, a methyl group, an ethyl group, a propyl group, etc.) having a number of 1 to 6.

In the 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, Is a hydrogen atom or a methyl group. In the formula (iv), it is particularly preferable that R ¹² and R ¹³ are each a hydrogen atom.

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

Y in the formula (v) represents a metha-popular or nitrogen atom.

L ₁ in formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, and a substituted alkenylene group) (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ '-, a substituted arylene group, and a substituted arylene group), a divalent heterocyclic group, Wherein R ³¹ 'represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), or a combination thereof.

L ₁ is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₁ may also include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by - (OCH ₂ CH ₂ ) _n -, and n is preferably an integer of 2 or more, more preferably an integer of 2 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, more preferably a carboxylic acid group.

R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine or bromine), an alkyl group having 1 to 6 carbon atoms (for example, A methyl group, an ethyl group, a propyl group, etc.), -Z ₁ , or -L ₁ -Z ₁ . Here, L ₁ and Z ₁ is, and L ₁ and Z ₁ and copper in the above, preferred examples are the same. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

The monomers represented by formula (iv) are those wherein R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or a methyl group, L ₁ is a divalent linking group containing an alkylene group or an oxyalkylene structure, X is an oxygen atom Or an imino group, and Z is a carboxylic acid group. The monomer represented by the formula (v) is preferably a compound wherein 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 meta-hapten. The monomer represented by the formula (vi) is preferably a compound wherein 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 compound described in paragraphs 0127 to 0129 of Japanese Laid-Open Patent Publication No. 2013-249417, the contents of which are incorporated herein by reference.

[Chemical formula 10]

Specific examples of the dispersant are DA-7301 manufactured by Gusumoto Kasei Co., Ltd., DISPERBYK-101 (polyamide amine phosphate) manufactured by BYK Chemie, 107 (carboxylic acid ester), 110 (Polyphosphate), 130 (polyamide), 140, 142, 145, 161, 162, 163, 164, 165, 166, 170, 180, 187, 190, 191, 2001, (High molecular weight unsaturated polycarboxylic acid), 9076 ", EFKA manufactured by EFKA 4047, 4050 to 4165 (polyurethane-based), EFKA 4330 to 4340 Block copolymers), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 Pigment TG-710 (trade name, manufactured by Ajinomoto Fine Techno Co., Ltd., Ajisper PB821, PB822, PB880, and PB881 manufactured by Kyoeisha Chemical Co., 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (poly (methacrylic acid)), "Polyol No. 50E, No. 300 (acrylic copolymer) ", manufactured by Kusumoto Chemical Industry Co., (Naphthalene sulfonic acid-formaldehyde condensate), MS, C, SN-B (aromatic sulfonic acid-formaldehyde-formaldehyde condensate), DA-703-50, DA-705, DA- Emulsion 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ", "acetamine 86 (stearylamine acetate)" , 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (having a functional part at the terminal end) NIKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", manufactured by Nikko Chemicals Co., Ltd., Kawaken Co., Fine Chemicals Co., Ltd. " Noact T-8000E "manufactured by Shin-Etsu Chemical Co., Ltd.," Organosiloxane polymer KP341 "manufactured by Shin-Etsu Chemical Co., Ltd., EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aide 9100, manufactured by SANKON KOKO Co., L121, P-123 "manufactured by Sanyo Chemical Industries, Ltd., and" Ionet " (Trade name) S-20 ". Acrylic FFS-6752, Acribe FFS-187, ARC Liqueur RD-F8 and Cyclamer P can also be used.

<< Radical Polymerizable Compound >>

The active energy ray curable composition may contain a radically polymerizable compound. The radically polymerizable compound is preferably a polymerizable compound having an ethylenic unsaturated bond. The radically polymerizable compound is preferably a compound having at least one group having an ethylenically unsaturated bond, more preferably at least two compounds, and more preferably at least three. The upper limit is, for example, preferably 15 or less, more preferably 6 or less. Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The radical polymerizable compound may be, for example, a monomer, a prepolymer, that is, a chemical form such as a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred.

The molecular weight of the radical polymerizing compound is preferably 100 to 3,000, more preferably 250 to 1,500.

The radical polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functional groups, and more preferably a (meth) acrylate compound having 3 to 6 functional groups.

Examples of monomers and prepolymers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters, amides, Preferably, it is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and a multimer thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, or a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group are reacted with monofunctional or polyfunctional alcohols, amines, reactants with thiols, Also suitable are unsaturated carboxylic acid esters or amides having a sex substituent and reacting with monofunctional or polyfunctional alcohols, amines and thiols. It is also possible to use a group of compounds substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like instead of the above unsaturated carboxylic acid.

As specific compounds of these compounds, compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can be suitably used in the present invention.

As the radical polymerizing compound, a compound having at least one group having an ethylenic unsaturated bond and having a boiling point of 100 占 폚 or more at normal pressure is also preferable. For example, reference can be made to paragraphs 0227 and 02257 of Japanese Laid-Open Patent Publication No. 2013-29760 and paragraphs 0254 to 0257 of Japanese Laid-Open Patent Publication No. 2008-292970, all of which are incorporated herein by reference.

Radical polymerizable compounds include dipentaerythritol triacrylate (KAYARAD D-330, Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (KAYARAD D-320, Nippon Kayaku Kabushiki Kaisha, (KAYARAD D-310 manufactured by Nippon Kayaku Kabushiki Kaisha), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd.), dipentaerythritol penta A-DPH-12E manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded through ethylene glycol or propylene glycol residues For example, SR454, SR499 commercially available from Satomaru Co., Ltd.). These oligomer types can also be used. NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.) and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) may also be used.

Preferred embodiments of the radically polymerizable compound are shown below.

The radically polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. As the radically polymerizable compound having an acid group, an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid are preferable, and a radically polymerizable compound having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride Compound is more preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co.,

The preferred acid value of the radically polymerizable compound is 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g. If the acid value of the radical polymerizing compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in terms of production and handling. Further, the photopolymerization performance is good and the curability is excellent.

As the radical polymerizing compound, a compound having a caprolactone structure is also a preferable embodiment.

The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta (Meth) acrylic acid and? -Caprolactone obtained by esterifying a polyhydric alcohol such as trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, (Meth) acrylate. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferable.

(11)

In the formula (Z-1), all six R's are groups represented by the following formula (Z-2), or one to five of the six R's are groups represented by the following formula (Z-2) Is a group represented by the formula (Z-3).

[Chemical Formula 12]

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

[Chemical Formula 13]

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

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

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

[Chemical Formula 14]

E in the formulas (Z-4) and (Z-5) each independently represents - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) , Y 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 sum of the (meth) acryloyl groups is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40.

The total number of (meth) acryloyl groups in the formula (Z-5) is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.

The - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the formula (Z-4) or the formula (Z- The form of bonding to X is preferred.

The compounds represented by the formula (Z-4) or (Z-5) may be used singly or in combination of two or more. Particularly, in the embodiment in which all of the six X's are acryloyl groups in the formula (Z-5), and the compound in which all the six X's are acryloyl groups in the formula (Z-5) And a compound in which one is a hydrogen atom are preferable. According to this aspect, developability can be further improved.

The content of the compound represented by the formula (Z-4) or (Z-5) in the radical polymerizing compound 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) can be obtained by subjecting a pentaerythritol or dipentaerythritol, which is a conventionally known process, to ring-opening addition reaction of ethylene oxide or propylene oxide And (meth) acryloyl group by introducing a (meth) acryloyl group into the terminal hydroxyl group of the ring-opening skeleton, for example, by reacting it with (meth) acryloyl chloride. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the formula (Z-4) and (Z-5).

Among the compounds represented by the formula (Z-4) or (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

(A), (b), (f), (f), and (f) are examples of the compounds represented by the following formulas , (e) and (f) are preferable.

[Chemical Formula 15]

[Chemical Formula 16]

Examples of commercially available radically polymerizable compounds represented by the formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

The content of the radical polymerizing compound is preferably 0.1 to 40 mass% with respect to the total solid content of the active energy ray curable composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30 mass% or less, for example, and more preferably 20 mass% or less. The radical polymerizing compound may be used singly or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.

<< Cationic Polymerizable Compound >>

The active energy ray curable composition may contain a cationic polymerizable compound. As the cationic polymerizable compound, a compound having a cyclic ether group can be mentioned. Examples of the cyclic group include an epoxy group and an oxetanyl group, and an epoxy group is preferable.

The cationic polymerizable compound is preferably a compound having two or more cyclic ethers in one molecule.

The cationic polymerizable compound may be a low molecular weight compound (for example, having a molecular weight of less than 2,000, further having a molecular weight of less than 1,000), a macromolecule (for example, a molecular weight of 2,000 or more, . The weight average molecular weight of the cationic polymerizable compound is preferably 200 to 100,000, more preferably 500 to 50,000.

Specific examples of the compound having two or more epoxy groups in the molecule include aliphatic epoxy compounds and the like. Reference may also be made to the description of paragraphs 0021 to 0031 of WO2012 / 093591, the contents of which are incorporated herein by reference.

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- -321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-821, EX-821, DLC-204, DLC-205, DLC-206, DLC-201, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX- -301, DLC-402 (manufactured by Nagase ChemteX), Celloxide 2021P, 2081, 3000, EHPE3150, EPOLED GT400, Selbinase B0134 and B0177 (manufactured by Daicel).

These may be used alone or in combination of two or more.

As specific examples of the compound having two or more oxetane groups in the molecule, AOXTENE OXT-121, OXT-221, OX-SQ and PNOX (manufactured by DOA Corporation) can be used.

The compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.

The content of the cationic polymerizable compound is preferably 0.1 to 40 mass% with respect to the total solid content of the active energy ray curable composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30 mass% or less, for example, and more preferably 20 mass% or less. The cationic polymerizable compound may be used singly or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.

<< Photopolymerization initiator >>

The active energy ray curable composition may contain a photopolymerization initiator. When the active energy ray-curable composition contains a radically polymerizable compound, it preferably contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the radical polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. It may also be an activator that generates an active radical by generating some action with a photo-excited sensitizer and may be an initiator that initiates cationic polymerization depending on the type of monomer.

The photopolymerization initiator preferably contains at least one compound having a molar absorptivity 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 (such as those having a triazine skeleton and an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, , Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. As the halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Compounds described in GB-A-5313428, compounds described in German Patent Publication No. 3337024, compounds described in J. Org., &Lt; RTI ID = 0.0 &gt; . Chem .; 29, 1527 (1964), compounds described in Japanese Laid-Open Patent Publication No. 62-58241, compounds described in Japanese Laid-Open Patent Publication No. 5-281728, compounds described in Japanese Laid-Open Patent Publication No. 5-34920, Compounds described in Japanese Patent Publication No. 4212976, and the like.

From the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, oxime A benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, a 3- Aryl-substituted coumarin compounds are preferable.

More preferably, it is a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound or an acetophenone compound , A trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound are more preferable.

As specific examples of the photopolymerization initiator, reference can be made, for example, to paragraphs 0265 to 0268 of Japanese Laid-Open Patent Publication No. 2013-29760, which disclosure is incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm may be used.

As the acylphosphine-based initiator, commercially available IRGACURE-819 or Lucirin-TPO (trade name, all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound.

As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used.

Examples of oxime compounds that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan- , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

J. C. S. Perkin II (1979) pp. Pp. 1653-1660, J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. The compounds described in the respective publications of JP-A-202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797 and JP-A 2006-342166.

As commercial products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are suitably used. Also, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Aches NCI-831 and Adeka Aches NCI-930 (manufactured by ADEKA) Can be used.

As oxime compounds other than the above-mentioned materials, compounds described in Japanese Patent Publication No. 2009-519904 in which oxime is linked to N of a carbazole ring, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in Japanese Unexamined Patent Application Publication Nos. 2002-15025 and 2009-292039 wherein nitroxide groups are introduced, ketoxime compounds disclosed in WO2009 / 131189, triazine skeleton and oxime skeleton, The compound described in U.S. Patent Publication No. 7556910, the compound described in JP-A-2009-221114 which has an absorption maximum at 405 nm and a good sensitivity to a g-ray light source, or the like may be used.

Preferably, for example, refer to Japanese Patent Application Laid-Open No. 2013-29760, paragraphs 0274 to 0275, the content of which is incorporated herein by reference.

Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the form (E) form and the form (Z) form.

[Chemical Formula 17]

In the 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 non-metallic atomic group.

Examples of the monovalent nonmetal 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. These groups may have one or more substituents. The substituent described above may be substituted with 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. As the substituent, there may be mentioned the above substituents.

In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group or an alkane-ylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. As the substituent, there may be mentioned the above substituents.

The present invention can also use an oxime compound having a fluorine atom as a photopolymerization initiator. Specific examples of the fluorine atom-containing oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A No. 2014-500852, compounds described in JP-A-2013-164471 (C-3), and the like. The contents of which are incorporated herein by reference.

The present invention may use a compound represented by the following formula (1) or (2) as a photopolymerization initiator.

[Chemical Formula 18]

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

In the formula (2), R ^1, R ^2, R ³ and R ^4, and R ^1, R ^2, R ³ and R ⁴ with the consent of 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 , A halogen atom or a hydroxyl group, and 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, 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 each preferably 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 the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. The contents of which are incorporated herein by reference.

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

[Chemical Formula 19]

The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a 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, and still more preferably 5,000 to 200,000 from the viewpoint of sensitivity.

The molar extinction coefficient of the compound can be measured by a known method. For example, the measurement is preferably performed at a concentration of 0.01 g / L using an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

The photopolymerization initiator used in the present invention may be used in combination of two or more as necessary.

The content of the photopolymerization initiator is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and still more preferably 1 to 20 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 photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more kinds are included, it is preferable that the total amount is within the above range.

<< Acid Generator >>

The active energy ray curable composition may 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 which generates an acid upon irradiation with an active energy ray (radiation). Examples of the acid generating agent include light (400 to 200 nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h-line, i-line, and the like) used in a photocationic polymerization initiator, a colorant of a dye, a photochromic agent, , KrF excimer laser light), an ArF excimer laser light, an electron beam, an X-ray, a molecular beam, or an ion beam, and selecting an acid generator having sensitivity to ultraviolet rays desirable.

Examples of the acid generator include an onium salt compound such as a diazonium salt, a phosphonium salt, a sulfonium salt, and an iodonium salt, which decomposes upon irradiation with radiation, an onium salt compound such as imidosulfonate, oxime sulfonate, , Sulfone compounds such as di- sulfone and ortho-nitrobenzyl sulfonate, and the like. Specific examples of the acid generator, specific compounds, and preferred examples include the compounds described in Japanese Patent Application Laid-Open No. 2008-13646, paragraphs 0066 to 0122, and they can be also applied to the present invention.

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

[Chemical Formula 20]

In formula (b1), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group. X ^- represents an unsubstituted anion, preferably a sulfonic acid anion, a carboxylic acid anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- And groups represented by the following formulas, and BF ₄ ^- , PF ₆ ^- , and SbF ₆ ^- are preferable.

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

The content of the acid generator is preferably from 0.1 to 50 mass%, more preferably from 0.5 to 30 mass%, and still more preferably from 1 to 20 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 kind of acid generator or two or more kinds thereof. When two or more kinds are included, it is preferable that the total amount is within the above range.

<< Silane coupling agent >>

The active energy ray-curable composition may contain a silane coupling agent for the purpose of improving adhesion with a 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 at a low temperature process of 100 占 폚 or less by using an active energy ray curable composition containing a thermosetting resin, adhesion with a substrate can be sufficiently secured by further containing a silane coupling agent.

In the present invention, the silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. The hydrolyzable group such as an alkoxy group is preferably bonded to a silicon atom. The hydrolyzable group means a substituent which is directly connected to a silicon atom and capable of generating 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 carbon atoms, the number of carbon atoms thereof is preferably 6 or less, more preferably 4 or less. Particularly, 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, it is preferable that the silane coupling agent does not contain a fluorine atom and a silicon atom (however, excluding the silicon atom bonded to the hydrolyzable group) in order to improve the adhesion of the cured film, But excluding the silicon atom bonded to the hydrolyzable group), an alkylene group substituted with a silicon atom, a straight chain alkyl group having a carbon number of 8 or more, and a branched alkyl group having a carbon number of 3 or more.

The silane coupling agent preferably has a group represented by the following formula (Z). * Indicates the binding position.

(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 alkyl group represented by R ^z1 preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. The definition of the hydrolyzable group represented by R ^z2 is as described above.

The silane coupling agent preferably has a curable functional group. Examples of the curable functional group include a (meth) acryloyloxy group, an epoxy group, an oxetanyl group, an isocyanate group, a hydroxyl group, an amino group, a carboxyl group, a thiol group, an alkoxysilyl group, a methylol group, An amido group, a styryl group, and a maleimide group, and more preferably at least one member selected from the group consisting of a (meth) acryloyloxy group, an epoxy group and an oxetanyl group. The curable functional group may be directly bonded to a silicon atom, or may be bonded to a silicon atom through a linking group.

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

One suitable embodiment of the silane coupling agent is the silane coupling agent X represented by the formula (W).

(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 represents an integer of 1 to 3.

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 preferable range is as described above.

Lz represents a single bond or a divalent linking group. As the divalent connecting group, 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 number of carbon atoms of the alkylene group is preferably 1 to 20. The alkylene group may be either straight chain 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 member selected from the group consisting of an alkylene group having from 2 to 10 carbon atoms and an arylene group having from 6 to 12 carbon atoms, or a group selected from the group consisting of -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ - -SO ₂ NR ¹² -, -O-, -S-, and -SO ₂ -, an alkylene group having 2 to 10 carbon atoms, -CO ₂ -, -O-, -CO-, -CONR ¹² -, or a group formed by a combination of these groups. Here, R ¹² represents a hydrogen atom or a methyl group.

m represents 1 to 3, preferably 2 to 3, and more preferably 3.

Examples of the silane coupling agent X include N -? - aminoethyl-? -Aminopropylmethyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N -? - aminoethyl- (Trade name: KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Trade name: KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (Trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), and glycidoxypropyltrimethoxysilane (trade name: KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd.).

The silane coupling agent is also preferably a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to a silicon atom.

The silane coupling agent Y may have at least one silicon atom in the molecule, and the silicon atom may be bonded to the following atoms or substituents. They can be the same atom, substitution or different. The substitutable group may be 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 amino group which may be substituted with an alkyl group and / An alkoxy group of 1 to 20 carbon atoms, an aryloxy group, and the like. These substituents may also be substituted with at least one substituent selected from the group consisting of a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group which may be substituted with an alkyl group and / or an aryl group, , An amide group, an urea group, an ammonium group, an alkylammonium group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof.

At least one hydrolysable 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 preferably has at least one nitrogen atom in the molecule and the nitrogen atom is present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom has at least one organic group as a substituent desirable. The structure of the amino group may be either in the form of a partial structure of a nitrogen-containing heterocycle or in the form of a substituted amino group such as aniline. Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and combinations thereof. These substituents may be further substituted. Examples of the substituent which 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, a sulfonamido group, An amide group, an urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group or a salt thereof, and a sulfo group.

The nitrogen atom is preferably bonded to the curable functional group through an arbitrary organic linking group. Preferable examples of the organic linking group include substituents that can be introduced into the aforementioned nitrogen atom and 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 preferable range is as described above.

The silane coupling agent Y may have at least one curable functional group in one molecule, and it is also possible to have two or more curable functional groups in one molecule. From the viewpoints of sensitivity and stability, it is preferable to have 2 to 20 curable functional groups in one molecule, more preferably 4 to 15, and still more preferably 6 to 10.

The silane coupling agent Y may be, for example, a compound represented by the following 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 an (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 formula (Y) are respectively the same as R ^z1 , R ^z2 , R ^z3 and m in formula (W), and preferable ranges are also the same.

N in the formula (Y) represents an integer of 1 or more. The upper limit is, for example, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The lower limit is, for example, preferably 2 or more, more preferably 4 or more, and more preferably 6 or more. N may be set to 1.

The LN of formula (Y) represents a group having a nitrogen atom.

And to, as a group having nitrogen formula (LN-1) ~ at least one type of, or the formula is selected from (LN-4) (LN- 1) ~ (LN-4), -CO-, -CO 2 -, -O-, -S-, and -SO ₂ -. The alkylene group may be either straight chain 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.

[Chemical Formula 21]

In the formula, * indicates a connected hand.

Specific examples of the silane coupling agent Y include, for example, the following compounds. Et represents an ethyl group. And compounds described in paragraphs 0018 to 0036 of JP-A No. 2009-288703, the contents of which are incorporated herein by reference.

[Chemical Formula 22]

The content of the silane coupling agent is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the active energy ray curable composition. The lower limit is more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, and still more preferably 0.5 mass% or more. The silane coupling agent may be used singly or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.

<< Colored colorant >>

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

In the present invention, the chromatic coloring agent may be a pigment or a dye. It is preferably a pigment.

The pigment satisfies an average particle diameter (r) of preferably 20 nm? R? 300 nm, more preferably 25 nm? R? 250 nm, more preferably 30 nm? R? 200 nm. The "average particle diameter" as used herein means an average particle diameter of secondary particles in which the primary particles of the pigment are aggregated.

It is preferable that the secondary particles of the secondary particles of the pigment that can be used (hereinafter, simply referred to as "particle diameter distribution") have a secondary particle content of 70% by mass or more in total (average particle diameter ± 100) More preferably at least% by mass. The particle size distribution of the secondary particles can be measured using the scattering intensity distribution.

The average particle diameter of the primary particles can be determined by observing with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring the particle size of 100 particles at the portion where particles are not aggregated, and calculating an average value .

The pigment is preferably an organic pigment, and the following may be mentioned. However, the present invention is not limited thereto.

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, , 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,

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 (Above, orange pigment),

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: , 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: , 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, 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, violet pigment)

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64,

These organic pigments can be used singly or in various combinations.

The dye is not particularly limited, and known dyes can be used. Examples of the chemical structure include a pyrazole azo group, an anilino group, a triarylmethane group, an anthraquinone group, an azomethine group, an anthrapyridone group, a benzylidene group, an oxolane group, a pyrazolotriazoazo group, , A phenothiazine-based dye, a pyrrolopyrazole azo dye-based dye, a zethene dye, a phthalocyanine dye, a benzopyran dye, an indigo dye, and a pyromethene dye. It is also possible to use a multimer of these dyes. Also, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 may be used.

As the dyes, acid dyes and / or derivatives thereof may be suitably used.

In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azo dyes, disperse dyes, useful dyes, food dyes, and / or derivatives thereof can also be usefully used.

Specific examples of the acidic dyes are given below, but the present invention is not limited thereto. For example, the following dyes and derivatives of these dyes.

Acid alizarin violet N,

Acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40 to 45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 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, 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, 243,

Food Yellow 3

Acid dyes based on azo dyes, xanthane dyes and phthalocyanines other than the above are also preferable, and C. I. Solvent Blue 44, 38; C. I. Solvent orange 45; Rhodamine B and Rhodamine 110, and derivatives of these dyes are also preferably used.

Among them, examples of the dye include triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyan, phenothiazine, pyrrolopyrazole, trimethyene, It is preferable that the colorant is a colorant selected from the group consisting of benzopyran, indigo, pyrazole, anilino azo, pyrazolotriazoazo, pyridino azo, anthrapyridone and pyromethene.

Further, a pigment and a dye may be used in combination.

When the active energy ray-curable composition contains a chromatic coloring agent, the content of the chromatic coloring agent is preferably 1 to 80 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, still more preferably 10% by mass or more, and still more preferably 20% by mass or more. The upper limit is more preferably 75 mass% or less, and still more preferably 70 mass% or less.

<< Black colorant >>

The active energy ray curable composition may contain a black colorant. As the black colorant, any of an organic black colorant and an inorganic black colorant may be used. You can also use both. The composition containing the black colorant has low curability due to exposure and has conventionally been subjected to heat treatment at a high temperature. According to the method of the present invention, however, even an active energy ray curable composition containing a black colorant can exhibit reliability This excellent cured film can be produced, and the effect of the present invention is remarkable.

(Organic black coloring agent)

Examples of the organic-based black colorant include a bisbenzofuranone compound, an azomethine compound, a perylene compound, and an azo-based compound. Examples of bisbenzofuranone compounds include those described in JP-A No. 2010-534726, JP-A No. 2012-515233, JP-A No. 2012-515234, and the like, for example, "IRGAPHOR Black" &Lt; / RTI &gt; Examples of the perylene compound include CI 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. Examples of the azomethine compound include azo compounds such as those available as "chromopine black A1103 &quot; . The azo-based compound is not particularly limited, but a compound represented by the following formula (A-1) and the like are suitably exemplified.

(23)

(Inorganic black coloring agent)

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 with a small amount. Among them, it is preferable to include at least one of carbon black and titanium black, and particularly, titanium black is preferable.

Titanium black is a black particle containing a titanium atom. Preferably low-order titanium oxide or titanium oxynitride. The titanium black particles can be surface-modified as needed for the purpose of improving dispersibility and inhibiting cohesiveness. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and the water repellent material such as that shown in Japanese Patent Laid-Open Publication No. 2007-302836 is also possible.

Titanium black is typically titanium black particles, and it is preferable that the primary particle diameter and the average primary particle diameter of each particle are small.

Concretely, it is preferable that the average primary particle diameter is in the range of 10 nm to 45 nm. The particle diameter, that is, the particle diameter in the present invention is the diameter of a circle having the same area as the projected area of the outer surface of the particle. The projected area of the particle is obtained by measuring an area obtained by photographing with an electron microscope photograph and correcting the photographing magnification.

The specific surface area of the titanium black is not particularly limited. However, the value measured by the BET (Brunauer, Emmett, Teller) method is preferably set so that the water repellency after surface treatment of the titanium black with the water repellent agent becomes a predetermined performance More preferably 5 to 150 m ² / g, and more preferably 20 to 120 m ² / g.

Examples of commercially available products of 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 (Manufactured by Kasei Corporation).

It is also preferable that titanium black be contained as a pigment dispersion containing titanium black and Si atoms.

In this embodiment, the titanium black is contained in the composition as a dispersoid, and the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersoid is preferably 0.05 or more, more preferably 0.05 to 0.5 And more preferably 0.07 to 0.4.

Here, the above-described dispersed body includes both of the titanium black in the primary particle state and the aggregate (secondary particle) state.

In order to change the Si / Ti of the object to be dispersed (for example, to be 0.05 or more), the following means can be used.

First, titanium oxide and silica particles are dispersed using a dispersing machine to obtain a dispersion, and the dispersion is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C) to form titanium black particles as a main component and Si and Ti And the like can be obtained. The reduction treatment may be performed in an atmosphere of a reducing gas such as ammonia. Examples of the titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo Co., Ltd.) and the like. Examples of commercial products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: Ebonic).

A dispersing agent may be used for dispersing the titanium oxide and the silica particles. As the dispersant, those described in the section of the above-mentioned dispersant can be mentioned.

The above dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. Specific examples include those described below in the column of organic solvents.

Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, can be manufactured by the method described in, for example, Japanese Patent Application Laid-Open No. 2008-266045, paragraph No. 0005 and paragraphs 0016 to 0021.

In the pigment dispersion containing titanium black and Si atoms, the above-mentioned titanium black can be used.

In addition, in the dispersoid, titanium black, a composite oxide of Cu, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide, carbon black, aniline black, and the like for the purpose of adjusting the dispersibility, One or more of black pigments may be used in combination.

In this case, it is preferable that 50% by mass or more of the entire dispersoid is occupied by the to-be-dispersed body made of titanium black.

Further, in the pigment dispersion, other colorants (organic pigments, dyes, etc.) may be used in combination with the titanium black in accordance with the object, so long as the effect of the present invention is not impaired for the purpose of adjusting the light shielding property .

Hereinafter, a material used for introducing Si atoms into the object to be dispersed will be described. When a Si atom is introduced into the object to be dispersed, a Si-containing substance such as silica may be used.

Examples of usable silica include precipitated silica, fumed silica, colloidal silica, synthetic silica and the like, and these may be appropriately selected and used.

In addition, since the particle diameter of the silica particles is smaller than the film thickness when the light shielding film is formed, the silica particles are preferably used as the silica particles because of better light shielding properties. Further, as an example of the particulate type silica, there may be mentioned, for example, silica described in Japanese Patent Application Laid-Open No. 2013-249417, paragraph No. 0039, the content of which is incorporated herein by reference.

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

The total content of the black coloring agent and the chromatic coloring agent is preferably 1 to 80 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, still more preferably 10% by mass or more, and still more preferably 20% by mass or more. The upper limit is more preferably 75 mass% or less, and still more preferably 70 mass% or less.

<< Infrared absorbent >>

The active energy ray curable composition may contain an infrared absorbing agent.

In the present invention, the infrared absorbing agent means a compound having a maximum absorption in a wavelength region of an infrared region (preferably a wavelength of 800 to 1300 nm).

Examples of the infrared absorber include a pyrrolopyrrole compound, a copper compound, a cyanide compound, a phthalocyanine compound, an iminium compound, a thiol complex compound, a transition metal oxide compound, a squarylium compound, Compounds, quaternary compounds, dithiol metal complex compounds, and croconium compounds.

The pyrrolopyrrole compound may be a compound described in Japanese Patent Application Laid-Open No. 2009-263614, paragraphs 0049 to 0058, the contents of which are incorporated herein by reference. As the phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanide compound, the squarylium compound and the croconium compound, the compounds disclosed in Japanese Patent Application Laid-Open No. 2010-111750, paragraphs 0010 to 0081 may be used , The contents of which are incorporated herein by reference. The cyanide compound can also be referred to, for example, as "functional coloring matter, Makawa Ogawa / Masaru Matsuoka / Gitao Daiziro / Hirashimatsuaki Aichi, Kodansha Scientific" .

Further, as the infrared absorbent, a compound disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729, a compound disclosed in paragraphs 0027 to 0062 of Japanese Patent Application Laid-Open No. 2002-146254, a compound disclosed in Japanese Patent Application Laid- Near-infrared absorbing particles consisting of crystallites of oxides containing Cu and / or P disclosed in JP-A Nos. 0034 to 0067 and having a number-average aggregate particle diameter of 5 to 200 nm may be used, and these contents are incorporated herein. FD-25 (made by Yamada Kagaku Co., Ltd.) and IRA842 (manufactured by Exiton) can also be used.

When the active energy ray-curable composition contains an infrared absorbing agent, the content of the infrared absorbing agent is preferably 1 to 80% by mass based on the total solid content of the active energy ray curable composition. The lower limit is more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably 20% by mass or more. The upper limit is more preferably 75 mass% or less, and still more preferably 70 mass% or less.

The total content of the infrared absorbing agent, the black coloring agent and the chromatic coloring agent is preferably 1 to 80 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, still more preferably 10% by mass or more, and still more preferably 20% by mass or more. The upper limit is more preferably 75 mass% or less, and still more preferably 70 mass% or less.

<< Pigment Derivatives >>

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 the organic pigment is substituted with an acidic group, a basic group or a phthalimide methyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferable.

<< Organic solvents >>

The active energy ray curable composition may contain an organic solvent.

The organic solvent is basically not particularly limited as long as solubility of each component and applicability of the composition are satisfied.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, (For example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate, and the like) such as methyl lactate, ethyl lactate, and alkyloxyacetate Ethyl acetate and the like), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl propionate, ethyl 3-ethoxypropionate)), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, Ethyl propionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like) (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, , Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as 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 Propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like, and as ketones, for example, Methyl propionate, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbon compounds such as toluene and xylene.

These organic solvents are preferably used in combination of two or more kinds in view of solubility of the polymerizable compound, alkali-soluble resin, etc., and improvement of the application surface shape. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- A mixed solution composed of two or more kinds selected from methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate to be.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably 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 mass%, more preferably 5 to 60 mass%, and most preferably 10 To 50% by mass is more preferable.

The active energy ray curable composition may contain only one type of organic solvent or two or more kinds of organic solvents. When two or more kinds are included, it is preferable that the total amount is within the above range.

<< Polymerization inhibitor >>

In the active energy ray curable composition, it is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during the preparation of the composition.

Examples of the polymerization inhibitor include hydroquinone, para-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'- -tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxyamine cetylsulfate.

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 based on the total solid content of the active energy ray curable composition.

The active energy ray curable composition may contain only one kind of polymerization inhibitor or two or more kinds thereof. When two or more kinds are included, it is preferable that the total amount is within the above range.

<< Surfactant >>

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

For example, by containing a fluorine-based surfactant, the liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved. That is, in the case of forming a cured film using a coloring composition containing a fluorine-containing surfactant, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, do. Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoints of the uniformity of the thickness of the coating film and the liquid-repellency, and the solubility in the coloring composition is also good.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, and SC-101 (manufactured by Sumitomo 3M Limited), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, (Manufactured by ASAHI GLASS CO., LTD.), PF636, and SC-103, SC-104, SC-105, SC1068, SC- PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

As the fluorine-based surfactant, a block polymer may be used. Specific examples thereof include the compounds described in Japanese Laid-Open Patent Publication No. 2011-89090.

The following compounds are also exemplified as the fluorine-based surfactants used in the present invention.

&Lt; EMI ID =

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

A fluorine-containing polymer having an ethylenic unsaturated group in its side chain may also be used as a fluorine-containing surfactant. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A No. 2010-164965, for example, Megapark RS-101, RS-102 and RS-718K manufactured by DIC. The fluorinated polymer having an ethylenic unsaturated group in the side chain is a compound different from the above-mentioned radically polymerizable compound.

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol di-laurate, polyethylene glycol di Lactic acid esters such as stearate and consumptive fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 manufactured by BASF) Ltd.) and the like. Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001 and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also 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.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

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

Examples of silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," Tory Silicone SH8400 "and" TSF-4440 "manufactured by Momentive Performance Materials "KF341", "KF6001", and "KF6002" manufactured by Shin-Etsu Silicones Co., Ltd., "BYK307", "BYK323", and "BYK330" manufactured by Big Chemie.

When the active energy ray-curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the active energy ray- .

The active energy ray-curable composition may contain only one type of surfactant, or may contain two or more types of surfactant. When two or more kinds are included, it is preferable that the total amount is within the above range.

<< Other additives >>

The active energy ray curable composition may contain various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor and the like, if necessary. Examples of these additives include those described in Japanese Patent Application Laid-Open No. 2004-295116, paragraphs 0155 to 0156, the content of which is incorporated herein by reference.

The active energy ray curable composition may contain a sensitizer or light stabilizer described in Japanese Patent Application Laid-Open No. 2004-295116, paragraph number 0078, and a thermal polymerization inhibitor described in paragraph No. 0081 of the same publication.

&Lt; Example of active energy ray curable composition >

In the production method of the present invention, when the curable film having a thickness of 0.5 m is formed, the active energy ray curable composition preferably has an optical density at any wavelength in the range of 260 to 440 nm (preferably 2 or more , More preferably not less than 3).

When the curable film having a thickness of 0.5 m is formed, the active energy ray curable composition preferably has a minimum value of optical density in the range of 260 to 440 nm, more preferably 2 or more, and more preferably 3 or more desirable.

When the curable film having a thickness of 0.5 m is formed, the active energy ray curable composition preferably has an optical density of 1 or more, more preferably 2 or more, and more preferably 3 or more at a wavelength of 365 nm.

The optical density is a value expressed by a logarithm of the degree of absorption and is a value defined by the following formula. In the present invention, the optical density of the cured film is a value measured by a spectrometer (UV4100 (trade name)) manufactured by Hitachi High-Technologies Corporation, in which light having a wavelength of 365 nm is incident and its transmittance is measured.

OD (?) = Log ₁₀ [T (?) / I (?)]

represents the optical density at the wavelength?, T (?) represents the amount of transmitted light at the wavelength?, and I (?) represents the amount of incident light at the wavelength? .

In order to set the minimum value of the optical density in the wavelength region of the cured film to 1 or more, a coloring agent that absorbs light in a wavelength range of 260 to 440 nm is contained, or the content of the coloring agent in all the solid components is appropriately adjusted .

As the active energy ray curable composition having the above optical density, for example, an active energy ray curable composition containing a black colorant (preferably, an inorganic black colorant) can be mentioned.

As another example of the above-mentioned active energy ray-curable composition, the ratio A / B of the maximum value A of the absorbance in the wavelength range of 400 nm or more and less than 580 nm and the maximum value B of the absorbance in the wavelength range of 580 nm or more and 750 nm or less, B is 0.3 to 3, the ratio C / D of the maximum value D of the absorbance in the wavelength range of 1000 nm to 1300 nm and the minimum value of the absorbance C in the wavelength range of 400 nm to 750 nm is 5 or more Curable compositions may also be mentioned. By using a composition having this spectroscopic property, a cured film having a maximum transmittance of 20% or less in a wavelength range of 400 to 700 nm and a spectral characteristic in which a minimum value in a specific range of a wavelength of 850 to 1300 nm is 80% .

The absorbance A? At a certain wavelength? Is defined by the following equation (1).

A? = -Log (T?) ... (One)

A? Is the absorbance at the wavelength?, And T? Is the transmittance at the wavelength?.

In the present invention, the value of the absorbance may be a value measured in a solution state or a value in a film state formed by using the composition. In the case of measuring the absorbance in the film state, the composition is coated on a glass substrate so as to have a predetermined film thickness after drying by a method such as spin coating and dried at 100 DEG C for 120 seconds using a hot plate It is preferable to use a prepared film. The film thickness of the film was measured by using a contact-type surface shape measuring device (DEKTAK150 manufactured by ULVAC Co., Ltd.).

The absorbance can be measured using a conventionally known spectrophotometer. The conditions for measuring the absorbance are not particularly limited, but the minimum value of the absorbance in a wavelength range of from 580 nm to 750 nm is preferably set to be B under the condition that the maximum value A of the absorbance in a wavelength range of 400 nm or more and less than 580 nm is adjusted to 0.1 to 3.0 , The minimum value C of the absorbance in the wavelength range of 400 nm to 750 nm and the maximum value D of the absorbance in the wavelength range of 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 of adjusting the maximum value A of the absorbance in the wavelength range of 400 nm or more and less than 580 nm to 0.1 to 3.0. For example, when the absorbance is measured in the composition (solution) state, a method of adjusting the optical path length of the sample cell can be mentioned. In the case of measuring the absorbance in the film state, a method of adjusting the film thickness and the like can be mentioned.

The measurement method of the spectroscopic characteristics, the film thickness and the like of the film is shown below.

The composition was coated on a glass substrate by a spin coat method or the like so that the film thickness after drying was the predetermined film thickness described above and dried at 100 DEG C for 120 seconds using a hot plate. The film thickness of the film was measured by using a contact-type surface shape measuring device (DEKTAK150 manufactured by ULVAC Co., Ltd.) after the dried substrate having the film. The dried substrate having this film 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).

The active energy ray curable composition having the above spectroscopic characteristics includes a composition containing a colorant shielding visible light. The color material shielding visible light is preferably a material that absorbs light in the wavelength range from violet to red. The color material shielding visible light preferably satisfies at least one of the following requirements (A) and (B).

(A): two or more kinds of chromatic coloring agents are included, and a combination of two or more chromatic coloring agents forms black.

(B): organic black coloring agent.

Examples of the chromatic coloring agent and the organic black coloring agent include those described above.

In the present invention, the coloring material shielding visible light has, for example, a ratio A / B of the maximum value A of the absorbance in the wavelength range of 450 to 650 nm and the minimum value B of the absorbance in the wavelength range of 900 to 1300 nm of 4.5 Or more. The above characteristics may be satisfied by one type 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 kinds of coloring agents selected from a red colorant, a yellow colorant, a blue colorant, and a purple colorant. Further, it is preferable to contain at least one kind selected from a red coloring agent, a yellow coloring agent and a purple coloring agent, and a blue coloring agent. Among them, any one of the following (1) to (3) is preferable.

(1) A mode containing red colorant, yellow colorant, blue colorant, and purple colorant.

(2) an aspect containing a red colorant, a yellow colorant, and a blue colorant.

(3) a mode containing a yellow colorant, a blue colorant, and a purple colorant.

Wherein the coloring agent comprises a red colorant, a yellow colorant, a blue colorant and a purple colorant, wherein the mass ratio of the red colorant to the chromatic colorant is in the range of 0.1 to 0.6, 0.4, the mass ratio of the blue colorant is 0.1 to 0.6, and the mass ratio of the purple colorant is preferably 0.01 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, the mass ratio of the blue colorant is 0.2 to 0.5, and the mass ratio of the purple colorant is 0.05 to 0.25.

When a red colorant, a yellow colorant and a blue colorant are contained as the chromatic colorant, the mass ratio of the red colorant to the chromatic colorant is in the range of 0.2 to 0.7, the mass ratio of the yellow colorant is 0.1 to 0.4, And the mass ratio of the blue colorant is preferably 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.

In the case of containing a yellow coloring agent, a blue coloring agent and a purple coloring agent as the chromatic coloring agent, the mass ratio of the yellow coloring agent to the chromatic coloring agent in the mass ratio is 0.1 to 0.4, the mass ratio of the blue coloring agent is 0.1 to 0.6, The mass ratio of the colorant is preferably 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.

In the active energy ray curable composition having the spectroscopic characteristics, an infrared absorbing agent (preferably an infrared absorbing agent having an absorption maximum in the wavelength range of 800 to 900 nm) may be further contained. As a result, a cured film having a maximum transmittance of 20% or less in a wavelength range of 400 to 830 nm and a spectral characteristic of a transmittance of at least 80% in a wavelength range of 1000 to 1300 nm can be suitably formed.

In this embodiment, the infrared absorbing agent is preferably contained in an amount of 10 to 200 parts by mass based on 100 parts by mass of the coloring material shielding visible light. The content of the infrared absorbing agent is preferably 1 to 60 mass%, more preferably 10 to 40 mass%, of the total solid content of the composition. The content of the coloring material shielding visible light is preferably 10 to 60 mass%, more preferably 30 to 50 mass%, of the total solid content of the composition. The total amount of the infrared absorber and the coloring material shielding visible light is preferably from 1 to 80 mass%, more preferably from 20 to 70 mass%, and even more preferably from 30 to 70 mass%, based on the total solid content of the composition .

&Lt; Preparation method of active energy ray curable composition >

The active energy ray curable composition can be prepared by mixing the above-described components.

When the active energy ray curable composition is prepared, each component may be blended at one time or each component may be dissolved and dispersed in a solvent and then blended continuously. The order of addition and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving or dispersing the entire components in a solvent at the same time. If necessary, the components may be appropriately mixed into two or more solutions and dispersions, and they are mixed at the time of use .

In the preparation of the active energy ray-curable composition, it is preferable to filter with a filter for the purpose of removing foreign matters or reducing defects. The filter is not particularly limited as long as it is conventionally used for filtration and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) And / or ultra high molecular weight polyolefin resin). Of these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably about 0.01 to 7.0 mu m, preferably about 0.01 to 3.0 mu m, and more preferably about 0.05 to 0.5 mu m. By setting this range, it is possible to reliably remove minute foreign matter which inhibits the preparation of a uniform and smooth composition in the subsequent steps. Examples of the filter material include polypropylene fiber, nylon fiber, and glass fiber. Specific examples thereof include SBP type series (such as SBP008) manufactured by Loki Techno, TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) filter cartridges can be used.

When using a filter, other filters may be combined. At this time, the filtering by the first filter may be performed once, or may be performed twice or more.

The first filter having different pore diameters may be combined within the above-described range. The hole diameter here can refer to the nominal value of the filter manufacturer. As commercially available filters, there may be mentioned, for example, Nippon Oil Corporation (DFA4201NXEY, etc.), Advantech Toyobo Co., Ltd., Nippon Integrity Corporation (formerly Nippon Mics Co., Ltd.) Can be selected from among various filters provided by the user.

The second filter may be formed of the same material as the first filter described above.

For example, the filtering with the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing the other components.

<Cured film>

The cured film of the present invention is obtained by the method for producing the 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 more preferably 3 or more at any wavelength in the range of 260 to 440 nm.

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 still more preferably 3 or more.

The optical density at a wavelength of 365 nm is preferably 1 or more, more preferably 2 or more, and still more 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. As a result, the higher the optical density is, the more remarkable the effect of the present invention is.

It is preferable that the optical density is a value at a thickness of the cured film of 0.5 m or more.

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

The cured film of the present invention can be preferably used for a color filter, an infrared ray transmission filter, an infrared ray cut filter, a light shielding film, a transparent film, and a band pass filter. In addition, a printed matter may be formed by using an active energy ray curable composition as a printing ink.

In the present invention, the color filter means a filter that transmits light of a specific wavelength among lights of a visible light range and shields light of a specific wavelength. The infrared ray transmission filter means a filter that shields light having a wavelength in a visible range and transmits light (infrared rays) having a wavelength in a specific infrared range. The infrared cutoff filter means a filter that transmits light (visible light) of a visible light range and shields at least a part of light (infrared light) of an infrared range wavelength. Further, the light-shielding film means a film that shields light having a wavelength of at least the visible region. The transparent film means a film that transmits light having a wavelength of at least a visible light range.

The color filter, the infrared ray transmission filter and the infrared ray blocking filter can be used as solid-state image pickup devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), image display devices such as liquid crystal display devices, organic electroluminescence EL) device and the like.

The light shielding film can be formed and used in various components in an image display apparatus and a sensor module (for example, an infrared ray cut filter, an outer peripheral portion of a solid-state image pickup element, a wafer level lens outer peripheral portion, a solid-state image pickup element, etc.). Further, a light shielding film may be formed on at least a part of the surface of the infrared cut filter to form an infrared cut filter with a light shielding film.

The transparent film can be used, for example, for a protective film of an image display device, a solid-state image sensor, an organic EL device, or the like. It may also be used in an optical device.

The solid-state image pickup device is not particularly limited as long as the solid-state image pickup device has the cured film of the present invention and functions as a solid-state image pickup device.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode made of polysilicon or the like are formed on a support, and only a photodiode light- And 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 has a color filter on the device protective film.

Further, it may be a structure having a light-converging means (for example, a microlens or the like, hereinafter the same) on the device protective film and below the color filter (near the support) or a structure having the condensing means on the color filter.

Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of the display device and the details of each display device, refer to, for example, "Electronic display device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued by Sakai Corporation)", "Display device (Ibukisumi Akira, ) Published in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School, 1994)." The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to 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 device preferably has a tandem structure. The tandem structure of the organic EL device is disclosed in Japanese Laid-Open Patent Publication No. 2003-45676, Akiyoshi Mikami, "Frontline of Development of Organic EL Technology - High Brightness, High Precision, Long Life, and Know-How", Kozu Joho Kyo Kai, 326 -328 pages, 2008, and the like. It is preferable that the spectrum of the white light emitted by the organic EL element has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm) and the yellow region (580 nm-620 nm). In addition to these emission peaks, it is more preferable to have a maximum emission peak in the red region (650 nm-700 nm).

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures and the like shown in the following examples can be suitably changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise stated, "part" and "%" are based on mass.

&Lt; Test Example 1 >

[Production of Titanium Black A-1]

120 g of titanium oxide (trade name: "TTO-51N" manufactured by Ishihara Sangyo) having a BET specific surface area of 110 m ² / g and 25 g of silica particles having a BET surface area of 300 m ² / g ("AEROSIL (registered trademark) 300" And 100 g of dispersant ("DISPERBYK-190", manufactured by BYK Chemie) were weighed and 71 g of ion exchange water was added and treated for 30 minutes at revolution speed of 1360 rpm and revolution speed of 1047 rpm using MAURERSTAR KK-400W manufactured by KURABO A mixture aqueous solution was obtained. This aqueous solution was charged in a quartz container, heated to 920 DEG C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama), and then the atmosphere was replaced with nitrogen. At this temperature, ammonia gas was supplied at a rate of 5 mL / And then subjected to a nitriding reduction treatment. The powder recovered after completion was pulverized in a mortar and a titanium black (A-1) having a specific surface area of 85 m ² / g in powder form including Si atoms (a titanium black particle and a dispersed body containing Si atoms) &Lt; / RTI &gt;

[Preparation of Titanium Black Dispersion (TB Dispersion 1)] [

The components shown in the following composition 1 were mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion a.

The resulting dispersion a was subjected to dispersion treatment under the following conditions using Ultra Apex Mill UAM015 manufactured by Gotobuki Kogyo Co., Ltd., and a nylon filter (DFA4201NXEY, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 0.45 mu m was used And filtration was performed to obtain a titanium black dispersion (hereinafter referred to as TB dispersion 1).

(Composition 1)

The titanium black (A-1) obtained as described above 25 parts by mass

· 30% by mass solution of propylene glycol monomethyl ether acetate of Resin 1 ... 25 parts by mass

· Propylene glycol monomethyl ether acetate (PGMEA) ... 50 parts by mass

Resin 1: The following structure. Was synthesized by referring to the description of JP-A-2013-249417. Further, in the formula of Resin 1, x was 43 mass%, y was 49 mass%, and z was 8 mass%. The weight average molecular weight of Resin 1 was 30,000, the acid value was 60 mgKOH / g, and the number of atoms (excluding hydrogen atom) of the graft chain was 117.

(25)

(Dispersion condition)

· Bead diameter: 0.05mm in diameter

· Beads filling rate: 75 volume%

· Mill speed: 8m / sec

· Amount of mixed solution to be dispersed: 500 g

· Circulating flow rate (pump supply): 13 kg / hour

· Treatment temperature: 25 ~ 30 ℃

· Cooling water: Tap water

· Volume in the bead mill annular passage: 0.15L

· Number of passes: 90 passes

[Preparation of active energy ray curable composition]

The following composition was mixed, and then filtered using a nylon filter (DFA4201NXEY, manufactured by Nippon Poult Co., Ltd.) having a pore diameter of 0.45 mu m to prepare an active energy ray curable 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 (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

(Solid content: 30%, solvent: propylene glycol monomethyl ether acetate) (manufactured by DIC Corporation) having a side chain of ethylenic unsaturated group): 10.65 parts by mass

Silane coupling agent (KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.36 parts by mass

Alkali-soluble resin 1: The following structure. Was synthesized in accordance with the manufacturing method of paragraphs 0338 to 0340 of Japanese Laid-Open Patent Publication No. 2010-106268. In the following formulas, x is 90% by mass and z is 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 an atomic number of the graft chain (excluding hydrogen atom) of 117.

(26)

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

(27)

[Preparation of cured film]

Hexamethyldisilazane (HMDS) treatment was performed on a glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)) was used as a substrate. The HMDS treatment was conducted at 100 占 폚 for 60 seconds using ACT8 (trade name) manufactured by Tokyo Electron.

The active energy ray-curable composition prepared above was applied to a HMDS-treated glass base material by a spin coat method, and then subjected to heat treatment (prebaking) for 100 seconds using a hot plate at 65 占 폚. The coating film thickness of the active energy ray-curable composition was adjusted so that the film thickness after pre-baking became 4.0 m.

Subsequently, a transfer pattern (an island of 10 mu m x 10 mu m, pitch of 20 mu m) was formed using an i-line stepper exposure apparatus (FPA-3000i5 +, Canon Co., NA /? = 0.63 / 0.65, Focus offset = And exposed through a mask at an exposure amount of 8,000 J / m ² .

Subsequently, 0.3% by mass of a surfactant NCW-101 (nonionic surfactant) manufactured by Wako Pure Chemical Industries, Ltd. and 0.01 mass% of tetramethylammonium hydroxide (TMAH) were measured using AD-1200 %, For 40 seconds in a puddle.

Next, rinsing treatment was performed using pure water, and then dried at a high rotation 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 condition

Device: Electron beam irradiation device manufactured by Hamamatsu Photonics

Acceleration voltage: 5.0 kV to 200 kV, tube voltage: 4.0 mA

Absorbed dose: 145 kGy

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed at the time of processing): 100 mm / sec (2 sheets / sec on a substrate having a diameter of 200 mm)

Treatment temperature: 23 ° C or 50 ° C

(Measurement of optical density (OD value) of cured film)

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

(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 based on 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: The surface was cloudy, but no problem.

C: It is not practical because a lot of opacity occurs on the surface.

(Evaluation of Reliability of Cured Film)

· Temperature cycle test tolerance

The temperature cycle test of the cured film was carried out under the following conditions.

Apparatus: LTS-150-A / W (manufactured by Hutech)

Test conditions: Each cycle was allowed to stand for 15 minutes in an atmosphere of -45 占 폚 and 85 占 폚, followed by 50 cycles of 1 cycle. The temperature cycle test resistance was evaluated based on the following criteria.

A: There is no pattern peeling.

B: The surface was cloudy, but no problem. There is no pattern peeling.

C: It is not practical because a lot of opacity occurs on the surface. Pattern peeling is also mixed.

· Resistance to constant temperature and humidity test

The constant temperature and humidity test of the cured film was carried out under the following conditions.

After standing for 100 hours in an environment of 85 캜 and 85% relative humidity, the resistance to the constant temperature and humidity test was evaluated according to the following criteria.

A: There is no pattern peeling.

B: The surface was cloudy, but no problem. There is no pattern peeling.

C: It is not practical because a lot of opacity occurs on the surface. Pattern peeling is also mixed.

[Table 1]

As shown in the above table, the test No. 1 was irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. 101 to 108, a cured film excellent in reliability could be produced. Further, the obtained cured film had good adhesion and appearance.

On the other hand, in the test No. 10 in which the acceleration voltage is lower than 10 kV. C11, test No. 100 having an acceleration voltage of 100 kV or more. C12 and C13, the reliability of the obtained cured film was inferior.

&Lt; Test Example 2 &

[Preparation of active energy ray curable composition]

The following composition was mixed, and then filtered using a nylon filter (DFA4201NXEY, manufactured by Nippon Poult Co., Ltd.) having a pore diameter of 0.45 mu m to prepare an active energy ray curable composition.

(Furtherance)

Thermosetting resin (Cyclomer P (ACA) 230AA, (Daicel)) ... 10.96 mass%

Propylene glycol monomethyl ether acetate ... 89.03 mass%

Surfactant 1 ... 0.01 mass%

Silane coupling agent (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) ... The ratio shown in Table 2 (mass% based on the solid content in the composition)

Surfactant 1 was the same as Surfactant 1 of the active energy ray curable composition of Test Example 1.

[Preparation of cured film]

The active energy ray-curable composition prepared above was applied to a HMDS-treated glass base material by a spin coat method, and then subjected to heat treatment (prebaking) for 100 seconds using a hot plate at 65 占 폚. The coating film thickness of the active energy ray curable composition was adjusted so that the film thickness after pre-baking became 0.3 m.

Next, electron beam irradiation was performed under the following conditions to produce a cured film.

Electron beam irradiation condition

Device: Electron beam irradiation device manufactured by Hamamatsu Photonics

Acceleration voltage: 70kV, tube voltage: 4.0mA

Absorbed dose: 145 kGy

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed at the time of processing): 100 mm / sec (2 sheets / sec on a substrate having a diameter of 200 mm)

Treatment 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 mu m) was measured.

(Evaluation of adhesion (crosscut)) [

The adhesion of the cured film prepared above was evaluated by a cross-cut test (according to JIS K5600, but in a lattice pattern composed of 100 pieces of film). In the cross-cut test, the cured film was cut at a depth up to reaching the substrate in eleven positions in the longitudinal direction and in the transverse direction.

The number of peeled film pieces out of 100 films was evaluated according to the following evaluation criteria, and the obtained results are shown in Table 2 below.

A: 0

B: 1 to less than 100

C: 100

(Appearance Evaluation of Cured Film)

The appearance of the cured film was evaluated in the same manner as in Test Example 1.

(Evaluation of Reliability of Cured Film)

· Temperature cycle test tolerance

In the same manner as in Test Example 1, the temperature cycle test resistance of the cured film was evaluated.

· Resistance to constant temperature and humidity test

In the same manner as in Test Example 1, the resistance of the cured film to the constant temperature and humidity test was evaluated.

[Table 2]

As shown in the above table, the test No. 1 was irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. From 201 to 206, it was possible to produce a cured film having excellent reliability.

&Lt; Test Example 3 >

[Preparation of active energy ray curable composition]

The following composition was mixed, and then filtered using a nylon filter (DFA4201NXEY, manufactured by Nippon Poult Co., Ltd.) having a pore diameter of 0.45 mu m to prepare an active energy ray curable composition.

(Furtherance)

Resin (ARC Liqueur RD-F8, Nippon Shokubai Corporation) ... 19.08 parts by mass

Radical Polymerizable Compound (Aronix TO-2349, manufactured by Toagosei Co., Ltd.) 47.7 parts by mass

Photopolymerization initiator (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, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.05 parts by mass

Surfactant (NCW-101, manufactured by Wako Pure Chemical Industries, Ltd.) ... 0.01 parts by mass

Propylene glycol monomethyl ether acetate ... 28.62 parts by mass

[Preparation of cured film]

The active energy ray curable composition prepared above was applied to a glass substrate (diameter 200 mm (8 inch), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)) under the following conditions, Followed by heat treatment (prebaking) for 100 seconds.

Coating: spray coat method

Atomization pressure: 450 Pa

Flow rate: 3.0 cm ³ / min

Distance between nozzle and substrate: 30 mm

Coating speed of scanning: 200 mm / sec (2 sheets / second on a substrate having a diameter of 200 mm)

Scan Pitch: 5.0mm

Coating film thickness: 10.0 占 퐉 - 50.0 占 퐉 (film thickness after prebaking, film thickness is defined as the number of scans)

Subsequently, a transfer pattern (island of 500 mu m x 500 mu m, pitch of 1000 mu m) was formed using an i-line stepper exposure apparatus (FPA-3000i5 +, Canon Co., NA /? = 0.63 / 0.65, Focus offset = And exposed through a mask at an exposure amount of 8000 J / m &lt; ² &gt;.

Subsequently, the resist film was developed with an alkali developer (aqueous solution of tetramethylammonium hydroxide (TMAH), 0.3 mass%) for 60 seconds in a puddle using AD-1200 (manufactured by Mikasa).

Next, rinsing treatment was performed using pure water, and then dried at a high rotation 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 condition

Device: Electron beam irradiation device manufactured by Hamamatsu Photonics

Acceleration voltage: 95kV, tube voltage: 4.0mA

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed at the time of processing): 100 mm / sec (2 sheets / sec on a substrate having a diameter of 200 mm)

Treatment 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.

(Evaluation of Reliability of Cured Film)

· Temperature cycle test tolerance

In the same manner as in Test Example 1, the temperature cycle test resistance of the cured film was evaluated.

· Resistance to constant temperature and humidity test

In the same manner as in Test Example 1, the resistance of the cured film to the constant temperature and humidity test was evaluated.

[Table 3]

As shown in the above table, the test No. 1 was irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. From 201 to 206, it was possible to produce a cured film having excellent reliability.

<Test Example 4>

As the substrate, a glass substrate subjected to HMDS treatment, which was used in Test Example 1, was used.

A red resist (SR2000, manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.) Was applied by a spin coat method and then subjected to a heat treatment (prebaking) using a hot plate at 65 DEG C for 150 seconds. The coating film thickness of the active energy ray curable composition was adjusted so that the film thickness after pre-baking was 2 占 퐉.

Subsequently, using a mask having a transferred pattern (pattern size: 100 mu m x 100 mu m) using an i-line stepper exposure apparatus (FPA-3000i5 +, Canon Co., NA /? = 0.63 / 0.65, Focus offset = 0 mu m) , And an exposure dose of 800 mJ / cm ² .

Subsequently, the resist film was developed with an alkali developer (aqueous solution of tetramethylammonium hydroxide (TMAH), 0.3 mass%) for 60 seconds in a puddle using AD-1200 (manufactured by Mikasa).

Next, rinsing treatment was performed using pure water, and then dried at a high rotation speed of 200 rpm for 30 seconds.

Next, a curing treatment was performed under any of the following conditions to produce a cured film (red coloring pattern).

(EB hardening 1)

Device: Electron beam irradiation device manufactured by Hamamatsu Photonics

Acceleration voltage: 70kV, tube voltage: 4.0mA

Absorbed dose: 145 kGy

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed at the time of processing): 100 mm / sec (2 sheets / sec on a substrate having a diameter of 200 mm)

Treatment temperature: 23 ° C

(EB hardening 2)

Device: Electron beam irradiation device manufactured by Hamamatsu Photonics

Acceleration voltage: 120kV, tube voltage: 4.0mA

Absorbed dose: 145 kGy

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed at the time of processing): 100 mm / sec (2 sheets / sec on a substrate having a diameter of 200 mm)

Treatment temperature: 23 ° C

(UV curing)

Exposure dose (ultraviolet ray): 3,000 mJ / cm ²

Temperature: 35 ℃

(Spectral evaluation)

Spectroscopic observation of the film before curing treatment and spectroscopy of the film after curing treatment under the condition of EB curing 1 were carried out using a spectroscope (MCPD3000, manufactured by Otsuka Chemical Co., Ltd.), but no spectral fluctuation was observed before and after the curing treatment.

(Reliability of Cured Film)

The cured film subjected to the curing treatment under the EB curing condition 1 was subjected to the temperature cycle test resistance and the resistance to the constant temperature and humidity test in the same manner as in Test Example 1 to evaluate the reliability of the cured film and there was no peeling of the pattern and the reliability was excellent .

(Evaluation of color mixture)

The maximum transmittance T0 in a wavelength range of 600 to 700 nm was measured using a spectroscope (MCPD3000, made by OTSUKA DENKI CO., LTD.) Before the curing treatment.

Next, a blue color-for-mixing evaluation (SB2000, manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.) Was spin-coated on the red coloring pattern prepared by performing each curing treatment so as to have a film thickness of 2 탆 after drying, Followed by a heat treatment (prebaking).

Then, using an i-line stepper exposure apparatus (FPA-3000i5 + manufactured by Canon Inc., NA / σ = 0.63 / 0.65, Focus offset = 0 μm) through a mask having a transferred pattern (pattern size: 100 μm × 100 μm) , And an exposure dose of 800 mJ / cm ² .

Subsequently, the resist film was developed with an alkali developer (aqueous solution of tetramethylammonium hydroxide (TMAH), 0.3 mass%) for 60 seconds in a puddle using AD-1200 (manufactured by Mikasa).

Next, rinsing treatment was performed using pure water, and then dried at a high speed of 200 rpm for 30 seconds to form a blue coloring pattern.

Next, the maximum transmittance T1 in a wavelength range of 600 to 700 nm was measured for a cured film (red coloring pattern) after formation of a blue coloring pattern using a spectroscope (MCPD3000, manufactured by Otsuka Chemical Co., Ltd.) (? T = T0 - T1).

Fig. 1 shows the spectrum of the curing treatment of the red coloring pattern, the EB curing 1, and the spectrum of the red coloring pattern after the curing treatment under the condition of UV curing after the color mixture.

[Table 4]

From the above results, it was confirmed that the test No. 1 in which the curing treatment was carried out under the conditions of EB hardening 1. 401, it was possible to effectively suppress the color mixture of the tincture.

&Lt; Test Example 5 >

The substrate shown in the following table was subjected to electron beam irradiation or heat treatment at 220 占 폚 for 5 minutes (hot plate) or 1 hour (oven), and the damage of the substrate was evaluated according to the following criteria.

The electron beam irradiation was performed under the following conditions.

Electron beam irradiation condition

Device: Electron beam irradiation device manufactured by Hamamatsu Photonics

Acceleration voltage: 95kV, tube voltage: 4.0mA

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed at the time of processing): 100 mm / sec (2 sheets / sec on a substrate having a diameter of 200 mm)

Treatment temperature: 23 ° C

Five substrates were used for each treatment condition. The numerical values in the parentheses in the table are defective rates.

A: The substrate after treatment has no warpage, damage, cracks, and discoloration.

B: Part of the substrate was cracked or damaged.

C: There were cracks or warps on 1 to 3 substrates.

D: There were cracks or warpage on four or more substrates.

As a method of curing the composition, a hot plate / oven at 220 占 폚 and an electron beam irradiation can be mentioned. The damage to the substrate by these curing methods was evaluated (five substrates were used).

[Table 5]

As is clear from the above results, even when the substrate subjected to the heat treatment was subjected to warping, damage, cracking, etc., the electron beam irradiation did not cause warping, damage and cracking.

&Lt; Test Example 6 >

[Preparation of pigment dispersion B-1]

The mixed liquid of the following composition was mixed and dispersed for 3 hours using a 0.3 mm diameter zirconia beads with a bead mill (NANO-3000-10 (manufactured by Nippon Bionics KK) equipped with a pressure reducing mechanism) Dispersion B-1 was prepared.

(CI Pigment Red 254: CI Pigment Yellow 139 = 4: 1 (by mass ratio)) consisting of a red pigment (CI Pigment Red 254) and a yellow pigment (CI Pigment Yellow 139) 11.8 parts by mass

Resin 1 (dispersant) (manufactured by 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]

The mixed liquid of the following composition was mixed and dispersed for 3 hours using a 0.3 mm diameter zirconia beads with a bead mill (NANO-3000-10 (manufactured by Nippon Bionics KK) equipped with a pressure reducing mechanism) Dispersion B-2 was prepared.

(CI Pigment Blue 15: 6: CI Pigment Violet 23 = 9: 4 (mass ratio)) comprising a blue pigment (C.I. Pigment Blue 15: 6) and a purple pigment (C.I. Pigment Violet 23) 12.6 parts by mass

Resin 1 (dispersant) (manufactured by BYK 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 (molar ratio in repeating units, Mw = 14,000)

Resin 2 is also an alkali-soluble resin.

(28)

[Preparation of active energy ray curable composition]

The following composition was mixed, and then filtered using a nylon filter (DFA4201NXEY, manufactured by Nippon Poult Co., Ltd.) having a pore diameter of 0.45 mu m to prepare an active energy ray curable composition.

(Furtherance)

· 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 parts by mass

· Silane coupling agent 1 ... 0.6 parts by mass

· Photopolymerization initiator 1 ... 0.9 parts by mass

· Surfactant 1: ... 4.2 parts by mass

· Polymerization inhibitor (para-methoxyphenol) ... 0.001 parts by mass

· PGMEA ... 7.8 parts by mass

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

[Chemical Formula 29]

Radical Polymerizable Compound 1: The following structure (a mixture of the left compound and the right compound in a molar ratio of 7: 3)

(30)

·

·

Silane coupling agent 1: The following structure

(31)

Photopolymerization initiator 1:

(32)

Surfactant 1 was the same as Surfactant 1 of the active energy ray curable composition of Test Example 1.

[Preparation of cured film]

The active energy ray-curable composition prepared above was applied to a glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)) and heat-treated for 120 seconds Pre-baking) was performed. The coating film thickness of the active energy ray curable composition was adjusted so that the film thickness after pre-baking was 2 占 퐉.

Subsequently, using a mask having a transferred pattern (pattern size: 100 mu m x 100 mu m) using an i-line stepper exposure apparatus (FPA-3000i5 +, Canon Co., NA /? = 0.63 / 0.65, Focus offset = 0 mu m) , And exposed at an exposure dose of 500 mJ / cm ² .

Subsequently, the resist film was developed with an alkali developer (aqueous solution of tetramethylammonium hydroxide (TMAH), 0.3 mass%) for 60 seconds in a puddle using AD-1200 (manufactured by Mikasa).

Then, rinsing treatment was carried out using pure water, followed by drying at a high speed of 200 rpm for 30 seconds.

Subsequently, after the curing treatment was performed under any of the conditions described below, a further baking treatment was performed at 240 캜 for 5 minutes using a hot plate.

(EB curing)

Device: Electron beam irradiation device manufactured by Hamamatsu Photonics

Acceleration voltage: 70kV, tube voltage: 4.0mA

Absorbed dose: 145 kGy

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed at the time of processing): 100 mm / sec (2 sheets / sec on a substrate having a diameter of 200 mm)

Treatment temperature: 23 ° C

(UV curing)

Exposure dose (ultraviolet ray): 3,000 mJ / cm ²

Temperature: 35 ℃

(Heat curing)

In an oven at 220 &lt; 0 &gt; C for 1 hour

(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 mu m) was measured.

(Evaluation of Reliability of Cured Film)

· Temperature cycle test tolerance

In the same manner as in Test Example 1, the temperature cycle test resistance of the cured film was evaluated.

· Resistance to constant temperature and humidity test

In the same manner as in Test Example 1, the resistance of the cured film to the constant temperature and humidity test was evaluated.

(Exterior)

The appearance of the film after the curing treatment, after the curing treatment, and after the additional baking was evaluated.

A: No problem

B: Wrinkles on the surface

[Table 6]

As shown in the above table, the test No. 1 was irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. Reference numeral 601 denotes the No. 1 subjected to heat curing. A cured film excellent in reliability equivalent to 603 could be produced. Further, after the curing treatment, the film after the additional baking had no wrinkles and had a good appearance.

On the other hand, in the case of the test No. 1 in which UV curing was performed. 602 was inferior in reliability. Further, wrinkles occurred in the film after the additional baking. This is presumed to be due to the fact that the surface of the exposed pattern is accelerated in curing and the polymerization inside the pattern is insufficient, so that wrinkles have occurred on the surface due to the film shrinkage difference between the surface and the inside due to treatment at a high temperature.

&Lt; Test Example 7 >

[Preparation of active energy ray curable composition]

The following composition was mixed, and then filtered using a nylon filter (DFA4201NXEY, manufactured by Nippon Poult Co., Ltd.) having a pore diameter of 0.45 mu m to prepare an active energy ray curable composition.

(Furtherance)

· Cationic polymerizable compound (EHPE3150, manufactured by Daicel Chemical Industries, Ltd.) ... 4.0 mass%

· Acid generator (WPAG-469, 20% propylene glycol monomethyl ether acetate solution, manufactured by Wako Pure Chemical Industries, Ltd.) ... 1.0 mass%

· Surfactant 1 ... 0.1 mass%

· Propylene glycol monomethyl ether acetate (PGMEA) ... 94.9 mass%

Surfactant 1 was the same as Surfactant 1 of the active energy ray curable composition of Test Example 1.

[Preparation of cured film]

The active energy ray curable composition prepared above was applied to a glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)) by spin coating, Followed by a heat treatment (prebaking) for 120 seconds. The coating film thickness of the active energy ray curable composition was adjusted so that the film thickness after pre-baking became 0.1 mu m.

Subsequently, electron beam irradiation (manufactured by Hamamatsu Photonics Co., Ltd.) was performed under the following conditions to produce a cured film.

(EB condition 1)

Acceleration voltage: 70kV, tube voltage: 4.0mA

Absorbed dose: 145 kGy

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed during processing): 100 mm / sec × 1 scan

Treatment temperature: 23 ° C

(EB condition 2)

Acceleration voltage: 50 kV, tube voltage: 2.6 mA

Absorbed dose: 15 kGy

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed during processing): 100 mm / sec × 1 scan

Treatment temperature: 23 ° C

(EB condition 3)

Acceleration voltage: 50 kV, tube voltage: 2.6 mA

Absorbed dose: 30 kGy

Clearance between substrate and electron irradiation source: 10 mm

Oxygen concentration ≤1000 volume ppm

Transfer speed (scan speed during processing): 100 mm / sec × 2 scan

Treatment temperature: 23 ° C

(Solvent resistance)

After the obtained cured film was immersed in PGMEA or cyclohexanone for 5 minutes, the solvent resistance of the cured film was evaluated according to the following criteria.

A: Abnormal film surface, and no change in film thickness

B: there is an abnormality on the film surface or there is a change in the film thickness

(Evaluation of Reliability of Cured Film)

· Temperature cycle test tolerance

In the same manner as in Test Example 1, the temperature cycle test resistance of the cured film was evaluated.

· Resistance to constant temperature and humidity test

In the same manner as in Test Example 1, the resistance of the cured film to the constant temperature and humidity test was evaluated.

[Table 7]

As shown in the above table, the test No. 1 was irradiated with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV. 701 to 703, a cured film excellent in reliability could be produced.

Claims (23)

A process for producing a cured film comprising a step of irradiating a layer of an active energy ray-curable composition on a substrate with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV, the process comprising the steps of: . The method according to claim 1,
Wherein the active energy ray-curable composition comprises an alkali-soluble resin. The method according to claim 1 or 2,
Wherein the substrate is a thermoplastic substrate composed of a thermoplastic resin having a glass transition temperature of 100 占 폚 or less. The method according to claim 1 or 2,
Wherein the base material is a glass base material having a thickness of 0.5 mm or less. The method according to claim 1 or 2,
Wherein the substrate comprises an organic semiconductor layer. The method according to claim 1 or 2,
Wherein the base material has an organic semiconductor layer on its surface. The method according to any one of claims 1 to 6,
Further comprising the step of exposing a layer of the active energy ray-curable composition,
Wherein the step of irradiating the electron beam is performed after the exposing step. The method according to any one of claims 1 to 6,
Further comprising a step of exposing a layer of the active energy ray-curable composition, and a step of forming a pattern by developing the layer of the active energy ray-curable composition after the step of exposing,
Wherein the step of irradiating the electron beam is performed after the step of forming the pattern. The method according to claim 7 or 8,
Wherein the step of exposing is performed using ultraviolet light. The method according to any one of claims 1 to 9,
Wherein the active energy ray curable composition contains 0.01 to 5.0% by mass of a silane coupling agent in the solid content of the active energy ray curable composition. The method of claim 10,
Wherein the active energy ray curable composition comprises a thermosetting resin. The method 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 according to any one of claims 1 to 12,
Wherein the cured film has an optical density of at least one of wavelengths in a range of 260 to 440 nm. 14. The method of claim 13,
Wherein the cured film has a minimum value of optical density in a range of 260 to 440 nm in wavelength of 1 or more. 14. The method of claim 13,
Wherein the cured film has an optical density of 1 or more at a wavelength of 365 nm. The method according to any one of claims 1 to 15,
Wherein the active energy ray curable composition contains a photopolymerization initiator and a radical polymerizable compound. The method according to any one of claims 1 to 15,
Wherein the active energy ray curable composition contains an acid generator and a cationic polymerizable compound. The method according to any one of claims 1 to 17,
Wherein the cured film has a thickness of 0.1 to 45 占 퐉. The method according to any one of claims 1 to 18,
Applying the active energy ray-curable composition to the substrate, and then drying to form a layer of the active energy ray-curable composition. The method according to any one of claims 1 to 19,
And a step of performing vacuum drying. The method according to any one of claims 1 to 20,
Further comprising the step of heat-treating the layer irradiated with the electron beam at a temperature of 100 캜 or lower. 23. The method of claim 21,
Wherein the base material is a thermoplastic resin base material and the heat treatment step is performed at a temperature of not higher than a glass transition temperature of the thermoplastic resin base material and at a temperature of not higher than 100 占 폚. A cured film obtained by the method for producing a cured film according to any one of claims 1 to 22.

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