TWI693484B - Method for manufacturing cured film and cured film - Google Patents

Abstract

The present invention provides a method for manufacturing a cured film that can produce a cured film with excellent reliability by a low-temperature process and a cured film. The method for manufacturing a cured film of the present invention includes the steps of irradiating an electron beam with an acceleration voltage of 10 kV or more and less than 100 kV to a layer of an active energy ray-curable composition possessed on a substrate, wherein all steps are generally at 100°C Performed at the following temperature.

Description

Method for manufacturing cured film and cured film

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

In the method for producing a cured film, heat treatment is performed to sufficiently cure the curable composition. For example, the color filter is manufactured as follows. First, a curable composition (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 coloring composition layer formed with the pattern is subjected to heat treatment (post-baking) to sufficiently harden the coloring composition layer. The color filter is manufactured in the described manner.

In addition, a method of manufacturing a cured film by irradiating an electron beam to the curable composition is known (see Patent Document 1 to Patent Document 5).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 10-268515

[Patent Document 2] Japanese Patent Laid-Open No. 2004-12843

[Patent Document 3] Japanese Patent Laid-Open No. 2010-107928

[Patent Document 4] Japanese Patent Laid-Open No. 2009-244689

[Patent Document 5] Japanese Patent Laid-Open No. 2004-123802

Previously, the cured film was manufactured on a substrate including a material such as silicon having excellent heat resistance.

In recent years, it has been required to produce a cured film on a substrate having deteriorated heat resistance. When manufacturing a cured film on a substrate with deteriorated heat resistance, it is desirable to produce the cured film by, for example, a low-temperature process of 100° C. or less to suppress heat damage to the substrate. However, in the case of manufacturing a cured film by a low-temperature process, the following problems are likely to occur: after the temperature cycle test or the constant temperature and humidity test, abnormal appearance is likely to occur, the film thickness varies greatly, the transmittance varies greatly, etc.; and Compared with a cured film produced by heat treatment at a high temperature, the reliability of the cured film tends to deteriorate.

Therefore, an object of the present invention is to provide a method for manufacturing a cured film and a cured film that can produce a cured film with excellent reliability by a low-temperature process.

The present inventors conducted various studies and found that by irradiating an active energy ray-curable composition with an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV, a low-temperature process can be used to produce a cured film with excellent reliability, thereby completing The present invention. The present invention provides the following.

<1> A method for manufacturing a cured film, comprising: a step of irradiating an electron beam with an acceleration voltage of 10 kV or more and less than 100 kV to a layer of an active energy ray-curable composition possessed on a substrate, wherein all steps are generally 100 The temperature is below ℃.

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

<3> The method for producing a cured film according to <1> or <2>, wherein the substrate is a thermoplastic resin substrate containing a thermoplastic resin having a glass transition temperature of 100° C. or lower.

<4> The method for producing a cured film according to <1> or <2>, wherein the substrate is a glass substrate having a thickness of 0.5 mm or less.

<5> The method for producing a cured film according to <1> or <2>, wherein the base material includes an organic semiconductor layer.

<6> The method for manufacturing a cured film according to <1> or <2>, wherein the substrate includes an organic semiconductor layer on the surface.

<7> The method for manufacturing a cured film according to any one of <1> to <6>, which further includes a step of exposing the active energy ray curable composition layer, and irradiating after the step of exposing Steps of electron beam.

<8> The method for manufacturing a cured film according to any one of <1> to <6>, further comprising: a step of exposing the active energy ray curable composition layer; and after the step of exposing, The step of developing the layer of the active energy ray curable composition to form a pattern; and the step of irradiating an electron beam after the step of forming the pattern.

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

<10> The method for producing a cured film according to any one of <1> to <9> Method, wherein the active energy ray-curable composition contains 0.01% by mass to 5.0% by mass of a silane coupling agent in the 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 a color 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 (optical density) of 1 or more for any wavelength in the range of 260 nm to 440 nm.

<14> The method for producing a cured film according to <13>, wherein the minimum value of the optical density of the cured film in the wavelength range of 260 nm to 440 nm is 1 or more.

<15> The method for producing a cured film according to <13>, wherein the optical density of the cured film at a wavelength of 365 nm is 1 or more.

<16> The method for producing a cured film according to any one of <1> to <15>, wherein the active energy ray curable composition contains a photopolymerization initiator and a radical polymerizable compound.

<17> The method for producing a cured film according to any one of <1> to <15>, wherein the active energy ray curable composition contains an acid generator and a 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 μm to 45 μm.

<19> The method for producing a cured film according to any one of <1> to <18>, wherein the active energy ray-curable composition is applied to a substrate and then dried to form the active energy ray-curable composition Layer.

<20> The method for producing a cured film according to any one of <1> to <19>, which includes the step of vacuum drying.

<21> The method for producing a cured film according to any one of <1> to <20>, which includes a step of heat-treating the layer to which the electron beam has been irradiated 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 a step of performing heat treatment at a temperature below the glass transition temperature of the thermoplastic resin base material and at a temperature below 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 is possible to provide a method for producing a cured film and a cured film that can produce a cured film with excellent reliability by a low-temperature process.

FIG. 1 is a graph showing the spectrum of a cured film before and after color mixing evaluation.

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

In the description of "group (atomic group)" in this specification, the substitution and The unsubstituted expression means not only those without a substituent but also those with a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group), but also an substituted alkyl group (substituted alkyl group).

In this specification, "light" refers to actinic rays or radiation. In addition, the term "actinic rays" or "radiation" refers to, for example, the bright-line spectrum of mercury lamps and the extreme ultraviolet rays, extreme ultraviolet rays (extreme ultraviolet (EUV) light) represented by excimer lasers, X-rays, E-beam etc.

Unless otherwise specified, the "exposure" in this specification is not only the exposure of far ultraviolet, X-ray, EUV light, etc. represented by mercury lamps and excimer lasers, but also includes the description of particle beams such as electron beams and ion beams.

The numerical range indicated by "~" in this specification refers to a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

In this specification, the "total solid content" refers to the total mass of the components from which the solvent is removed from the entire composition.

In this specification, "(meth)acrylate" means either or both of acrylate and methacrylate, "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, " "(Meth)allyl" means both or either allyl and methallyl, and "(meth)acryl" means both or any of propenyl and methacryl One.

The term "step" in this specification refers not only to an independent step, but when it cannot be clearly distinguished from other steps, it is also included in this term if it achieves the desired effect of the step.

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

<Manufacturing method of cured film>

The method for producing a cured film of the present invention includes: irradiating an acceleration voltage of 10 kV or more and less than 100 kV to an active energy ray-curable composition layer (hereinafter also referred to as an active energy ray-curable composition layer) provided on a substrate The steps of the electron beam, and all steps of the method of manufacturing the cured film are generally performed at a temperature of 100°C or lower.

According to the present invention, by irradiating an active energy ray-curable composition layer with an electron beam with an acceleration voltage of 10 kV or more and less than 100 kV, even if all steps are performed at a low temperature of 100° C. or less (hereinafter also referred to as a low-temperature process), It is also possible to produce cured films with excellent reliability.

In addition, in the present invention, "all the steps are performed at a temperature of 100°C or less" means that all steps of curing the active energy ray-curable composition layer to form a cured film are performed at a temperature of 100°C or less, respectively Each step of the production step of the cured film is performed at a temperature of 100° C. or lower. That is, in addition to the step of irradiating the electron beam, the manufacturing step of the cured film includes other steps, and the other steps are also performed at a temperature of 100° C. or lower. For example, when the step of forming the active energy ray-curable composition layer on the substrate is further included, the step of forming the active energy ray-curable composition layer is also performed at a temperature of 100° C. or lower. In addition, when the step of exposing the active energy ray-curable composition layer on the substrate is further included, the step of exposing is also performed at a temperature of 100° C. or lower. In addition, Yu includes In the case of the step of patterning the active energy ray-curable composition layer on the substrate, the step of patterning is also performed at a temperature of 100° C. or lower. In addition, in the case where the active energy ray-curable composition layer after the electron beam irradiation is further subjected to post-processing such as heat treatment, the post-processing is also performed at a temperature of 100° C. or lower.

In addition, after the formation of the cured film, dicing (dividing into wafers), bonding, or the like may be further performed. The steps after the formation of the cured film are not included in the "all steps" in the present invention. That is, the step after forming the cured film can also be performed at a temperature exceeding 100°C. The reason for this is that, for example, when a thin film glass substrate is used as the substrate, if it is performed at a temperature exceeding 100°C during the formation of the cured film, cracks or warpage may occur on the substrate, but cutting Even after heating to a temperature exceeding 100°C, it is difficult to cause cracking or warping.

Hereinafter, the method of manufacturing the cured film of the present invention will be described in order for each step.

Using the active energy ray-curable composition, an active energy ray-curable composition layer is formed on the substrate. In addition, the active energy ray-curable composition will be described later.

Examples of the base material include base materials including glass, silicon, resin, and the like. The glass can be exemplified by glass used in optical devices or display devices such as Eagle series, 1737, etc. of alkali-free glass manufactured by Corning; formed to have ultraviolet (UV) cutoff or infrared cutoff function The organic layer of glass in which the pigment is dispersed or pulverized (including the form sandwiched by the glass). Examples of the resin include polyethylene, polypropylene, vinyl chloride, polystyrene, acrylonitrile-styrene copolymer, Acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, acrylic acid, polyvinyl alcohol, vinylidene chloride, polycarbonate, polyamide, polyacetal, polybutylene terephthalate Diesters, fluororesins, etc., can be used alone or in combination of two or more. Organic semiconductor layers such as organic light-emitting layers or organic photoelectric conversion layers can also be formed on these substrates. Examples of organic semiconductors include organic electroluminescence (Organic Light Emitting Diode (OLED)), organic field effect transistor (OFET), organic solar cell (Organic Photovoltaic, OPV) ))Wait. In addition, in the present invention, an organic semiconductor layer can also be used as a base material.

The film thickness of the substrate varies depending on the application and material, and the thickness of a general substrate can be applied.

According to the present invention, a cured film can be formed without damaging the base material of the base material having deteriorated heat resistance, so it is particularly effective for a base material having low heat resistance. Examples of the substrate having low heat resistance include glass substrates having a thickness of 0.5 mm or less, thermoplastic resin substrates, substrates including an organic semiconductor layer (preferably substrates including an organic semiconductor layer on the surface), and the like.

Among the thermoplastic resin substrates, for example, in the case of a substrate including a thermoplastic resin having a glass transition temperature of 95° C. or lower, the effect of the present invention is remarkable. Especially for flexible substrates, thermoplastic resins with a glass transition temperature of 90° C. or less are used more. Especially in recent years, those with a glass transition temperature lower than 70° C. can be used particularly well. The lower limit of the glass transition temperature of the thermoplastic resin is not particularly limited. For example, it can also be set to normal temperature (23 degreeC) or more. In addition, the temperature below normal temperature can also be set as the lower limit value. For example, when it is 0°C or higher, it may be -50°C or higher, -100°C or higher, or -150°C or higher.

In addition, in the present invention, when the thermoplastic resin has two or more glass transition temperatures, a low temperature is used as the value of the glass transition temperature of the present invention.

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

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

In the present invention, the active energy ray-curable composition layer formed on the substrate may be dried. Examples of drying include room temperature drying, heating drying, and vacuum drying. In terms of drying speed and drying at low temperature, vacuum drying is preferred.

The vacuum drying is preferably performed under the conditions of a vacuum degree of 0.02 PaG or more and a temperature of 100° C. or less. The vacuum degree is more preferably 0.05 PaG or more, and particularly preferably 0.09 PaG or more. The higher the vacuum, the faster the drying speed, which can shorten the drying time. The temperature conditions are particularly preferably below 70°C. The lower limit may be, for example, 23°C or higher, or 30°C or higher. The drying time is preferably 30 seconds to 1 hour, more preferably 1 minute to 30 minutes, and particularly preferably 2 minutes to 20 minutes.

The heating and drying is preferably performed at 100°C or lower, more preferably 80°C or lower, and particularly preferably 70°C or lower. The lower limit can be set to 23° C. or higher, for example. The heating time is preferably 30 seconds to 1 hour, more preferably 1 minute to 30 minutes, and particularly preferably 2 minutes to 20 minutes.

In addition, drying may be performed before the step of irradiating the electron beam to be described later, or may be performed after the step of irradiating the electron beam. In addition, it may be carried out before development processing described later or after development processing.

In the present invention, the active energy ray-curable composition layer formed on the substrate can be exposed. The exposure can be full exposure or can be exposed in a pattern through a mask.

For example, the pattern exposure can be performed by exposing the active energy ray-curable composition layer formed on the substrate using an exposure device such as a stepper through a mask having a predetermined mask pattern. By this, the exposed portion can be hardened.

The radiation (light) usable in the exposure is preferably ultraviolet light. Examples of ultraviolet rays include g-rays, i-rays, KrF, and ArF, and i-rays are preferred. Irradiation amount (exposure amount), for example, is preferably ^{30mJ / cm 2 ~ 5000mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 4000mJ / cm} 2, and particularly preferably ^{80mJ / cm 2 ~ 3000mJ / cm} 2.

When exposing the active energy ray-curable composition layer to a pattern, it is preferable to develop and remove the unexposed portion to form a pattern. The development and removal of the unexposed portion can be performed using a developer. Thereby, the active energy ray-curable composition layer of the unexposed portion dissolves in the developer, and only the photocured portion remains.

The developer is ideally an alkaline developer that does not damage the substrate.

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

Examples of the alkaline agent used in the developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylhydroxide Ammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and other organic basic compounds.

In addition, as the alkaline agent used in the developer, an inorganic alkaline compound can also be used. The inorganic basic compound is preferably sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, or the like.

The alkaline aqueous solution in which these alkaline agents are diluted with pure water so that the concentration becomes 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass can be preferably used as the developer.

In addition, a surfactant can also be used in the developer. Examples of the surfactant include the surfactants described in the active energy ray-curable composition described below, and nonionic surfactants are preferred. When the developer contains a surfactant, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.01% by mass to 1.0% by mass relative to the total mass of the developer.

In the case of using a developing solution containing an alkaline aqueous solution as described above, it is usually preferably washed (rinsed) with pure water after development.

Preferably, after washing, for example, after spin drying, the drying is performed.

Then, the active energy ray-curable composition layer on the substrate is irradiated with an electron beam. In the case where the active energy ray-curable composition layer is subjected only to the above-mentioned exposure without performing the above-mentioned development, it is preferable to irradiate an electron beam after the exposure. In addition, Yu Duohuo When the energy-ray curable composition layer is patterned (when exposure and development are performed), it is preferable to irradiate an electron beam after patterning 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 particularly preferably 30 kV or more. The upper limit is preferably 99 kV or less, more preferably 98 kV or less, and particularly preferably 97 kV or less. If the acceleration voltage of the electron beam is within the above range, a cured film with excellent reliability can be manufactured. Furthermore, the appearance and spectral characteristics of the obtained cured film are also good.

The tube current of the electron beam is preferably 0.01 mA 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 having excellent reliability can be manufactured. Furthermore, the appearance and spectral characteristics of the obtained 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 particularly preferably 1 mA or more. The upper limit is preferably 10 mA or less, more preferably 9 mA or less, and particularly preferably 8 mA or less. If the durability of the filament is maintained, the tube current setting is preferably the larger.

The electron beam is preferably irradiated within a range in which the absorption line amount of the electron beam of the cured film is 10 kGy or more. When the amount of absorbed rays of the electron beam is within the above range, a cured film excellent in reliability can be manufactured. The absorption line quantity of the electron beam is more preferably 15 kGy or more, and particularly preferably 20 kGy or more.

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

In addition, the irradiation of the electron beam is preferably performed in an environment with an oxygen concentration of 3000 volume ppm or less. The oxygen concentration is more preferably 1000 ppm by volume or less.

In addition, the gap between the substrate and the electron irradiation source is preferably 1 mm to 30 mm, and more preferably 5 mm 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 heat-treated at a temperature of 100° C. or lower. By heat treatment, drying of the cured film can be promoted, and the curability of the cured film can be stabilized.

The heat treatment temperature is preferably, for example, a temperature exceeding 23°C to 100°C or lower. The upper limit is more preferably 80°C or lower, and particularly preferably 70°C or lower. In addition, when a thermoplastic resin substrate is used as the substrate, the upper limit of the heat treatment temperature is a temperature of 100° C. or lower, preferably a temperature of the thermoplastic resin substrate or lower than the glass transition temperature. In addition, when the glass transition temperature of the thermoplastic resin substrate exceeds 100°C, the upper limit of the heat treatment temperature is 100°C.

The heat treatment can be a method of the above conditions, using a heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, and other heating mechanisms to harden the active energy rays after continuous or batch irradiation of electron beams Sexual composition layer.

In addition, vacuum drying can be performed instead of heat treatment. In addition, heat treatment and vacuum drying can also be used together.

<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, if the active energy ray curable composition is Any composition that is hardened by irradiation can be preferably used. Here, the active energy ray refers to a person who can impart energy that can generate the initial species in the composition by irradiation, and examples include α rays, γ rays, X rays, ultraviolet rays, visible rays, and electron beams. Wait.

<<Resin>>

The active energy ray-curable composition preferably contains a resin. The resin is prepared, for example, for the purpose of dispersing pigments and the like in the composition and the use of a binder. In addition, resins mainly used for dispersing pigments and the like are also called dispersants. Among them, the use of the resin is an example, and it may be used for purposes other than such use.

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 particularly preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and particularly preferably 5,000 or more.

Examples of resins include (meth)acrylic resins, epoxy resins, and olefins. Thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polyphenol resin, polyether resin, polyparaphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide Acetylene imide resin, polyolefin resin, cyclic olefin resin, polyester resin, siloxane resin. One kind of these resins may be used alone, or two or more kinds may be used in combination.

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

<<<Alkali Soluble Resin>>>

The active energy ray-curable composition preferably contains an alkali-soluble resin as the resin. By containing an alkali-soluble resin, the developability and pattern formability are improved. In addition, alkali-soluble resins can also be used as dispersants or binders.

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

The alkali-soluble resin may be a linear organic polymer polymer, and may be a resin having at least one group that promotes alkali dissolution in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) Choose appropriately.

From the viewpoint of heat resistance, the alkali-soluble resin is preferably a polyhydroxystyrene-based resin, a polysiloxane-based resin, an acrylic resin, an acrylamide-based resin, and an acrylic/acrylamide-copolymer resin to control development From the viewpoint of sex, acrylic resins, acrylamide-based resins, and acrylic/acrylamide copolymer resins are preferred.

Examples of groups that promote alkali dissolution (hereinafter also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Preferably, they are soluble in organic solvents and can be developed with a weak alkaline aqueous solution. In particular, (meth)acrylic acid can be cited as particularly preferred. These acid groups may be only one kind, or two or more kinds.

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

The alkali-soluble resin is preferably a polymer having a carboxylic acid in the side chain, and examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, and maleic acid copolymers. Alkali-soluble phenol resins such as partially esterified maleic acid copolymers, novolac-type resins, etc., and acidic cellulose derivatives having a carboxyl group on the side chain, and resins having an acid anhydride added to a polymer having a hydroxyl group, etc. . In particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is preferable as an alkali-soluble resin. Other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds, and the like. Examples of alkyl (meth)acrylate and aryl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate Ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate , Toluene (meth)acrylate, Naphthyl (meth)acrylate, Cyclohexyl (meth)acrylate, etc. Vinyl compounds include styrene, α-methylstyrene, vinyltoluene, methacrylic acid Glycidyl ester, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. In addition, other monomers include N-substituted maleimide diimide monomers described in Japanese Patent Laid-Open No. 10-300922, for example: N-phenyl maleimide diimide, N-cyclohexyl Maleimide, etc. In addition, these other monomers copolymerizable with (meth)acrylic acid may be only one kind, or two or more kinds.

In addition, in order to improve the crosslinking efficiency of the active energy ray-curable composition layer, an alkali-soluble resin having a polymerizable group may also be used. The polymerizable group can be exemplified by: (A Group) allyl group, (meth)acryloyl group, etc. The alkali-soluble resin having a polymerizable group is effectively used for an alkali-soluble resin containing a polymerizable group on the 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 (polyurethane acrylate oligomer containing COOH , Diamond Shamrock Co., Ltd. (Diamond Shamrock Co., Ltd.), Viscoat (Viscoat) R-264, KS resist 106 (both made by Osaka Organic Chemical Industry Co., Ltd.), Sekuloma ( Cyclomer) P series (such as ACA230AA, thermosetting resin), Placcel CF200 series (all made by Daicel), Ebecryl 3800 (Dacel UCB) ) Manufacturing), Acrycure (Acrycure) RD-F8 (manufactured by Japan Catalyst Co., Ltd.), etc.

Alkali soluble resins can be preferably used: (meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer, (meth)acrylic acid benzyl ester/(meth)acrylic acid/(meth)acrylic acid 2-hydroxyethyl copolymer Multi-component copolymer containing benzyl (meth)acrylate/(meth)acrylic acid/other monomers. In addition, it can also be preferably used: 2-hydroxyethyl (meth)acrylate copolymerized, 2-hydroxypropyl (meth)acrylate/polymethacrylate described in Japanese Patent Laid-Open No. 7-140654 Styrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methyl Acrylic copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl Benzyl acrylate/methacrylic acid copolymer Wait.

In addition, as a commercially available product, for example, FF-426 (manufactured by Fujikura Kasei Corporation) can also be used.

It is also preferable that the alkali-soluble resin contains a polymer which contains a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, sometimes These compounds are also known as "ether dimers".

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a C 1-25 hydrocarbon group which may have a substituent.

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

In the formula (ED1), the hydrocarbon groups having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² are not particularly limited, and examples include methyl, ethyl, n-propyl, isopropyl, and n Linear or branched alkyl groups such as butyl, isobutyl, third butyl, third pentyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, Alicyclic groups such as tributylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; 1-methoxyethyl, Alkoxy substituted alkyl such as 1-ethoxyethyl; aryl substituted alkyl such as benzyl. Among these hydrocarbon groups, in terms of heat resistance, particularly preferred are substituents of primary or secondary carbons such as methyl, ethyl, cyclohexyl, and benzyl that are difficult to be removed by acid or heat.

For a specific example of the ether dimer, for example, refer to paragraph No. 0317 of Japanese Patent Laid-Open No. 2013-29760, and this content can be incorporated into this specification. The ether dimer may be only one kind, or two or more kinds.

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

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

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

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

For the alkali-soluble resin, reference can be made to the descriptions of paragraph number 0558 to paragraph number 0571 of Japanese Patent Laid-Open No. 2012-208494 (corresponding paragraph number 0685 to paragraph number 0700 of the specification of US Patent Application Publication No. 2012/0235099). Can be incorporated into this manual.

Furthermore, the copolymer (B) described in Paragraph No. 0029 to Paragraph No. 0063 of Japanese Patent Laid-Open No. 2012-32767 and the alkali-soluble resin used in the examples, and Japanese Patent Laid-Open No. 2012-208474 can also be used. Paragraph number 0088 to the binder resin described in paragraph No. 0098 and the binder resin used in the examples, the binder resin described in paragraph No. 0022 to paragraph No. 032 of Japanese Patent Laid-Open No. 2012-137531 and the ones used in the examples Binder resin, binder resin described in paragraph number 0132 to paragraph number 0143 of Japanese Patent Laid-Open No. 2013-024934 and binder resin used in the examples, paragraph number 0092 of Japanese Patent Laid-Open No. 2011-242752 ~Paragraph No. 0098 and the binder resin used in the examples, and the binder resin described in Paragraph No. 0030 of Japanese Patent Laid-Open No. 2012-032770 to Paragraph No. 072. These contents can be incorporated into this specification.

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

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

<<<Dispersant>>>

The active energy ray-curable composition may contain a dispersant as a resin.

The resin used as the dispersant preferably contains a repeating unit having an acid group. Since the resin contains repeating units having acid groups, when the photolithography method is used to form the pattern, the residue generated in the substrate can be further reduced.

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 vinyl monomers having a carboxyl group include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, and crotonic acid , Cinnamic acid, acrylic acid dimer, etc. In addition, the addition of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, and cyclohexane dicarboxylic anhydride can also be used. Into reactants, ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride, or the like can also be used as a carboxyl group precursor. Among them, from the viewpoint of developmental removability of unexposed portions, monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and maleic anhydride, phthalic anhydride, and succinic anhydride are preferred , Cyclohexane dicarboxylic anhydride and other cyclic anhydride addition reactants.

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 phosphoric acid mono(2-propenyloxyethyl), phosphoric acid mono(1-methyl-2-propenyloxyethyl), and the like.

In addition, for the repeating unit having an acid group, refer to the descriptions in paragraph No. 0067 to paragraph No. 0069 of Japanese Patent Laid-Open No. 2008-165059, which can be incorporated into In this manual.

In addition, the resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has affinity with the solvent through the graft chain, it has excellent pigment dispersibility and dispersion stability over time. In addition, the composition has an affinity with a polymerizable compound, an alkali-soluble resin, etc. due to the presence of a graft chain, so that it is difficult to generate residues during alkali development.

In the present invention, the graft copolymer refers to a resin having a graft chain. In addition, the graft chain means from the root of the main chain of the polymer to the end of the group branched from the main chain.

In the present invention, the graft copolymer is preferably a resin having a graft chain in the range of 40 to 10,000 atoms other than hydrogen atoms.

In addition, the number of atoms other than hydrogen atoms in each grafted chain is preferably 40 to 10,000, more preferably 50 to 2,000, and particularly preferably 60 to 500.

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

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

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

The macromonomer used when producing a graft copolymer by radical polymerization can use a well-known macromonomer, and examples include the macromonomer AA-6 (terminal group is methacrylonitrile) manufactured by East Asia Synthetic Co., Ltd. Based polymethyl methacrylate), AS-6 (polystyrene with methacryloyl group as the terminal group), AN-6S (copolymer of styrene and acrylonitrile with methacryloyl group as the terminal group) , AB-6 (polybutyl acrylate with a methacryloyl group as the terminal group), Placcel FM5 (2-hydroxyethyl methacrylate ε- manufactured by Daicel) Caprolactone 5 molar equivalents plus product), FA10L (2-hydroxyethyl acrylate epsilon-caprolactone 10 molar equivalents plus product), and the polyester-based giant described in Japanese Patent Laid-Open No. 2-272009 Monomer etc.

In the present invention, a graft copolymer including a repeating unit represented by any of the following formula (1) to formula (4) may also be used as the resin. These graft copolymers can be particularly well used as dispersants for black pigments.

[Chem 5]

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

In Formula (1) to Formula (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthesis constraints, 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, more preferably independently A hydrogen atom or a methyl group, particularly preferably a methyl group.

In Formula (1) to Formula (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the linking is not particularly restricted based on the structure. Specific examples of the divalent linking groups represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups of (Y-1) to (Y-21). In the structures shown below, A and B refer to the bonding sites to the left terminal group and the right terminal group in formula (1) to formula (4), respectively.

[化6]

In Formula (1) to Formula (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples include alkyl groups, hydroxyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkyl sulfide groups, aryl sulfide groups, and heteroaryl sulfide groups Groups and amine groups. Among these organic groups, particularly from the viewpoint of improving dispersibility, the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ are preferably those having a stereoscopic repulsion effect, and are preferably independently carbon numbers 5-24 alkyl or alkoxy groups, particularly preferably branched alkyl groups having 5-24 carbon atoms, cyclic alkyl groups having 5-24 carbon atoms, or alkoxy groups having 5-24 carbon atoms . In addition, the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

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

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

In formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same as or different from each other.

In 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 preferably includes a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group, and particularly preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. More preferably, it is a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same as or different from each other.

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

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

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

In the formula ^{(1A), X 1, Y} 1, Z 1 and n of formula X (1) is ^1, Y ^1, Z ¹ and n have the same meaning as the preferred range is also the same.

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

In formula (3A) or the formula ^{(3B), X 3, Y} 3, Z 3 and p of formula X (3) is ^3, Y ^3, Z ³ and p have the same meaning as the preferred range is also the same.

In addition, the graft copolymer also preferably has the formula (1) ~ In addition to the repeating unit represented by formula (4), it also has a hydrophobic repeating unit. Among them, in the present invention, the hydrophobic repeating unit is a repeating unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

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

AJ Leo, "Comprehensive Medicinal Chemistry" Issue 4, C. Hansch, PG Sammons, and JB Taylor (CABTaylor) and CA Chief Editor, CARamsden, page 295, Pergamon Press, 1990; C. Hansch and AJ Leo, "Chemical and Biological Substituent Constants For Correlation Analysis in Chemistry and Biology", John. John Wiley & Sons. A.J. Leo, "From the structure Calculating log Poct from structure”, Chemical Reviews (Chem. Rev.), No. 93, pages 1281-1306, 1993.

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

logP=log(Coil/Cwater)

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

If the value of logP increases positively with 0 in between, it means that the oil solubility increases. If the absolute value increases in the negative direction, it means that the water solubility increases. There is a negative correlation with the water solubility of the organic compound as an estimate. The parameters of the hydrophilicity and hydrophobicity of organic compounds are widely used.

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

[Chem 8]

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

R ¹ , R ² and R ^{3 are} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. R ² and R ^{3 are} particularly preferably 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: divalent aliphatic group (for example: alkylene group, substituted alkylene group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group), divalent Valence aromatic group (for example: arylene group, substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), A substituted imino group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), a combination of these groups, or the like.

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

Z can be exemplified by aliphatic groups (for example: alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (for example: arylene groups, substituted arylene groups) , Heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ³¹ -, here, R ³¹ is aliphatic Group, aromatic group or heterocyclic group), carbonyl group (-CO-), or a combination of these groups.

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

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

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. Other heterocycles, aliphatic rings or aromatic rings can also be condensed on the heterocycle. In addition, the heterocyclic group may have a substituent. Examples of the substituent include halogen atom, hydroxyl group, oxo group (=O), thio group (=S), imino group (=NH), substituted imino group (=NR ³² , here, R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Among them, the heterocyclic group does not have an acid group as a substituent.

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

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

Examples of representative compounds represented by formula (i) to formula (iii) include radical polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like. In addition, for examples of the compounds represented by the formula (i) to the formula (iii), reference may be made to the compounds described in paragraph No. 0089 to paragraph No. 0993 of Japanese Patent Laid-Open No. 2013-249417, and this content can be incorporated into this specification .

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

The graft copolymer preferably contains, in addition to the repeating units represented by the formula (1) to the formula (4), a functional group (for example, acid group, base, etc.) that can interact with the pigment and the like. Repeating units such as sex groups, coordination groups, reactive groups, etc.).

The acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, etc., preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, particularly preferably for coloring black pigments, etc. Carboxylic acid group with good adsorption and high dispersibility.

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

The graft copolymer may contain repeating units with acid groups or may not contain acid groups In the case where the repeating unit having an acid group is included, the content of the repeating unit having an acid group is preferably 5 to 80% by mass relative to the total mass of the graft copolymer in terms of mass conversion , More preferably 10% by mass to 60% by mass.

The basic group includes, for example, a primary amine group, a secondary amine group, a tertiary amine group, a heterocyclic ring containing an N atom, an amide group, etc., particularly preferred are those having good adsorption to colorants and high dispersibility. Tertiary amine group. The graft copolymer may have one kind or two or more kinds of these basic groups.

The graft copolymer may contain a repeating unit having a basic group or may not contain a repeating unit having a basic group. In the case of containing a repeating unit having a basic group, the content of the repeating unit having a basic group is converted by mass It is preferably 0.01% by mass to 50% by mass relative to the total mass of the graft copolymer, and more preferably 0.01% by mass to 30% by mass from the viewpoint of suppressing development resistance.

Examples of the coordination group and the functional group having reactivity include acetylacetylacetoxy, trialkoxysilyl, isocyanate group, acid anhydride, and acetyl chloride. A particularly preferred one is acetoacetoxy, which has good adsorption to colorants and high dispersibility. The graft copolymer may also have one kind or two or more kinds of these groups.

The graft copolymer may include a repeating unit having a coordination group, or a repeating unit containing a reactive functional group, or may not include the repeating unit. When the repeating unit is included, those repeating units The content in terms of mass conversion is preferably 10% by mass to 80% by mass relative to the total mass of the graft copolymer, and from the viewpoint of suppressing the hindrance of developability, it is more preferably 20% by mass to 60% by mass.

In addition to the graft chain, the graft copolymer also has In the case of interacting functional groups, there is no particular limitation on how these functional groups are introduced, and the graft copolymer preferably has a monomer selected from the group consisting of the following formula (iv) to formula (vi) More than one type of repeating unit in the repeating unit.

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

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

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

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

L _{1 in} formula (iv) to formula (v) represents a single bond or a divalent linking group. Examples of divalent linking groups include: divalent aliphatic groups (eg, alkylene groups, substituted alkylene groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, and substituted alkynyl groups) , Divalent aromatic groups (for example: arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH- ), substituted imino bond (-NR ³¹ '-, where, R ^31' is an aliphatic group, an aromatic group or a heterocyclic group), carbonyl bond (-CO-), or a group of the plurality of Combination etc.

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

In formula (iv) to formula (vi), Z ₁ represents a functional group that can form an interaction with the pigment in addition to the graft chain, preferably a carboxylic acid group, a tertiary amine group, and more preferably a carboxylic acid group.

In formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ independently represent a hydrogen atom, a halogen atom (for example: a fluorine atom, a chlorine atom, a bromine atom, etc.) and an alkyl group having 1 to 6 carbon atoms (for example: methyl, ethyl, propyl, etc.), - Z ₁ or -L ₁ -Z _1. Here, L ₁ and Z ₁ have the same meanings as the above-mentioned L ₁ and Z ₁ , and the preferred examples are also 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, more preferably a hydrogen atom.

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

Specific examples of the graft copolymer include the following. In addition, reference may be made to the polymer compounds described in paragraph No. 0127 to paragraph No. 0129 of Japanese Patent Laid-Open No. 2013-249417, and the contents can be incorporated into this specification.

Dispersants can also be obtained as commercially available products. Examples of such specific examples include: "DA-7301" manufactured by Nanben Chemical Industry Co., Ltd. and "DISPERBYK" manufactured by BYK Chemie. -101 (polyamide amine phosphate), 107 (carboxylate), 110 (copolymer containing acid group), 111 (phosphate dispersant), 130 (polyamide), 140, 142, 145, 161 , 162, 163, 164, 165, 166, 170, 180, 187, 190, 191, 2001, 2010, 2012, 2025 (polymer copolymer)'', ``BYK-P104, P105 (high molecular weight not Saturated polycarboxylic acid), 9076", "EFKA (EFKA) 4047, 4050~4165 (polyurethane)), EFKA (EFKA) 4330~EFKA (43KA) 4340 (EFKA) Block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo Pigment Derivatives)", "Ajisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno Company, "Fuji" manufactured by Kyoeisha Chemical Company "Flowlen TG-710 (urethane oligomer)", "Polyflow No.50E, No.300 (acrylic copolymer)", "Emperor" manufactured by Nanben Chemical Co., Ltd. Disparlon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyetherester), DA-703-50, DA-705, DA-725", manufactured by Kao Corporation "Demol RN, N (naphthalenesulfonic acid formaldehyde polycondensate), MS, C, SN-B (aromatic sulfonic acid formaldehyde polycondensate)", "Homogenol L-18 ( High molecular polycarboxylic acid), ``Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)'', ``Acetamin 86 (stearylamine ethyl Acid ester), "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine) manufactured by Lubrizol (shares), Japan 3000, 12000, 17000, 20000, 27000 (polymer with functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer)", Nikkol T106 (Nikkol) manufactured by Nikko Chemical Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", "Hinoact T-8000E" manufactured by Chuan Yan Fine Chemicals Co., Ltd., letter "Organic Siloxane Polymer KP341" manufactured by Vietnam Chemical Industry Co., Ltd., "EFKA (46), EFKA (47)-47, EFKA (EFKA)" manufactured by Morishita Industries (Co., Ltd.) -47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", San Nopko Nopco (shares) ``Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 15, Disperse Aid (Disperse Aid) 9100", "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84" manufactured by ADEKA Corporation , F87, P94, L101, P103, F108, L121, P-123", and "Ionet (trade name) S-20" manufactured by Sanyo Chemical Co., Ltd., etc. In addition, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can also be used.

<<Free Radical Polymerizable Compound>>

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

Radical polymerizable compounds can be, for example, monomers, prepolymers, ie dimerization Chemical forms such as substances, trimers and oligomers, or mixtures and polymers of these. It is preferably a monomer.

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

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

Examples of monomers and prepolymers include unsaturated carboxylic acids (for example: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) and their esters and amides , And these polymers, preferably esters of unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, amides of unsaturated carboxylic acid and aliphatic polyhydric amine compound, and these polymers. In addition, it is also preferable to use unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group, addition reaction products with monofunctional or polyfunctional isocyanates or epoxy compounds, or Dehydration condensation reactant with monofunctional or polyfunctional carboxylic acid, etc. In addition, it is also preferred that: unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups, epoxy groups, etc. react with monofunctional or polyfunctional alcohols, amines, thiols The reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as halogen groups or tosyloxy groups, and monofunctional or polyfunctional alcohols, amines and thiols. In addition, instead of the unsaturated carboxylic acid, a group of compounds substituted with vinyl benzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether and the like may be used.

As these specific compounds, in the present invention, paragraph No. 0095 to paragraph No. 0108 in Japanese Patent Laid-Open No. 2009-288705 can also be preferably used. Contained compounds.

The radically polymerizable compound is also preferably a compound containing one or more groups having an ethylenically unsaturated bond and having a boiling point of 100° C. or higher under normal pressure. For example, reference can be made to paragraph number 0227 of Japanese Patent Laid-Open No. 2013-29760, paragraph number 0254 to paragraph No. 0257 of Japanese Patent Laid-Open No. 2008-292970, and these contents can be incorporated into this specification.

The radically polymerizable compound is preferably: dipentaerythritol triacrylate (commercially available product is KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product is card KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol penta(meth)acrylate (commercially available as Kayarad D-310, Nippon Kayaku) Manufacturing), dipentaerythritol hexa(meth)acrylate (commercially available product is KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.; A-DPH-12E, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), And the structure in which these (meth)acryloyl groups are bonded via ethylene glycol residues and propylene glycol residues (for example: SR454 and SR499 sold by Sartomer). These oligomer types can also be used. In addition, NK ester (NK Ester) A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), etc. can also be used .

The preferred form of the radical polymerizable compound is shown below.

The radical polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The radical polymerizable compound having an acid group is preferably an aliphatic polyhydroxy compound The ester of the compound and the unsaturated carboxylic acid is more preferably a radically polymerizable compound having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, particularly preferably a fat in the ester Group polyhydroxy compounds are pentaerythritol and/or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by East Asia Synthetic Corporation.

The preferred acid value of the radically polymerizable compound is 0.1 mgKOH/g~40 mgKOH/g, particularly preferably 5 mgKOH/g~30 mgKOH/g. If the acid value of the radical polymerizable 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 manufacturing or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

As a radical polymerizable compound, a compound having a caprolactone structure is also a preferred form.

The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples include ε-caprolactone modified polyfunctional (meth)acrylates, and the ε-caprolactone modified The quality polyfunctional (meth)acrylate is composed of trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. , Glycerin, diglycerin, trimethylolmelamine and other polyols are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferable.

[Chem 11]

In formula (Z-1), all 6 Rs are groups represented by the following formula (Z-2), or 1 to 5 of the 6 Rs are represented by the following formula (Z-2) The rest of the groups are represented by the following formula (Z-3).

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

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

Radical polymerizable compounds having a caprolactone structure are sold by, for example, Kayrad DPCA series from Nippon Kayaku Co., Ltd., including: DPCA-20 (the formula (Z-1) to formula ( Z-3) m=1, the number of groups represented by formula (Z-2)=2, and all compounds where R ¹ is a hydrogen atom), DPCA-30 (the above formula (Z-1) to formula (Z-1) Z-3) m=1, the compound represented by the formula (Z-2) = 3, and all R ¹ are hydrogen atoms), DPCA-60 (the formula (Z-1) to the formula (Z-1) (Z-3) m=1, compound represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms), DPCA-120 (the formula (Z-1) to formula ( In Z-3), m=2, the number of groups represented by formula (Z-2)=6, and all R ¹ are hydrogen atoms), etc.

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

In formula (Z-4) and formula (Z-5), E independently represents -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ )O)-, y independently represents an integer of 0 to 10, and X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group.

In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.

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

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

In addition, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

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

In addition, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

In addition, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in formula (Z-4) or formula (Z-5) is preferably an oxygen atom The end of the side is bonded to X.

The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. Particularly preferred are: a form in which 6 Xs in formula (Z-5) are all acryl; and a compound in which 6 Xs are all acryl in formula (Z-5), and at least one of the 6 Xs is The form of a mixture of hydrogen atoms. With such a configuration, the developability can be further improved.

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

The compound represented by formula (Z-4) or formula (Z-5) can be synthesized by a conventionally known procedure, that is, by ring-opening addition of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol The step of bonding a ring-opening skeleton by reaction; and the step of introducing (meth)acryl acetyl group by reacting (meth)acryl acetyl chloride with the terminal hydroxyl group of the ring-opening skeleton, for example. Each step is a well-known step, and those skilled in the art can easily Compounds represented by formula (Z-4) and formula (Z-5) are synthesized.

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

Specifically, the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to exemplified compounds (f)") are mentioned, and among them, preferred are exemplified compounds (a ), exemplified compound (b), exemplified compound (e), exemplified compound (f).

[Chem 16]

Examples of the commercially available products of the radical polymerizable compound represented by the formula (Z-4) and the formula (Z-5) include tetrafunctional four-ethyloxy chains produced by Sartomer Co., Ltd. Acrylate is SR-494, hexafunctional acrylate with 6 pentanyloxy chains manufactured by Nippon Kayaku Co., Ltd. is DPCA-60, and trifunctional acrylate with 3 isobutyloxy chains is TPA-330 and so on.

The content of the radical polymerizable compound is preferably 0.1% by mass to 40% by mass relative to the total solid content of the active energy ray-curable composition. Lower limit is better It is 0.5 mass% or more, and particularly preferably 1 mass% or more. For example, the upper limit is more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The radical polymerizable compound may be a single kind, or two or more kinds may be used in combination. When two or more types 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. Examples of the cationic polymerizable compound include compounds having a cyclic ether group. Examples of cyclic ether groups include epoxy groups and oxetanyl groups, and epoxy groups are preferred.

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

The cationic polymerizable compound may be a low-molecular compound (for example, a molecular weight of less than 2,000, and further, a molecular weight of less than 1,000) or a high molecular compound (macromolecule) (for example, a molecular weight of 2,000 or more, in the case of a polymer, the weight Any one with an average molecular weight of 2,000 or more). The weight average molecular weight of the cationic polymerizable compound is preferably 200 to 100,000, and more preferably 500 to 50,000.

Specific examples of compounds having two or more epoxy groups in the molecule include aliphatic epoxy compounds. In addition, reference can be made to the descriptions of paragraph numbers 0021 to 0003 of WO2012/093591, and this content can be incorporated into this specification.

These compounds are available as commercial products. Examples include: Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313 , EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX- 931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 ( The above are manufactured by Nagase ChemteX), Celloxide 2021P, 2081, 3000, EHPE3150, Epolead GT400, Celvenus B0134, B0177 (Daicel ) (Share manufacturing) etc.

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

As specific examples of compounds having two or more oxetanyl groups in the molecule, Aron Oxetane (Aron Oxetane) OXT-121, OXT-221, OX-SQ, PNOX (above, East Asia Synthesis (share )manufacture).

In addition, the oxetanyl-containing compound is preferably used alone or in combination with an epoxy group-containing compound.

The content of the cationic polymerizable compound is preferably 0.1% by mass to 40% by mass relative to the total solid content of the active energy ray-curable composition. For example, the lower limit is more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The cationic polymerizable compound may be a single kind, or two or more kinds may be used in combination. When two or more types 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 is preferably contained Photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of a radically polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to ultraviolet rays to visible rays are preferred. In addition, it may be an active agent that produces a certain action with a photo-excited sensitizer to generate active radicals, or may be an initiator that initiates cationic polymerization according to the type of monomer.

In addition, the photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), amide phosphine compounds such as amide phosphine oxide, hexaarylbiimidazole, and oxime derivatives Such as oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc. Examples of halogenated hydrocarbon compounds having a triazine skeleton include: "Bulletin of the Chemical Society of Japan (Bull. Chem. Soc. Japan)", Wakabayashi et al., No. 42, page 2924 (1969) Compounds, compounds described in British Patent No. 1384492, compounds described in Japanese Patent Laid-Open No. 53-133428, compounds described in German Patent No. 3337024, FC Schaefer, etc. "Journal of Organic Chemistry (J. Org. Chem.)" No. 29, page 1527 (1964), compounds described in Japanese Patent Laid-Open No. 62-58241, Japanese Patent Laid-Open No. 5 -281728 Compounds, compounds described in Japanese Patent Laid-Open No. 5-34920, compounds described in US Patent No. 4212976, and the like.

In addition, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acetylphosphine compounds, Phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene- Compounds in the group consisting of iron complexes and their salts, halomethyloxadiazole compounds, and coumarin compounds substituted with 3-aryl groups.

Particularly preferred are: trihalomethyltriazine compounds, α-aminoketone compounds, acetylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, benzene The ketone compound is more preferably at least one selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds Compound.

For a specific example of the photopolymerization initiator, for example, reference can be made to paragraph number 0265 to paragraph number 0268 of Japanese Patent Laid-Open No. 2013-29760, and this content can be incorporated into this specification.

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

Hydroxyacetophenone-based initiators can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all made by BASF).

Aminoacetophenone-based initiators can be used as commercial products, IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all BASF (Manufactured by BASF). As the aminoacetophenone-based initiator, a compound described in Japanese Patent Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wave light source such as 365 nm or 405 nm can also be used.

Acylphosphine-based initiators can be used as commercial products, IRGACURE-819, or Lucirin-TPO (trade names: all manufactured by BASF).

The photopolymerization initiator is more preferably an oxime compound.

Specific examples of the oxime compound include compounds described in Japanese Patent Laid-Open No. 2001-233842, compounds described in Japanese Patent Laid-Open No. 2000-80068, and compounds described in Japanese Patent Laid-Open No. 2006-342166.

In the present invention, examples of the oxime compound that can be preferably used include, for example, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, 3 -Propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one , 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one and the like.

In addition, you can also list: "Journal of the Chemical Society: Perkin Transactions II (Journal of the Chemical Society Perkin Transactions II, JCS Perkin II)" (1979), pages 1653-1660, "Journal of the Chemical Society: Berkin. "Journal of the Chemical Society Perkin Transactions II (JCS Perkin II)" (1979) pages 156-162, "Journal of Photopolymer Science and Technology (Journal of Photopolymer Science and Technology)" (1995) page Pages 202-232, Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797, Japanese Patent Laid-Open No. 2006-342166 Compounds etc.

Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (AI (Made by ADEKA).

In addition, oxime compounds other than those described above can also be used: compounds described in Japanese Patent Publication No. 2009-519904 having an oxime linked to the N position of the carbazole ring, and a hetero substituent introduced into the benzophenone site The compounds described in US Patent No. 7626957, the compounds described in Japanese Patent Laid-Open No. 2010-15025 and the US Patent Publication No. 2009-292039, and the International Publication WO2009/131189 The ketoxime compound described in US Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule The compound described in the gazette, the compound described in Japanese Patent Laid-Open No. 2009-221114, which has a maximum absorption at 405 nm and has a good sensitivity to a g-ray light source, and the like.

It is preferable to refer to, for example, paragraph number 0274 to paragraph number 0275 of Japanese Patent Laid-Open No. 2013-29760, and this content can be incorporated into this specification.

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

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

Examples of monovalent non-metallic atomic groups include alkyl groups, aryl groups, acetyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. In addition, these groups may have more than one substituent. In addition, the substituent may be further substituted with other substituents.

Examples of the substituent include halogen atom, aryloxy group, alkoxycarbonyl group or aryloxycarbonyl group Group, acetyloxy group, acetyl group, alkyl group, aryl group, etc.

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 more than one substituent. Examples of the substituent include the aforementioned substituents.

In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkyl group, or an alkynyl group. These groups may have more than one substituent. Examples of the substituent include the aforementioned substituents.

The present invention can also use an oxime compound having a fluorine atom as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Laid-Open No. 2010-262028, Compound 24 and Compounds 36 to 40 described in Japanese Patent Laid-Open No. 2014-500852, and Japanese Patent No. The compound (C-3) and the like described in Japanese Patent Publication No. 2013-164471 are disclosed. These contents can be incorporated into this specification.

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

In formula (1), R ¹ and R ² each independently represent a chain alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 carbon atoms ~30 arylalkyl group, when R ¹ and R ² are phenyl groups, phenyl groups can be bonded to each other to form a fluorenyl group, and R ³ and R ⁴ each independently represent a hydrogen atom and a carbon number of 1-20 An alkyl group, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group.

Formula ^{(2), R 1, R 2, R} 3 and R ⁴ of the formula R (1) is ^1, R ^2, R ³ and R ⁴ are the same meanings, R ⁵ represents -R ^6, -OR ^6, -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or Hydroxyl group, R ⁶ represents a C 1-20 alkyl group, a C 6-30 aryl group, a C 7-30 aryl alkyl group or a C 4-20 heterocyclic group, X represents a direct bond or Carbonyl, a represents an integer from 0 to 4.

In the above formula (1) and formula (2), R ¹ and R ^{2 are} preferably independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R ^{3 is} preferably methyl, ethyl, phenyl, tolyl or xylyl. R ^{4 is} preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ^{5 is} preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond.

Specific examples of the compounds represented by formula (1) and formula (2) include, for example, the compounds described in paragraph numbers 0076 to paragraph number 0079 of Japanese Patent Laid-Open No. 2014-137466. This content can be incorporated into this manual.

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

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

From the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000.

The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using ethyl acetate solvent to measure at a concentration of 0.01 g/L .

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

The content of the photopolymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and particularly preferably 1% by mass relative to the total solid content of the active energy ray-curable composition. 20% by mass. The active energy ray-curable composition may contain only one kind of photopolymerization initiator or two or more kinds. When two or more types are included, the total amount is preferably within the 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 that generates an acid by irradiation with active energy rays (radiation). The acid generator can be appropriately selected from the following compounds used in photocationic polymerization initiators, pigment-based photobleaching agents, photochromic agents, or micro-resists, etc. The compounds are used by light (400 nm to 200 nm Ultraviolet and far-ultraviolet, particularly preferably g-rays, h-rays, i-rays, KrF excimer laser), ArF excimer laser, electron beam, X-ray, molecular beam or ion beam, etc. to generate acid, preferably To select an acid generator that is sensitive to ultraviolet rays.

Examples of acid generators include onium salt compounds such as diazonium salts, phosphonium salts, ammonium salts, and iodonium salts that decompose and generate acids by irradiation with radiation, amide imine sulfonate, oxime sulfonate, and diazo bis Sulfonate compounds such as ballast, erlene, ortho-nitrobenzyl sulfonate, etc. Examples of the type, specific compound, and preferred examples of the acid generator include compounds described in Paragraph No. 0066 to Paragraph No. 0122 of Japanese Patent Laid-Open No. 2008-13646, and these compounds can also be applied to the present invention.

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

In formula (b1), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group. X ^- represents a non-nucleophilic anion, preferably, sulfonate anion, carboxylate anion, bis(alkylsulfonyl)amide anion, tri(alkylsulfonyl)methylate anion, BF _{4 ^{-, PF 6 -, SbF 6}} - or a group shown below and the like, preferably _{^{BF 4 -, PF 6 -,}} SbF 6 -.

Examples of commercially available products of the acid generator include WPAG-469 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

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

<<Silane coupling agent>>

The active energy ray-curable composition may contain a silane coupling agent for the purpose of improving the adhesion to the substrate. In particular, when the active energy ray-curable composition contains a thermosetting resin, it is preferable to further contain a silane coupling agent. Even when an active energy ray-curable composition containing a thermosetting resin is used to produce a cured film by a low-temperature process of 100° C. or lower, it is possible to sufficiently ensure the density with the substrate by further containing a silane coupling agent Fit.

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 so-called hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond through a hydrolysis reaction and/or a condensation reaction. Examples of hydrolyzable groups include: Halogen atom, alkoxy, acetyloxy, alkenyloxy. When the hydrolyzable group has a carbon atom, its carbon number is preferably 6 or less, and more preferably 4 or less. Particularly preferred is an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms.

In the present invention, in order to improve the adhesion of the cured film, the silane coupling agent preferably does not contain fluorine atoms and silicon atoms (except for the silicon atoms bonded to the hydrolyzable group), and preferably contains no fluorine atoms or silicon atoms. (Among them, except for silicon atoms bonded to hydrolyzable groups), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched chain alkyl groups having 3 or more carbon atoms.

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

Formula (Z) *-Si(R ^z1 ) _3-m (R ^z2 ) _m

R ^z1 represents an alkyl group, R ^z2 represents a hydrolyzable group, and m represents an integer of 1 to 3. The carbon number of the alkyl group represented by R ^z1 is preferably 1 to 5, more preferably 1 to 3. The definition of the hydrolyzable group represented by R ^z2 is as described above.

The silane coupling agent preferably has a hardening functional group. The curable functional group is preferably selected from the group consisting of (meth)acryloyloxy, epoxy, oxetanyl, isocyanato, hydroxy, amine, carboxy, thiol, alkoxysilyl, At least one member selected from the group consisting of hydroxymethyl, vinyl, (meth)acrylamide, styryl, and maleimide, more preferably selected from (meth)acryl One or more of the group consisting of oxy, epoxy and oxetanyl. Hardenable functional groups can be directly bonded to silicon Atoms can also be bonded to silicon atoms via linking groups.

The molecular weight of the silane coupling agent is not particularly limited, and it is preferably 100 to 1,000 in terms of operability, and preferably 270 or more and more preferably 270 to 1,000 in terms of more excellent effects of the present invention.

One of the preferable forms of the silane coupling agent includes the silane coupling agent X represented by the formula (W).

Formula (W) R ^z3 -Lz-Si(R ^z1 ) _3-m (R ^z2 ) _m

R ^z1 represents an alkyl group, R ^z2 represents a hydrolyzable group, R ^z3 represents a curable functional group, Lz represents a single bond or a divalent linking group, and m 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 preferred range is also as described above.

Lz represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene, aryl, -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, -SO ₂ NR ¹² -, -O-, -S-,- SO ₂ -, or a combination of these groups.

The carbon number of the alkylene group is preferably 1-20. The alkylene group may be either linear or branched. The alkylene group and aryl group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.

Lz is preferably at least one selected from the group consisting of alkylene groups having 2 to 10 carbon atoms and arylene groups having 6 to 12 carbon atoms, or containing these groups and selected from -NR ¹² -,- A group consisting of a combination of at least one group in the group consisting of CONR ¹² -, -CO-, -CO ₂ -, -SO ₂ NR ¹² -, -O-, -S-, and -SO ₂ -, and more It is preferably an alkylene group having 2 to 10 carbon atoms, -CO ₂ -, -O-, -CO-, -CONR ¹² -, or a group containing a combination of these groups. Here, R ¹² represents a hydrogen atom or a methyl group.

m represents 1~3, preferably 2~3, more preferably 3.

Examples of the silane coupling agent X include: N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), and N-β-aminoethyl -Γ-aminopropyltrimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Trade name KBE-602 made by Industrial Co., Ltd., γ-aminopropyltrimethoxysilane (trade name KBM-903 made by Shin-Etsu Chemical Industry Co., Ltd.), γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Industry) Product name KBE-903 manufactured by the company, 3-methacryloxypropyltrimethoxysilane (product name KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), glycidoxyoctyl trimethoxysilane (Shin-Etsu) Trade name KBM-4803 manufactured by Chemical Industry Corporation).

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

If the silane coupling agent Y has at least one silicon atom in the molecule, the silicon atom can be bonded to the following atoms and substituents. These may be the same atom, substituent, or different. Examples of the bondable atoms and substituents include hydrogen atom, halogen atom, hydroxyl group, C1-C20 alkyl group, alkenyl group, alkynyl group, aryl group, alkyl group and/or aryl group Amine groups, silane groups, C 1-20 alkoxy groups, aryloxy groups, etc. These substituents can be further substituted by silane, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amine groups and halogens which can be substituted by alkyl and/or aryl groups Atom, sulfonamide group, alkoxycarbonyl group, amide group, urea group, ammonium group, alkylammonium group, carboxyl group or its salt, sulfo group or its salt are substituted.

In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.

The silane coupling agent Y may contain a group represented by formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule. The nitrogen atom preferably exists in the form of a secondary amine group or a tertiary amine group, that is, the nitrogen atom preferably has at least one organic group as a substituent. In addition, the structure of the amine group may exist in the form of a partial structure of a nitrogen-containing heterocyclic ring, or may exist as a substituted amine group such as aniline. Here, the organic group may include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination of these groups. These organic groups may further have a substituent, and the substituents that can be introduced include silane group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, amine group, halogen atom, Sulfonamide group, alkoxycarbonyl group, carbonyloxy group, amide group, ureido group, alkyleneoxy group, ammonium group, alkylammonium group, carboxyl group or salt thereof, sulfo group and the like.

In addition, the nitrogen atom is preferably bonded to the curable functional group via an arbitrary organic linking group. Preferred organic linking groups include the nitrogen atom and the substituents that can be introduced into the organic group bonded to the nitrogen atom.

The definition of the hardening functional group contained in the silane coupling agent Y is as described above As mentioned, the preferred range is also as described above.

In the silane coupling agent Y, the hardening functional group may have at least one or more in one molecule, but may have two or more hardening functional groups in one molecule. From the viewpoint of sensitivity and stability, it is preferable to have 2 to 20 curable functional groups in one molecule, more preferably 4 to 15 and particularly preferably 6 to 10.

Examples of the silane coupling agent Y include compounds represented by the following formula (Y).

Formula (Y) (R ^y3 ) _n -LN-Si(R ^y1 ) _3-m (R ^y2 ) _m

R ^y1 represents an alkyl group, R ^y2 represents a hydrolyzable group, R ^y3 represents a curable functional group, LN represents a (n+1)-valent linking group having a nitrogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 or more .

R ^y1 , R ^y2 , R ^y3 and m of formula (Y) have the same meanings as R ^z1 , R ^z2 , R ^z3 and m of formula (W), respectively, and the preferred ranges are also the same.

N in 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 particularly preferably 10 or less. For example, the lower limit is preferably 2 or more, more preferably 4 or more, and particularly preferably 6 or more. In addition, n can also be set to 1.

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

The group having a nitrogen atom may be at least one selected from the following formula (LN-1) to formula (LN-4), or include the following formula (LN-1) to formula (LN-4) and selected A group selected from a combination of at least one of -CO-, -CO ₂ -, -O-, -S-, and -SO ₂ -. The alkylene group may be either linear or branched. The alkylene group and aryl group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.

In the formula, * represents the link key.

As specific examples of the silane coupling agent Y, for example, the following compounds may be mentioned. In the formula, Et represents ethyl. In addition, the compounds described in Paragraph No. 0018 to Paragraph No. 0036 of Japanese Patent Laid-Open No. 2009-288703 can be cited, and this content can be incorporated into this specification.

The content of the silane coupling agent is preferably 0.01% by mass to 10% by mass relative to the total solid content of the active energy ray-curable composition, more preferably 0.01% by mass to 5 quality%. The lower limit is more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. The silane coupling agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

<<Color Colorant>>

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

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

The average particle diameter (r) of the pigment preferably satisfies 20 nm≦r≦300 nm, more preferably satisfies 25 nm≦r≦250 nm, and particularly preferably satisfies 30 nm≦r≦200 nm. Here, the "average particle diameter" refers to the average particle diameter of the secondary particles in which the primary particles of the pigment are aggregated.

In addition, the particle size distribution of the secondary particles of the pigment that can be used (hereinafter also simply referred to as "particle size distribution") is preferably (average particle diameter ± 100). The secondary particles in nm are 70% by mass or more of the whole, more It is preferably at least 80% by mass. In addition, the particle size distribution of the secondary particles can be measured using the scattering intensity distribution.

In addition, the average particle size of the primary particles can be observed by using a scanning electron microscope (SEM) or transmission electron microscope (TEM). The aggregated part measures 100 particle sizes and calculates the average value to obtain it.

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

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

The dye is not particularly limited, and known dyes can be used. The chemical structure can be used: pyrazole azo system, anilino azo system, triarylmethane system, anthraquinone system, azomethine system, anthrapyridone (anthrapyridone) system, benzylidene (benzylidene) system, oxygen Oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine (pyrrolopyrazole azomethine) Dyes such as xanthene, phthalocyanine, benzopyran, indigo, pyromethene and other dyes. In addition, polymers of these dyes can also be used. In addition, the dyes described in Japanese Patent Laid-Open No. 2015-028144 and Japanese Patent Laid-Open No. 2015-34966 can also be used.

In addition, as dyes, acid dyes and/or derivatives thereof may be preferably used in some cases.

In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and/or derivatives of these dyes can also be effectively used Wait.

Specific examples of acid dyes are listed below, but not limited to these specific examples. Examples include the following dyes and derivatives of these dyes.

Acid alizarin violet N, Acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40~45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1, Acid chrome violet K, Acid magenta (Acid Fuchsin); Acid green (Acid green) 1, 3, 5, 9, 16, 25, 27, 50, Acid orange (Acid orange) 6, 7, 8, 10, 12, 50, 51, 52, 56, 63 , 74, 95, Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66 , 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215 , 216, 217, 249, 252, 257, 260, 266, 274, Acid violet 6B, 7, 9, 17, 19, Acid yellow 1, 3, 7, 9, 11, 17 , 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243, Food yellow (Food yellow) 3.

In addition, azo, xanthene, and phthalocyanine acid dyes other than those mentioned above are also preferred, and CI solvent blue (Solvent Blue) 44, 38; CI solvent orange (Solvent orange) 45 are also preferably used; Acid dyes such as Rhodamine B and Rhodamine 110 and derivatives of these dyes.

Among them, the dye is preferably selected from triarylmethane-based, anthraquinone-based, azomethine-based, benzylidene-based, oxacyanine-based, cyanine-based, phenothiazine-based, pyrrolopyrazoleazomethine Alkali, xanthene, phthalocyanine, benzopyran, indigo, pyrazolyl azo, anilinoazo, pyrazolotriazole azo, pyridone azo, anthracene A coloring agent in the pyridone system and the pyrrole methylene system.

Furthermore, pigments and dyes may be used in combination.

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

<<Black Colorant>>

The active energy ray-curable composition may contain a black colorant. As the black colorant, any one of an organic black colorant and an inorganic black colorant can be used. In addition, the two can also be used in combination. Regarding the composition containing the black colorant, the curability obtained by exposure is low, and the heat treatment at high temperature was previously performed, but according to the method of the present invention, even It is an active energy ray-curable composition containing a black colorant, and a cured film with excellent reliability can also be produced by a low-temperature process, and the effect of the present invention is particularly remarkable.

(Organic black colorant)

Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. Examples of the bisbenzofuranone compounds include those described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, etc., for example, BASF (BASF) Obtained by "IRGAPHOR Black" manufactured by the company. Examples of perylene compounds include C.I. Pigment Black 31 and 32. Examples of the azomethine compounds include those described in Japanese Patent Laid-Open No. 1-170601, Japanese Patent Laid-Open No. 2-34664, and the like, for example, "Chromofine Black A1103" manufactured by Dairi Seiki Co., Ltd. And get. The azo-based compound is not particularly limited, and preferably includes compounds represented by the following formula (A-1).

(Inorganic black colorant)

Examples of the inorganic black colorant include carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, and graphite. These can achieve high optical density in small amounts. Among them, it is preferable to include at least one of carbon black and titanium black, and particularly preferable is titanium black.

Titanium black is black particles containing titanium atoms. Preferably, low-valent titanium oxide, titanium oxynitride, or the like is used. The titanium black particles can modify the surface as needed for the purpose of improving dispersibility, suppressing cohesiveness, and the like. It may be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and may also be treated with a water-repellent substance shown in Japanese Patent Laid-Open No. 2007-302836.

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

Specifically, the average primary particle size is preferably in the range of 10 nm to 45 nm. In addition, the particle diameter in the present invention, that is, the particle diameter is the diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles can be obtained by measuring the area obtained by photography in an electron microscope photograph and correcting the photographic magnification.

The specific surface area of titanium black is not particularly limited, in order to make the water repellent after surface treatment of titanium black with a water repellent agent a predetermined performance, the value measured by the method of Brunauer (Emmett, Teller, BET) preferably ^{5m 2 / g ~ 150m 2 /} g, more preferably ^{20m 2 / g ~ 120m 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 Co., Ltd.), Tilack (Tilack) ) D (trade name: Akaho Chemical Co., Ltd.), etc.

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.

In this form, the titanium black is contained in the composition as a dispersion, and the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersion is preferably 0.05 or more in terms of mass, and more preferably It is 0.05~0.5, especially good is 0.07~0.4.

Here, the to-be-dispersed body includes both the state in which titanium black is a primary particle and the state in agglomerates (secondary particles).

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

First, a titanium oxide and silicon dioxide particles are dispersed by using a dispersing machine to obtain a dispersion, and the dispersion is reduced at a high temperature (for example, 850°C to 1000°C) to obtain titanium black particles The composition contains Si and Ti to be dispersed. The reduction treatment can also be performed in an environment of reducing gas such as ammonia. Examples of titanium oxide include TTO-51N (trade name: manufactured by Ishihara Industries). Examples of commercially available products of silicon dioxide particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name: manufactured by Evonik).

A dispersant can also be used in the dispersion of titanium oxide and silicon dioxide particles. Examples of the dispersant include those described in the column of the dispersant.

The dispersion can be carried out in a solvent. Examples of the solvent include water and organic solvents. Specific examples include those described in the column of organic solvents described later.

Titanium black with Si/Ti adjusted to, for example, 0.05 or more can be obtained from paragraph number 0005 and paragraph number 0016 to paragraph of Japanese Patent Laid-Open No. 2008-266045, for example. Created by the method described in the registration number 0021.

Among the dispersions containing titanium black and Si atoms, titanium black can be used as described above.

In addition, in this to-be-dispersed body, together with titanium black, for the purpose of adjusting the dispersibility, coloring property, etc., a composite oxide containing Cu, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide may also be used , Carbon black, aniline black and other black pigments, or a combination of two or more.

In this case, it is preferable that the to-be-dispersed body containing titanium black accounts for 50 mass% or more of all to-be-dispersed bodies.

In addition, in this to-be-dispersed body, for the purpose of adjusting light-shielding properties and the like, as long as the effect of the present invention is not impaired, other colorants (organic pigments or dyes) may be used together with titanium black as necessary.

Hereinafter, materials used when Si atoms are introduced into the dispersion will be described. When introducing Si atoms into the dispersion, a substance containing Si such as silicon dioxide may be used.

Examples of usable silica include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These can be used as appropriate.

Furthermore, if the particle diameter of the silicon dioxide particles is smaller than the film thickness when the light-shielding film is formed, the light-shielding property is more excellent. Therefore, it is preferable to use fine particle type silicon dioxide as the silicon dioxide particles. In addition, examples of fine particle type silicon dioxide include, for example, the silicon dioxide described in paragraph No. 0039 of Japanese Patent Laid-Open No. 2013-249417, and this content can be incorporated into this specification.

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

In addition, the total content of the black colorant and the color colorant is preferably 1% by mass to 80% by mass relative to the total solid content of the active energy ray-curable composition. The lower limit is more preferably 5% by mass or more, particularly preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit is more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

<<Infrared Absorbent>>

The active energy ray curable composition may contain an infrared absorber.

In the present invention, the infrared absorber refers to a compound having a maximum absorption in the wavelength range of the infrared region (preferably, the wavelength is 800 nm to 1300 nm).

Examples of the infrared absorber include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, and squarylium salts (squarylium) compound, naphthalocyanine compound, quaterrylene compound, dithiol metal complex compound, croconium compound, etc.

As the pyrrolopyrrole compound, the compounds described in Paragraph No. 0049 to Paragraph No. 0058 of Japanese Patent Laid-Open No. 2009-263614 can be used, and the contents can be incorporated into this specification. Phthalocyanine compounds, naphthalocyanine compounds, ammonium compounds, cyanine compounds, squarylium compounds and keto acid compounds can also be used in Japan The compounds disclosed in paragraph number 0010 to paragraph number 0081 of Japanese Patent Laid-Open No. 2010-111750 can be incorporated into this specification. In addition, for cyanine compounds, for example, please refer to "Functional Pigments, Ogawahara Letters/Matsuoka Ken/ Kitao Tiejiro/Hirashima Hiroshi ‧ Work, Kodansha Technology", which can be incorporated into this specification.

In addition, infrared absorbers can be used: the compounds disclosed in paragraph No. 0004 to paragraph No. 0016 of Japanese Patent Laid-Open No. 07-164729, or the paragraph No. 0027 to paragraph No. 0062 disclosed in Japanese Patent Laid-Open No. 2002-146254 Compound, Japanese Patent Laid-Open No. 2011-164583, Paragraph No. 0034 to Paragraph No. 0067, which discloses crystallites containing oxides containing Cu and/or P and has a near-infrared absorption with a number average aggregate particle size of 5 nm to 200 nm Particles, these contents can be incorporated into this description. In addition, FD-25 (manufactured by Yamada Chemical Co., Ltd.), IRA842 (manufactured by Exiton), or the like can also be used.

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

In addition, the total content of the infrared absorber, the black colorant, and the color colorant is preferably 1% by mass to 80% by mass relative to the total solid content of the active energy ray-curable composition. The lower limit is more preferably 5% by mass or more, particularly preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit is more preferably 75% by mass or less, and particularly preferably 70% by 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 acid group, a basic group, or phthalimide methyl group. The pigment derivative is preferably a pigment derivative having an acidic group or a basic group.

<<Organic Solvent>>

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

The organic solvent is basically not particularly limited if it satisfies the solubility of each component or the applicability of the composition.

As the organic solvent, esters are preferably exemplified by ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate Ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (example: methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc. (eg: Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionate (example : Methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example: methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate Esters, ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-oxypropionate (example: methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxyl Propyl propionate, etc. (for example: methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate, etc.)), 2-oxy-2-methyl propionate methyl ester and 2-oxy-2-methyl propionate ethyl ester (for example: 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate Etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.; and Examples of the ethers are preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; and The ketones can be preferably exemplified by methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc.; and the aromatic hydrocarbons can be preferably exemplified by toluene, xylene Wait.

From the viewpoints of solubility of polymerizable compounds, alkali-soluble resins, etc., and improvement of coating surface shape, these organic solvents are also preferably used in combination of two or more kinds. In this case, it is particularly preferable to contain the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol di Methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol A mixed solution of two or more of methyl ether acetate.

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

From the viewpoint of applicability, the content of the active energy ray-curable composition of the organic solvent is preferably an amount such that the total solid content concentration of the composition becomes 5% by mass to 80% by mass, more preferably 5% by mass % To 60% by mass, especially 10% to 50% by mass.

The active energy ray-curable composition may contain only one organic solvent, or two or more types. When two or more types are included, the total amount is preferably within the range.

<<polymerization inhibitor>>

In order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition, the active energy ray-curable composition is preferably added with a small amount of a polymerization inhibitor.

Examples of polymerization inhibitors include hydroquinone, para-methoxyphenol, di-tert-butyl-p-cresol, and gallnut ( pyrogallol), tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2' -Methylene bis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, etc.

When the active energy ray-curable composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 5% by mass relative to the total solid content of the active energy ray-curable composition.

The active energy ray-curable composition may contain only one kind of polymerization inhibitor, or two or more kinds. When two or more types are included, the total amount is preferably within the range.

<<Surface Active Agent>>

In the active energy ray-curable composition, from the viewpoint of further improving the coatability, various surfactants may be added. Surfactant can be used: fluorine-based interface Various surfactants such as sex agents, nonionic surfactants, cationic surfactants, anionic surfactants, silicone surfactants, etc.

For example, by containing a fluorine-based surfactant, the liquid characteristics (especially fluidity) when prepared as a coating liquid are further improved. That is, when a coloring composition containing a fluorine-based surfactant is used to form a cured film, by reducing the interfacial tension between the coated surface and the coating liquid, the wettability of the coated surface is improved , The applicability to the coated surface is improved. Therefore, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in more appropriately forming a uniform thickness film with a small thickness unevenness.

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

Examples of the fluorine-based surfactants are Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141 、Megafac F142、Megafac F143、Megafac F144、Megafac R30、Megafac F437、Megafac F475、Megafac F479、 Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, manufactured by DIC), Fluorad FC430, Phnom Penh Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC- 104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc.

A block polymer can also be used as a fluorine-based surfactant, and specific examples include the compounds described in Japanese Patent Laid-Open No. 2011-89090.

In addition, the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

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

In addition, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples include Japanese Patent Laid-Open No. 2010-164965 The compounds described in Paragraph No. 0050 to Paragraph No. 0090 and Paragraph No. 0289 to Paragraph No. 0295 of No. Gazette are, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. In addition, the fluorine-containing polymer having an ethylenically unsaturated group in the side chain is a compound different from the radical polymerizable compound.

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates of these (for example: glycerol propoxylate) Compounds, glycerol ethoxylates, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether , Polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, manufactured by BASF) 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Solsperse 20000 (Lubrizol (share)), etc. In addition, Pionin D-6112-W manufactured by Takemoto Oil Co., Ltd., and NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactants include phthalocyanine derivatives (trade name: Efka (EFKA)-745, manufactured by Morishita Industry Co., Ltd.), and organosiloxane polymer KP341 (Shin-Etsu Chemical Industry Co., Ltd.) (Manufactured), (meth)acrylic (co)polymer Polyflow No.75, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yushang Co., Ltd.) Manufacturing) etc.

Specific examples of the anionic surfactants include W004, W005, W017 (manufactured by Yushang Co., Ltd.) etc.

Examples of silicone-based surfactants include: "Toray Silicone DC3PA" manufactured by Toray Dow Corning (Toray Dow Corning), "Toray Silicone SH7PA", and "Toray" Silicone (Toray Silicone DC11PA), ``Toray Silicone SH21PA'', ``Toray Silicone SH28PA'', ``Toray Silicone SH29PA'', ``Toray Silicone SH29PA'', ``Toray Silicone SH29PA'' (Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4445" manufactured by Momentive Performance Materials "TSF-4460", "TSF-4452", "KP341", "KF6001", "KF6002" made by Shin-Etsu Silicone Co., Ltd., "BYK307", "BYK323", "" made by BYK Chemie BYK330" etc.

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

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

<<Other additives>>

The active energy ray-curable composition may be formulated with various additives as needed, such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-agglomeration agents. Examples of these additives include those described in Paragraph No. 0155 to Paragraph No. 0156 of Japanese Patent Laid-Open No. 2004-295116, and this content can be incorporated into this specification.

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

<Example of active energy ray-curable composition>

In the production method of the present invention, when forming a cured film having a thickness of 0.5 μm, the optical density at any wavelength in the range of 260 nm to 440 nm becomes 1 or more (preferably 2 or more, more preferably 3 or more). In the case of an active substance, the active energy ray-curable composition is effective.

In addition, when the active energy ray-curable composition forms a cured film with a thickness of 0.5 μm, the minimum value of the optical density in the wavelength range of 260 nm to 440 nm is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more .

In addition, when the active energy ray-curable composition forms a cured film with a thickness of 0.5 μm, the optical density at a wavelength of 365 nm is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more.

The optical density is a value that expresses the degree of absorption in logarithm and is a value defined by the following formula. In the present invention, the optical density of the cured film is a value obtained by measuring the transmittance using a spectroscope (UV4100 (trade name)) manufactured by Hitachi High-Technologies Co., Ltd. with a wavelength of 365 nm.

OD(λ)=Log ₁₀ [T(λ)/I(λ)]

λ represents wavelength, OD(λ) represents optical density at wavelength λ, T(λ) represents transmitted light quantity at wavelength λ, and I(λ) represents incident light quantity at wavelength λ.

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 containing light in the wavelength region of 260 nm to 440 nm may be included, or the content of the coloring agent in the total solid content may be appropriately adjusted Awaited.

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

In addition, other examples of the active energy ray-curable composition having the optical density include the minimum value A of the absorbance in the range of wavelengths from 400 nm to less than 580 nm, and the absorbance in the range of wavelengths from 580 nm to 750 nm. The ratio A/B of the minimum value B of 0.3 to 3, and the ratio C of the minimum value C of the absorbance in the range of wavelengths from 400 nm to 750 nm and the maximum value D of the absorbance in the range of wavelengths from 1000 nm to 1300 nm /D becomes an active energy ray curable composition of 5 or more. By using a composition having this spectral characteristic, it is possible to preferably form a cured film having the spectral characteristic that the maximum value of the transmittance in the wavelength range of 400 nm to 700 nm is 20% or less and the wavelength The minimum value of a specific range of 850~1300nm is more than 80%.

The absorbance Aλ at a certain wavelength λ is defined by the following formula (1).

Aλ=-log(Tλ)‧‧‧‧(1)

Aλ is the absorbance at wavelength λ, and Tλ is the transmittance at wavelength λ.

In the present invention, the value of absorbance may be a value measured in the state of a solution, or may be a value in the state of a film formed by using the composition. In the case where the absorbance is measured in the state of a film, it is preferable to use a film obtained as follows, and apply the composition to the glass so that the film thickness after drying becomes a predetermined film thickness by a method such as spin coating. The substrate was prepared by drying on a hot plate at 100°C for 120 seconds. The film thickness of the film was measured on a substrate with a film using a stylus-type surface shape measuring instrument (DEKTAK 150 manufactured by ULVAC).

In addition, absorbance can be measured using a conventionally known spectrophotometer. The measurement conditions of absorbance are not particularly limited, but it is preferable to measure the range of wavelengths from 580 nm to 750 nm under the condition that the minimum value A of absorbance in the range of wavelengths from 400 nm to 580 nm is 0.1 to 3.0. The minimum value B of the absorbance in, the minimum value C of the absorbance in the range of 400 nm or more and 750 nm or less, and the maximum value D of the absorbance in the range of 1000 nm or more and 1300 nm or less. By measuring the absorbance under the above conditions, the measurement error can be made smaller. The method of adjusting so that the minimum value A of the absorbance in the wavelength range of 400 nm or more and less than 580 nm becomes 0.1 to 3.0 is not particularly limited. For example, when the absorbance is measured in the state of a composition (solution), a method of adjusting the optical path length of the sample unit can be cited. In addition, when the absorbance is measured in the state of the film, a method of adjusting the film thickness, etc. may be mentioned.

The measurement methods of the spectroscopic characteristics, film thickness, etc. of the film are shown below.

By a method such as spin coating, the composition is applied to the glass substrate so that the film thickness after drying becomes the predetermined film thickness, and is dried on a hot plate at 100° C. for 120 seconds. The film thickness of the film was measured on the dried substrate with the film using a stylus-type surface shape measuring instrument (DEKTAK 150 manufactured by ULVAC). Using a ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation), the transmittance in the wavelength range of 300 nm to 1300 nm was measured for the dried substrate with the film.

Examples of the active energy ray-curable composition having the above-mentioned spectral characteristics include a composition containing a color material that blocks visible light. The color material that blocks visible light is preferably a material that absorbs light in the wavelength range from purple to red. The color material that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).

(A): Two or more color colorants are included, and black is formed by a combination of two or more color colorants.

(B): Contains organic black colorants.

The color coloring agent and the organic black coloring agent may include the above.

In the present invention, the color material that blocks visible light is preferably, for example, a ratio A/B of 4.5 or more, which is the ratio of the minimum absorbance A in the wavelength range of 450 nm to 650 nm to the minimum absorbance B in the wavelength range of 900 nm to 1300 nm. . The characteristics can be satisfied by one kind of raw material, or by a combination of multiple raw materials.

In the case of the aspect (A), it is preferable to contain two or more colorants selected from the group consisting of red colorants, yellow colorants, blue colorants, and purple colorants. In addition, it preferably contains a coloring agent selected from the group consisting of a red coloring agent, a yellow coloring agent and a purple coloring agent At least one of the agents and the blue colorant. Among them, any of the following (1) to (3) is preferred.

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

(2) The form containing a red colorant, a yellow colorant, and a blue colorant.

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

In the case of containing a red colorant, a yellow colorant, a blue colorant, and a purple colorant as color colorants, the mass ratio of the red colorant is preferably based on the mass ratio with respect to the total amount of color colorants 0.1~0.6, the mass ratio of yellow colorant is 0.1~0.4, the mass ratio of blue colorant is 0.1~0.6, and the mass ratio of purple colorant is 0.01~0.3. 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.

In addition, when a red colorant, a yellow colorant, and a blue colorant are contained as a color colorant, it is preferable that the mass ratio of the red colorant is 0.2 to the mass ratio with respect to the total amount of the color colorant. 0.7, the mass ratio of yellow colorants is 0.1~0.4, and the mass ratio of blue colorants is 0.1~0.6. 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 addition, when a yellow colorant, a blue colorant, and a purple colorant are contained as color colorants, it is preferable that the mass ratio of the yellow colorant is 0.1 to the mass ratio with respect to the total color colorant. 0.4, the mass ratio of blue colorant is 0.1 ~0.6, the mass ratio of purple colorant is 0.2~0.7. 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 addition, the active energy ray-curable composition having the above-mentioned spectral characteristics may further contain an infrared absorber (preferably an infrared absorber having a maximum absorption in the wavelength range of 800 nm to 900 nm). With this, it is possible to preferably form a cured film having a spectral characteristic that the maximum value of the transmittance in the wavelength range of 400 nm to 830 nm is 20% or less and the minimum value of the transmittance in the wavelength range of 1000 nm to 1300 nm More than 80%.

In this form, the infrared absorber preferably contains 10 to 200 parts by mass with respect to 100 parts by mass of the color material that blocks visible light. In addition, the content of the infrared absorber is preferably 1% by mass to 60% by mass of the total solid content of the composition, and more preferably 10% by mass to 40% by mass. The content of the color material that blocks visible light is preferably 10% by mass to 60% by mass of the total solid content of the composition, and more preferably 30% by mass to 50% by mass. The total amount of the infrared absorber and the color material that blocks visible light is preferably 1% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and particularly preferably 30% by mass relative to the total solid content of the composition. 70% by mass.

<Preparation method of active energy ray hardening composition>

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

When preparing the active energy ray-curable composition, the ingredients can be formulated in batches or dissolved. After dispersing in the solvent, make up one by one. In addition, the order of input and operating conditions during deployment are not particularly restricted. For example, all the ingredients can be dissolved at the same time. Disperse in the solvent to prepare the composition, if necessary, you can make each component into two or more solutions beforehand. The dispersion liquid is prepared by mixing these at the time of use (during application) to prepare a composition.

In the preparation of the active energy ray-curable composition, for the purpose of removing foreign substances or reducing defects, it is preferable to perform filtration using a filter. The filter can be used without particular limitation as long as it is used for filtering purposes and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g. nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) may be used. (Including high-density and/or ultra-high molecular weight polyolefin resin) and other raw material filters. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is preferably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 3.0 μm, and particularly preferably about 0.05 μm to 0.5 μm. By setting it as this range, the fine foreign material which hinders the preparation of a uniform and smooth composition can be removed surely. In addition, it is also preferable to use a fibrous filter material. Examples of the filter material include polypropylene fibers, nylon fibers, and glass fibers. Specifically, SBP type series (SBP008, etc.) manufactured by Roki Techno can be used. ), TPR type series (TPR002, TPR005, etc.), SHPX type series (SHPX003, etc.) filter cartridge (filter cartridge).

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

In addition, the first filters with different pore sizes can also be combined within the range Together. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters can be obtained from, for example, Pall Japan Co., Ltd. (DFA4201NXEY, etc.), Advantec Toyo Co., Ltd., and Entegris Co., Ltd. (formerly Japan Mico) Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Micro Filter Co., Ltd.

The second filter may be formed of the same material as the first filter or the like.

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

<hardened 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 particularly preferably 3 or more for any wavelength in the wavelength range of 260 nm to 440 nm.

In addition, the minimum value of the optical density in the wavelength range of 260 nm to 440 nm is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more.

In addition, the optical density at a wavelength of 365 nm is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more.

According to the present invention, even a cured film with a high optical density in the wavelength region can be manufactured by a low-temperature process. Therefore, the higher the optical density, the more significant the effect of the present invention.

The optical density is preferably a value when the thickness of the cured film is 0.5 μm or more.

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

The cured film of the present invention can be preferably used for color filters, infrared transmission filters, infrared cut filters, light-shielding films, transparent films, band-pass filters, and the like. In addition, the active energy ray-curable composition may be used as a printing ink to form a printed matter.

In addition, in the present invention, the color filter refers to a filter that passes light of a specific wavelength among lights of wavelengths in the visible light range and blocks light of a specific wavelength. In addition, the infrared transmission filter refers to a filter that blocks light of wavelengths in the visible range and transmits light (infrared rays) of wavelengths in a specific infrared range. In addition, the infrared cut filter refers to a filter that transmits light (visible light) at a wavelength in the visible range and blocks at least a part of light (infrared light) at a wavelength in the infrared range. In addition, the light-shielding film refers to a film that shields light of a wavelength in at least the visible range. In addition, the transparent film refers to a film that transmits light of at least a wavelength in the visible light range.

Color filters, infrared transmission filters, and infrared cut filters can be preferably used for solid-state imaging devices such as charge coupled devices (CCD) or complementary metal oxide semiconductors (CMOS), Or an image display device such as a liquid crystal display device, or organic electroluminescence (organic electroluminescence, organic EL) components, etc.

The light-shielding film can be formed as various components in the image display device or sensor module (for example: infrared cut filter, outer periphery of the solid-state imaging element, outer periphery of the wafer-level size, back surface of the solid-state imaging element, etc.) . In addition, 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 a protective film of an image display device, a solid-state imaging element, an organic EL element, or the like, for example. In addition, it can also be used for optical devices.

The solid-state imaging element is not particularly limited as long as it includes the cured film of the present invention and functions as a solid-state imaging element. For example, the following configuration may be mentioned.

The structure is as follows: the support includes a plurality of photodiodes constituting the light-receiving area of the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transmission electrode including polysilicon, etc. The electrode includes a light-shielding film in which only the light-receiving portion of the photodiode is opened, and a device protection film including silicon nitride and the like formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode is provided for device protection A color filter is included on the film.

Furthermore, it may be configured to include a light condensing mechanism (such as a microlens, etc.; the same below) on the device protective film and under the color filter (the side close to the support), or include a light condensing device on the color filter The structure of the light mechanism, etc.

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 or details of each display device, for example, describe In "Electronic Display Devices (Showa Sasaki, published by the Industrial Survey Society (stock) in 1990)", and "Display Devices (written by Ibuki Shunzhang, Industrial Books (share) in 1989)", etc. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Uchida Ryuo, published by the Industrial Survey Association (stock) in 1994)." The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it 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 include a white organic EL element. The white organic EL element preferably has a tandem structure. The series structure of organic EL elements is described in: Japanese Patent Laid-Open No. 2003-45676, "The forefront of the development of organic EL technology-high brightness. High accuracy. Long life. Proprietary technology set -" "Technical Information Association, pages 326~328, 2008 etc. The spectrum of the white light emitted by the organic EL device is preferably one with a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm), and the yellow region (580 nm to 620 nm). In addition to these luminescence peaks, it is more preferable to have a maximum luminescence peak in the red region (650 nm to 700 nm).

[Example]

The following examples are given to further illustrate the present invention. The materials, usage amounts, ratios, processing contents, processing order, etc. shown in the following examples can be appropriately 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 specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards.

<Test Example 1>

[Production of Titanium Black A-1]

Weigh 120 g of titanium oxide with a BET specific surface area of 110 m ² /g (“TTO-51N” trade name: manufactured by Ishihara Industries), and 25 g of silica particles with a BET specific surface area of 300 m ² /g (“Aerosil ( AEROSIL) (registered trademark) 300", manufactured by Evonik), and 100g of dispersant ("DISPERBYK-190", manufactured by BYK Chemie), adding 71g The ion-exchange water was treated with MAZERSTAR KK-400W manufactured by KURABO at a revolution of 1360 rpm and a rotation speed of 1047 rpm for 30 minutes to obtain a homogeneous mixture aqueous solution. This aqueous solution was filled in a quartz container, using a small rotary kiln (manufactured by Motoyama Co., Ltd.), heated to 920°C in an oxygen atmosphere, the atmosphere was replaced with nitrogen, and flowed at 100 mL/min at the same temperature Ammonia gas was used for 5 hours to carry out nitriding reduction treatment. The powder recovered after the end was pulverized in a mortar to obtain titanium black (A-1) [dispersed dispersion containing titanium black particles and Si atoms] containing Si atoms and having a powdered specific surface area of 85 m ² /g.

[Preparation of titanium black dispersion (TB dispersion 1)]

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

For the obtained dispersion a, an ultra-apex mill (Ultra Apex Mill) UAM015 manufactured by Shou Industry Co., Ltd. was used for dispersion treatment under the following conditions, and a nylon filter (Pall (Pall), Japan, having a pore size of 0.45 μm was used Japan) (share) system (DFA4201NXEY) was filtered to obtain a titanium black dispersion (hereinafter referred to as TB dispersion 1).

(Composition 1)

‧Titanium black (A-1) obtained in the manner described ‧‧‧25 parts by mass

‧Propylene glycol monomethyl ether acetate 30 mass% solution of Resin 1‧‧‧‧25 mass parts

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

‧Resin 1: The following structure. It is synthesized by referring to the description in Japanese Patent Laid-Open No. 2013-249417. In addition, in the formula of the resin 1, x is 43% by mass, y is 49% by mass, and z is 8% by mass. In addition, the weight average molecular weight of the resin 1 was 30,000, the acid value was 60 mgKOH/g, and the number of atoms of the graft chain (excluding hydrogen atoms) was 117.

(Dispersion conditions)

‧Bead size: 0.05mm in diameter

‧Filling rate of beads: 75% by volume

‧Ground speed of mill: 8m/sec

‧Mixed liquid volume for dispersion treatment: 500g

‧Circulation flow rate (pump supply): 13kg/hr

‧Processing liquid temperature: 25℃~30℃

‧Cooling water: tap water

‧Inner volume of circular path of bead mill: 0.15L

‧Number of passes: 90

[Preparation of active energy ray-curable composition]

After mixing the following compositions, it was filtered using a nylon filter with a pore size of 0.45 μm (manufactured by Pall Japan Co., Ltd., DFA4201NXEY) 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 (manufactured by BASF)) ‧‧‧1.81 parts by mass

Radical polymerizable compound (KAYARAD DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.)) ‧‧‧6.29 parts by mass

Surfactant 1‧‧‧0.02 parts by mass

Solvent (cyclohexanone) ‧‧‧4.66 parts by mass

Fluorine-based surfactant (Megafac RS-72-K, a fluorine-containing polymer with an ethylenic unsaturated group on the side chain (manufactured by DIC), solid content 30%, solvent : Propylene glycol monomethyl ether acetate)): 10.65 parts by mass

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

Alkali soluble resin 1: The following structure. It was synthesized according to the manufacturing method of paragraph number 0338 to paragraph number 0340 of Japanese Patent Laid-Open No. 2010-106268. In the following formula, x is 90% by mass and z is 10% by mass. In addition, the weight-average molecular weight of the alkali-soluble resin 1 was 40,000, the acid value was 100 mgKOH/g, and the number of atoms of the graft chain (excluding hydrogen atoms) was 117.

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

[Manufacture of hardened film]

Use glass substrate (200mm (8 inches in diameter), thickness 0.7mm, 1737 (trade name, manufactured by Corning)) hexamethyldisilazane (HMDS) As a substrate. The HMDS treatment was performed at 100°C for 60 seconds using ACT8 (trade name) manufactured by Tokyo Electron.

After applying the prepared active energy ray-curable composition to the glass substrate that has been subjected to HMDS treatment by spin coating, a 65°C hot plate was used for heat treatment (pre-baking) for 100 seconds. The coating film thickness of the active energy ray-curable composition is adjusted so that the film thickness after prebaking becomes 4.0 μm.

Then, using an i-ray stepper exposure device (FPA-3000i5+, manufactured by Canon Co., Ltd., NA/σ=0.63/0.65, focus offset=0 μm), via a transfer pattern (10 μm ×10 μm island, mask with a pitch of 20 μm) was exposed at an exposure of 8,000 J/m ² .

Next, using AD-1200 (Mikasa (manufactured by Mikasa)), using 0.3% by mass of surfactants NCW-101 (nonionic surfactant) manufactured by Wako Pure Chemical Industries Ltd. and 0.01% by mass The developing solution of tetramethylammonium hydroxide (TMAH) was developed by puddle for 40 seconds.

Then, pure water was used for the rinsing treatment, and then dried by high-speed rotation at 200 rpm for 30 seconds.

Then, electron beam irradiation is performed under the following conditions to produce a cured film.

Electron beam irradiation conditions

Device: Electron beam irradiation device manufactured by Hamamatsu Photonics

Acceleration voltage: 5.0kV~200kV, tube current value: 4.0mA

Absorption line: 145kGy

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

Conveying speed (scanning speed during processing): 100mm/sec (200mm diameter substrate, 2 pieces/sec)

Processing temperature: 23℃ or 50℃

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

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

(Evaluation of adhesion of cured film)

After the obtained cured film was immersed in the cyclohexanone solution for 10 minutes, the adhesion was evaluated using the following criteria.

A: No pattern peeling

B: Pattern peeling occurs

(Appearance evaluation of cured film)

The appearance of the obtained cured film was evaluated.

A: Good

B: Although there is white turbidity on the surface, there is no problem.

C: A lot of white turbidity is generated on the surface, which is not practical.

(Evaluation of the reliability of the cured film)

‧Temperature cycle test resistance

Under the following conditions, a temperature cycle test of the cured film was performed.

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

Test conditions: Each was left for 15 minutes in an environment of -45°C and 85°C, and this was performed 50 cycles as one cycle, and the temperature cycle test resistance was evaluated using the following criteria.

A: No pattern peeling.

B: Although there is white turbidity on the surface, there is no problem and no pattern peeling.

C: A lot of white turbidity is generated on the surface, which is not practical. Pattern stripping is also mixed.

‧Temperature and humidity resistance

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

After being left in an environment of 85° C. and a relative humidity of 85% for 100 hours, the resistance to the constant temperature and humidity test was evaluated using the following criteria.

A: No pattern peeling.

B: Although there is white turbidity on the surface, there is no problem and no pattern peeling.

C: A lot of white turbidity is generated on the surface, which is not practical. Pattern stripping is also mixed.

As shown in the table, Test No. 101 to Test No. 108 to which an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV has been irradiated can produce a cured film with excellent reliability. In addition, the obtained cured film had good adhesion and appearance.

On the other hand, the reliability of the cured film obtained in the test number C11 with an acceleration voltage of less than 10 kV, the test number C12 with an acceleration voltage of 100 kV or more, and the test number 13 deteriorates.

<Test Example 2>

[Preparation of active energy ray-curable composition]

After mixing the following compositions, it was filtered using a nylon filter with a pore size of 0.45 μm (manufactured by Pall Japan Co., Ltd., DFA4201NXEY) to prepare an active energy ray-curable composition.

(composition)

Thermosetting resin (Cyclomer P (ACA) 230AA, (made by Daicel Corporation) ‧‧‧ 10.96 mass%

Propylene glycol monomethyl ether acetate‧‧‧‧89.03% by mass

Surfactant 1‧‧‧0.01% by mass

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

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

[Manufacture of hardened film]

After the active energy ray-curable composition prepared above was applied on a glass substrate that had been subjected to HMDS treatment by spin coating, a 65°C hot plate was used to perform heat treatment (pre-baking) for 100 seconds. The coating film thickness of the active energy ray-curable composition is adjusted so that the film thickness after prebaking becomes 0.3 μm.

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

Electron beam irradiation conditions

Device: Electron beam irradiation device manufactured by Hamamatsu Photoelectric Co., Ltd.

Acceleration voltage: 70kV, tube current value: 4.0mA

Absorption line: 145kGy

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

Conveying speed (scanning speed during processing): 100mm/sec (200mm diameter substrate, 2 pieces/sec)

Processing temperature: 23℃

(Measurement of optical density (OD value))

In the same manner as in Test Example 1, the obtained cured film (film thickness is 0.3 μm).

(Evaluation of adhesion (cross cutting))

The adhesiveness of the cured film produced as described above was evaluated by a cross-cut test (according to JIS K5600; among them, a grid pattern including 100 membrane sheets). In the cross-cut test, the cured film was cut at a depth of 11 points in the vertical and horizontal directions to the substrate.

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

A: 0

B: more than 1 and less than 100

C: 100

(Appearance evaluation of cured film)

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

(Evaluation of the reliability of the cured film)

‧Temperature cycle test resistance

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

‧Temperature and humidity resistance

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

[Table 2]

As shown in the table, Test No. 201 to Test No. 206 to which an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV has been irradiated can produce a cured film with excellent reliability.

<Test Example 3>

[Preparation of active energy ray-curable composition]

After mixing the following compositions, it was filtered using a nylon filter with a pore size of 0.45 μm (manufactured by Pall Japan Co., Ltd., DFA4201NXEY) to prepare an active energy ray-curable composition.

(composition)

Resin (Acrycure RD-F8, manufactured by Japan Catalyst Co., Ltd.) ‧‧‧19.08 parts by mass

Radical polymerizable compound (Aronix TO-2349, manufactured by East Asia Synthetic Co., Ltd.) ‧‧‧ 47.7 parts by mass

Photopolymerization initiator (IRGACURE-184, manufactured by BASF) ‧‧‧‧4.10 parts by mass

Photopolymerization initiator (Lucirin-TPO, BASF) (Made by the company) ‧‧‧0.57 parts

Silane coupling agent (KBM-602, manufactured by Shin-Etsu Chemical Industry) ‧‧‧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

[Manufacture of hardened film]

Under the following conditions, the prepared active energy ray-curable composition was applied to a glass substrate (200 mm (8 inches in diameter), thickness 0.7 mm, 1737 (trade name, manufactured by Corning) )) After that, a 65°C hot plate was used for 100 seconds of heat treatment (pre-baking).

Coating: spray coating method

Atomization pressure: 450Pa

Flow rate: 3.0cm ³ /min

Distance between nozzle and substrate: 30mm

Coating scanning speed: 200mm/sec (200mm diameter substrate, 2 pieces/sec)

Scanning distance: 5.0mm

Coating film thickness: 10.0μm~50.0μm (film thickness after pre-baking, the film thickness is specified by the number of scans)

Then, using an i-ray stepper exposure device (FPA-3000i5+, manufactured by Canon (share), NA/σ=0.63/0.65, focus offset=0 μm), via an island with a transfer pattern (500 μm×500 μm , A mask with a pitch of 1000 μm) is exposed at an exposure amount of 8000 J/m ² .

Then, using AD-1200 (manufactured by Mikasa Co., Ltd.), an alkaline developing solution (tetramethylammonium hydroxide (TMAH) 0.3% by mass aqueous solution) was used to develop for 60 seconds by a coating method.

Then, pure water was used for the rinsing treatment, and then dried by high-speed rotation at 200 rpm for 30 seconds.

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

Electron beam irradiation conditions

Device: Electron beam irradiation device manufactured by Hamamatsu Photoelectric Co., Ltd.

Accelerating voltage: 95kV, tube current value: 4.0mA

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

Conveying speed (scanning speed during processing): 100mm/sec (200mm diameter substrate, 2 pieces/sec)

Processing temperature: 23℃

(Measurement of optical density (OD value))

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

(Evaluation of the reliability of the cured film)

‧Temperature cycle test resistance

In the same manner as in Test Example 1, the resistance to the temperature cycle test of the cured film was improved. OK evaluation.

‧Temperature and humidity resistance

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

As shown in the table, Test No. 301 to Test No. 308 to which an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV has been irradiated can produce a cured film with excellent reliability.

<Test Example 4>

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

After the red resist (SR2000, manufactured by FUJIFILM Electronic Materials) was applied by a spin coating method, a 65°C hot plate was used for heat treatment (pre-baking) for 150 seconds. The coating film thickness of the active energy ray-curable composition is adjusted so that the film thickness after prebaking becomes 2 μm.

Then, using an i-ray stepper exposure device (FPA-3000i5+, manufactured by Canon Co., Ltd., NA/σ=0.63/0.65, focus offset=0 μm), via having a transfer pattern (pattern size: 100 μm× 100 μm) mask, exposure at an exposure amount of 800 mJ/cm ² .

Then, using AD-1200 (manufactured by Mikasa Co., Ltd.), an alkaline developing solution (tetramethylammonium hydroxide (TMAH) 0.3% by mass aqueous solution) was used to develop for 60 seconds by a coating method.

Then, pure water was used for the rinsing treatment, and then dried by high-speed rotation at 200 rpm for 30 seconds.

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

(Electron beam (EB) hardening 1)

Device: Electron beam irradiation device manufactured by Hamamatsu Photoelectric Co., Ltd.

Acceleration voltage: 70kV, tube current value: 4.0mA

Absorption line: 145kGy

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

Conveying speed (scanning speed during processing): 100mm/sec (200mm diameter substrate, 2 pieces/sec)

Processing temperature: 23℃

(EB hardening 2)

Device: Electron beam irradiation device manufactured by Hamamatsu Photoelectric Co., Ltd.

Acceleration voltage: 120kV, tube current value: 4.0mA

Absorption line: 145kGy

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

Conveying speed (scanning speed during processing): 100mm/sec (200mm diameter substrate, 2 pieces/sec)

Processing temperature: 23℃

(UV hardening)

Exposure (UV): 3,000mJ/cm ²

Temperature: 35℃

(Spectral evaluation)

Using a spectroscope (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.), the spectroscopic distribution of the film before the curing treatment and the spectroscopic coating after the curing treatment under the conditions of EB curing 1 were measured. As a result, no spectral change was observed before and after the curing treatment.

(Reliability of cured film)

The cured film cured under the conditions of EB curing 1 was subjected to temperature cycle test resistance and constant temperature and humidity test resistance by the same method as Test Example 1, and the reliability of the cured film was evaluated. As a result, there was no pattern peeling , Excellent reliability.

(Evaluation of color mixing)

Using a spectroscope (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.), the maximum transmittance T0 in the wavelength range of 600 nm to 700 nm was measured for the spectroscopic film before curing.

Then, on the red colored pattern produced by performing each curing treatment, a blue resist for color mixing evaluation (SB2000, manufactured by Fujifilm Electronic Materials Co., Ltd.) was spin-coated so that the film thickness after drying became 2 μm at 65° C. A heat treatment (pre-baking) was performed for 150 seconds.

Then, via a mask with a transfer pattern (pattern size: 100 μm×100 μm), using an i-ray stepper exposure device (FPA-3000i5+, manufactured by Canon (stock), NA/σ=0.63/0.65, focus (Offset = 0 μm), exposure was performed with an exposure amount of 800 mJ/cm ² .

Then, using AD-1200 (manufactured by Mikasa Co., Ltd.), an alkaline developing solution (tetramethylammonium hydroxide (TMAH) 0.3% by mass aqueous solution) was used to develop for 60 seconds by a coating method.

Then, pure water was used for the rinse treatment, and then dried at a high speed of 200 rpm for 30 seconds to form a blue colored pattern.

Then, with respect to the cured film (red colored pattern) after forming the blue colored pattern, the maximum transmittance T1 in the wavelength range of 600 nm to 700 nm was measured using a spectroscope (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.), and the maximum transmittance change was calculated ( △T=T0-T1).

In addition, the spectrum of the curing process of the red colored pattern and the spectrum after evaluation of the color mixing of the red colored pattern after the curing process under the conditions of EB curing 1 and UV curing are shown in FIG. 1.

[Table 4]

Based on the results, the test number 401, which is hardened under the conditions of EB hardening 1, can effectively suppress the mixing of other colors.

<Test Example 5>

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

Electron beam irradiation is performed under the following conditions.

Electron beam irradiation conditions

Device: Electron beam irradiation device manufactured by Hamamatsu Photoelectric Co., Ltd.

Accelerating voltage: 95kV, tube current value: 4.0mA

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

Conveying speed (scanning speed during processing): 100mm/sec (200mm diameter substrate, 2 pieces/sec)

Processing temperature: 23℃

In addition, 5 substrates were used for each processing condition. In addition, the numerical value in parentheses in the table is the defect rate.

A: No warpage, defect, cracking and discoloration on the treated substrate.

B: There is a crack or a defect in a part of the substrate.

C: There is cracking or warping on the substrate of 1 to 3 pieces.

D: There were cracks or warpage on 4 or more substrates.

The method of hardening the composition may include a hot plate/oven at 220° C. and electron beam irradiation. The damage of the substrates caused by these curing methods was evaluated (using five substrates).

As the results clearly show, even substrates that have warpage, defects, cracks, etc. during heat treatment will not have warpage, defects, or cracks during electron beam irradiation.

<Test Example 6>

[Preparation of Pigment Dispersion Liquid B-1]

Using 0.3 mm diameter zirconia beads, using a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Japan BEE)), the mixed liquid of the following composition was mixed and dispersed for 3 hours , Preparation of pigment dispersion B-1.

‧Mixed pigment (C.I. Pigment Red 254: C.I. Pigment Yellow 139=4:1 (mass ratio)) containing red pigment (C.I. Pigment Red 254) and yellow pigment (C.I. Pigment Yellow 139)‧‧‧11.8 parts by mass

‧Resin 1 (dispersant) (made by BYK Chemie, DISPERBYK-111) ‧‧‧9.1 parts by mass

‧Propylene glycol methyl ether acetate‧‧‧‧9.1 parts by mass

[Preparation of Pigment Dispersion Liquid B-2]

Using 0.3 mm diameter zirconia beads, using a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Japan BEE)), the mixed liquid of the following composition was mixed and dispersed for 3 hours , Preparation of pigment dispersion B-2.

‧Mixed pigments containing blue pigment (CI Pigment Blue 15:6) and purple pigment (CI Pigment Violet 23) (CI Pigment Blue 15:6: CI Pigment Violet 23=9:4 (mass ratio))‧‧‧12.6 Quality

‧Resin 1 (dispersant) (made 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 (the ratio of the repeating unit is Mohr ratio, Mw=14,000)

In addition, the resin 2 is an alkali-soluble resin.

[Chem 28]

[Preparation of active energy ray-curable composition]

After mixing the following compositions, it was filtered using a nylon filter with a pore size of 0.45 μm (manufactured by Pall Japan Co., Ltd., DFA4201NXEY) to prepare an active energy ray-curable composition.

(composition)

‧Pigment dispersion B-1‧‧‧‧46.5 parts by mass

‧Pigment Dispersion B-2‧‧‧37.1 parts by mass

‧Alkali soluble resin 1‧‧‧1.1 parts by mass

‧Free 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

‧Surface Active Agent 1‧‧‧4.2 parts by mass

‧ Polymerization inhibitor (p-methoxyphenol) ‧‧‧0.001 parts by mass

‧PGMEA‧‧‧7.8 parts by mass

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

[Chem 29]

‧Free radical polymerizable compound 1: the following structure (the mixture of the compound on the left and the compound on the right has a molar ratio of 7:3)

‧Silane coupling agent 1: the following structure

Photopolymerization initiator 1: the following structure

[化32]

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

[Manufacture of hardened film]

After applying the prepared active energy ray-curable composition to a glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning)), it was used A hot plate at 65°C was subjected to a heat treatment (pre-baking) for 120 seconds. The coating film thickness of the active energy ray-curable composition is adjusted so that the film thickness after prebaking becomes 2 μm.

Then, using an i-ray stepper exposure device (FPA-3000i5+, manufactured by Canon Co., Ltd., NA/σ=0.63/0.65, focus offset=0 μm), via having a transfer pattern (pattern size: 100 μm× 100 μm) mask, exposure at an exposure of 500 mJ/cm ² .

Then, using AD-1200 (manufactured by Mikasa Co., Ltd.), an alkaline developing solution (tetramethylammonium hydroxide (TMAH) 0.3% by mass aqueous solution) was used to develop for 60 seconds by a coating method.

Then, using pure water for rinsing treatment, and then by high-speed spin at 200rpm Turn to dry for 30 seconds.

Then, after curing treatment under any of the following conditions, an additional baking treatment was performed at 240°C for 5 minutes using a hot plate.

(EB hardening)

Device: Electron beam irradiation device manufactured by Hamamatsu Photoelectric Co., Ltd.

Acceleration voltage: 70kV, tube current value: 4.0mA

Absorption line: 145kGy

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

Conveying speed (scanning speed during processing): 100mm/sec (200mm diameter substrate, 2 pieces/sec)

Processing temperature: 23℃

(UV hardening)

Exposure (UV): 3,000mJ/cm ²

Temperature: 35℃

(Heat hardening)

Use an oven at 220°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 of 2 μm) was measured.

(Evaluation of the reliability of the cured film)

‧Temperature cycle test resistance

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

‧Temperature and humidity resistance

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

(Exterior)

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

A: No problem

B: Wrinkles are generated on the surface

As shown in the table, Test No. 601 which has been irradiated with an electron beam with an acceleration voltage of 10 kV or more and less than 100 kV can produce a cured film having excellent reliability equivalent to No. 603 which has been heat-cured. In addition, there was no wrinkle on the film after curing treatment and after additional baking, and the appearance was good.

On the other hand, the reliability of the test number 602 that has undergone UV curing deteriorates. Furthermore, wrinkles occurred in the film after the additional baking. Presumably it is: a table that only exposes the pattern The hardening of the surface is promoted, and the polymerization inside the pattern is insufficient. Therefore, due to the difference in film shrinkage between the surface and the inside due to the treatment at high temperature, wrinkles are generated on the surface.

<Test Example 7>

[Preparation of active energy ray-curable composition]

After mixing the following compositions, it was filtered using a nylon filter with a pore size of 0.45 μm (manufactured by Pall Japan Co., Ltd., DFA4201NXEY) to prepare an active energy ray-curable composition.

(composition)

‧Cationic polymerizable compound (EHPE 3150, manufactured by Daicel Chemical Industries) ‧‧‧4.0% by mass

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

‧Surface active agent 1‧‧‧0.1 mass%

‧Propylene glycol monomethyl ether acetate (PGMEA) ‧‧‧ 94.9% by mass

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

[Manufacture of hardened film]

Using the spin coating method, the active energy ray-curable composition produced as described above was applied to a glass substrate (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (trade name, manufactured by Corning) )) After the application, a 65°C hot plate was used for 120 seconds of heat treatment (pre-baking). The coating film thickness of the active energy ray-curable composition is adjusted so that the film thickness after prebaking becomes 0.1 μm.

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

(EB condition 1)

Acceleration voltage: 70kV, tube current value: 4.0mA

Absorption line: 145kGy

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

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

Processing temperature: 23℃

(EB condition 2)

Acceleration voltage: 50kV, tube current value: 2.6mA

Absorption line: 15kGy

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

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

Processing temperature: 23℃

(EB condition 3)

Acceleration voltage: 50kV, tube current value: 2.6mA

Absorption line: 30kGy

The gap between the substrate and the electron irradiation source: 10mm

Oxygen concentration ≦ 1000 volume ppm

Conveying speed (scanning speed during processing): 100mm/sec × 2 scans

Processing temperature: 23℃

(Solvent resistance)

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

A: Abnormality of film-free surface, and film thickness variation

B: There is an abnormality of the film surface, or there is a change in film thickness

(Evaluation of the reliability of the cured film)

‧Temperature cycle test resistance

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

‧Temperature and humidity resistance

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

As shown in the table, Test No. 701 to Test No. 703 to which an electron beam having an acceleration voltage of 10 kV or more and less than 100 kV has been irradiated can produce a cured film with excellent reliability.

Claims (30)

A method for manufacturing a hardened film, comprising: a step of irradiating an electron beam with an acceleration voltage of 10 kV or more and less than 100 kV to a layer of an active energy ray-curable composition possessed on a substrate, wherein all steps are generally below 100°C At a temperature, the cured film has an optical density of 1 or more for any wavelength in the range of 260 nm to 440 nm. A method for manufacturing a hardened film, comprising: a step of irradiating an electron beam with an acceleration voltage of 10 kV or more and less than 100 kV to a layer of an active energy ray-curable composition possessed on a substrate, wherein all steps are generally below 100°C At a temperature, the method of manufacturing the cured film further includes the step of exposing the layer of the active energy ray-curable composition, and the step of irradiating the electron beam after the step of exposing, and using ultraviolet rays To perform the exposure step. A method for manufacturing a cured film, comprising: a step of irradiating an electron beam with an acceleration voltage of 10 kV or more and less than 100 kV to a layer of an active energy ray-curable composition possessed on a substrate, wherein all the steps are generally below 100°C At a temperature, the method for manufacturing the cured film further includes: a step of exposing the active energy ray curable composition layer; and after the exposure step, the active energy ray curable composition The developed layer is subjected to a step of developing to form a pattern; and the step of irradiating the electron beam is performed after the step of forming the pattern. A method for manufacturing a hardened film, comprising: a step of irradiating an electron beam with an acceleration voltage of 10 kV or more and less than 100 kV to a layer of an active energy ray-curable composition possessed on a substrate, wherein all steps are generally below 100°C Under temperature To proceed, the substrate includes an organic semiconductor layer. The method for producing a cured film as described in any one of claims 1 to 4, wherein the active energy ray curable composition contains an alkali-soluble resin. The method for manufacturing a cured film according to any one of the first to third patent application ranges, wherein the substrate is a thermoplastic substrate including a thermoplastic resin having a glass transition temperature of 100° C. or lower. The method for manufacturing a cured film according to any one of the first to third patent application ranges, wherein the substrate is a glass substrate having a thickness of 0.5 mm or less. The method for manufacturing a cured film according to any one of claims 1 to 3, wherein the base material includes an organic semiconductor layer. The method for manufacturing a cured film according to any one of claims 1 to 3, wherein the substrate includes an organic semiconductor layer on the surface. The method for manufacturing a cured film as described in item 1 or item 4 of the patent application scope, which further includes a step of exposing the layer of the active energy ray curable composition, and performing the step after the step of exposing The steps of irradiating the electron beam are described. The method for manufacturing a cured film as described in item 1 or item 4 of the patent application scope, further comprising: a step of exposing the layer of the active energy ray curable composition; and after the step of exposing, The step of developing the layer of the active energy ray curable composition to form a pattern; and the step of irradiating the electron beam after the step of forming the pattern. The method for manufacturing a cured film as described in item 10 of the patent application range, wherein the step of exposing is performed using ultraviolet rays. The method for manufacturing a cured film according to any one of claims 1 to 4, wherein the active energy ray curable composition contains 0.01 in the solid content of the active energy ray curable composition Silane coupling agent with mass% to 5.0 mass%. The method for producing a cured film according to item 13 of the patent application range, wherein the active energy ray-curable composition contains a thermosetting resin. The method for producing a cured film according to any one of claims 1 to 4, wherein the active energy ray curable composition contains at least one selected from a color colorant and a black colorant. The method for manufacturing a cured film according to any one of claims 2 to 4, wherein the optical density of the cured film for any wavelength in the range of 260 nm to 440 nm is 1 or more. The method for manufacturing a cured film according to item 16 of the patent application range, wherein the minimum value of the optical density of the cured film in the wavelength range of 260 nm to 440 nm is 1 or more. The method for manufacturing a cured film as described in item 16 of the patent application range, wherein the optical density of the cured film at a wavelength of 365 nm is 1 or more. The method for producing a cured film according to any one of claims 1 to 4, wherein the active energy ray curable composition contains a photopolymerization initiator and a radical polymerizable compound. The method for producing a cured film according to any one of claims 1 to 4, wherein the active energy ray curable composition contains an acid generator and a cationic polymerizable compound. The method for manufacturing a cured film according to any one of claims 1 to 4, wherein the film thickness of the cured film is 0.1 μm to 45 μm. The method for manufacturing a cured film according to any one of the first to fourth patent application ranges, wherein the active energy ray-curable composition is applied to the substrate, followed by drying to form the active The layer of the energy ray hardening composition. The method for manufacturing a cured film as described in any one of claims 1 to 4 includes the step of vacuum drying. The method for manufacturing a cured film according to any one of claims 1 to 4 includes the following steps: the layer irradiated with electron beams is further heat-treated at a temperature of 100° C. or lower. The method for manufacturing a cured film according to item 24 of the patent application range, wherein the substrate is a thermoplastic resin substrate and is at a temperature below the glass transition temperature of the thermoplastic resin substrate and at a temperature below 100°C The step of heat treatment is performed. The method for manufacturing a cured film according to any one of claims 1 to 4, wherein the cured film is used for a solid-state imaging device. The method for manufacturing a cured film according to item 1 of the patent application range, wherein the active energy ray-curable composition contains 20% by mass or more and 80% by mass or less of the total solid content of the active energy ray-curable composition Colorant. The method for producing a cured film as described in item 1 of the patent application range, wherein the active energy ray-curable composition has a black colorant. The method for producing a cured film according to item 1 of the patent application range, wherein the active energy ray curable composition contains 20% by mass or more and 80% by mass or less of black relative to the total solid content of the active energy ray curable composition Colorant. A cured film obtained by using the method for producing a cured film as described in any one of claims 1 to 29.

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