KR102028938B1 - Manufacturing method of cured film, and cured film - Google Patents

Abstract

Provided are a method for producing a cured film and a cured film which can produce a cured film having excellent reliability by a low temperature process. As a manufacturing method of the cured film containing the process of irradiating the layer of the active energy ray curable composition on a base material with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV, it is performed at the temperature of 100 degrees C or less through all the processes.

Description

Manufacturing method of cured film, and cured film

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

In the manufacturing method of a cured film, in order to fully harden a curable composition, heat processing is performed. For example, a color filter is manufactured as follows. First, the curable composition (coloring composition) containing a coloring agent is applied on base materials, such as a glass base material, and a coloring composition layer is formed. Next, the coloring composition layer is exposed and developed to form a pattern. Subsequently, the patterned coloring composition layer is heat-treated (post-baked), and the coloring composition layer is fully hardened. In this way, a color filter is manufactured.

Moreover, the method of irradiating an electron beam to a curable composition and manufacturing a cured film is known (refer patent documents 1-5).

Patent Document 1: Japanese Patent Application Laid-Open No. 10-268515 Patent Document 2: Japanese Unexamined Patent Publication No. 2004-12843 Patent Document 3: Japanese Unexamined Patent Publication No. 2010-107928 Patent Document 4: Japanese Unexamined Patent Publication No. 2009-244689 Patent Document 5: Japanese Unexamined Patent Publication No. 2004-123802

Conventionally, the cured film was manufactured on the base material comprised from materials excellent in heat resistance, such as silicone.

In recent years, manufacturing a cured film on the base material inferior in heat resistance is calculated | required. In manufacturing a cured film on a base material inferior in heat resistance, it is preferable to manufacture a cured film by the low temperature process of 100 degrees C or less, for example, and to suppress thermal damage to a base material. However, when the cured film is produced by a low temperature process, after the temperature cycle test or the constant temperature and humidity test, the appearance abnormality is likely to occur, and problems such as large film thickness variation or large transmittance variation tend to occur. There existed a tendency for the reliability of a cured film to be inferior compared with the cured film manufactured through the heat processing at high temperature.

Therefore, the objective of this invention is providing the manufacturing method of the cured film which can manufacture the cured film excellent in reliability by a low temperature process, and a cured film.

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

As a manufacturing method of the cured film containing the process of irradiating the layer of the active-energy-ray-curable composition on a <1> base material with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV, the hardening performed at the temperature of 100 degrees C or less through all the processes. Method of Making Membranes.

The manufacturing method of the cured film as described in <1> in which a <2> active energy ray curable composition contains alkali-soluble resin.

The manufacturing method of the cured film as described in <1> or <2> whose <3> base material is a thermoplastic resin base material comprised from the thermoplastic resin whose glass transition temperature is 100 degrees C or less.

The manufacturing method of the cured film as described in <1> or <2> whose <4> base material is a glass base material of thickness 0.5mm or less.

The manufacturing method of the cured film as described in <1> or <2> in which a <5> base material contains an organic-semiconductor layer.

The <6> base material is a manufacturing method of the cured film as described in <1> or <2> which has an organic semiconductor layer on the surface.

The manufacturing method of the cured film in any one of <1>-<6> which further includes the process of exposing the layer of a <7> active energy ray curable composition, and performs the process of irradiating an electron beam after the process of exposing.

The process of exposing the layer of an <8> active-energy-ray-curable composition, and the process of exposing the layer of an active-energy-ray-curable composition after a process of exposing, and forming a pattern, The process of irradiating an electron beam is carried out. The manufacturing method of the cured film in any one of <1>-<6> performed after the process to form.

The manufacturing method of the cured film as described in <7> or <8> which performs the process to expose <9> using an ultraviolet-ray.

The manufacturing method of the cured film in any one of <1>-<9> in which a <10> active energy ray curable composition contains 0.01-5.0 mass% of silane coupling agents in solid content of an active energy ray curable composition.

The manufacturing method of the cured film as described in <10> in which a <11> active energy ray curable composition contains a thermosetting resin.

The manufacturing method of the cured film in any one of <1>-<11> containing the <12> active energy ray curable composition containing at least 1 sort (s) chosen from a chromatic colorant and a black colorant.

The manufacturing method of the cured film in any one of <1>-<12> whose <13> cured film is an optical density with respect to any wavelength in the range of wavelength 260-440 nm.

The manufacturing method of the cured film as described in <13> whose <14> cured film is a minimum of 1 or more of optical density in the range of wavelength 260-440 nm.

The manufacturing method of the cured film as described in <13> whose <15> cured film is 1 or more in optical density with respect to wavelength 365nm.

The <16> active energy ray curable composition is a manufacturing method of the cured film in any one of <1>-<15> containing a photoinitiator and a radically polymerizable compound.

The <17> active energy ray curable composition is a manufacturing method of the cured film in any one of <1>-<15> containing an acid generator and a cationically polymerizable compound.

The manufacturing method of the cured film in any one of <1>-<17> whose film thickness of a <18> cured film is 0.1-45 micrometers.

The manufacturing method of the cured film in any one of <1>-<18> which apply | coats an active energy ray curable composition on a <19> base material, and then dries to form the layer of an active energy ray curable composition.

The manufacturing method of the cured film in any one of <1>-<19> which has a process of performing a <20> vacuum drying.

The manufacturing method of the cured film in any one of <1>-<20> which further has a process of heat-processing at the temperature of 100 degrees C or less with respect to the layer which irradiated the <21> electron beam.

The <22> base material is a thermoplastic resin base material, The process of heat-processing is a manufacturing method of the cured film as described in <21> which is performed at the temperature below the glass transition temperature of a thermoplastic resin base material and 100 degrees C or less.

<23> Cured film obtained by the manufacturing method of the cured film in any one of <1>-<22>.

According to this invention, it became possible to provide the manufacturing method of the cured film which can manufacture the cured film excellent in reliability, and a cured film.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the spectrum of the cured film before and after mixed color evaluation.

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail.

In the description of "group (atom group)" in this specification, the description which is not describing substitution and unsubstitution means including what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In this specification, "light" means actinic light or radiation. "Active light" or "radiation" means, for example, the ultraviolet spectrum represented by the light spectrum of mercury lamp and excimer laser, extreme ultraviolet light (EUV light), X-ray, electron beam and the like.

In the present specification, "exposure" includes not only exposure using far ultraviolet rays, X-rays, EUV light, etc. represented by a mercury lamp and an excimer laser, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. .

The numerical range shown using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, "total solid content" means the total mass of the component remove | excluding the solvent from the whole composition of a composition.

In the present specification, "(meth) acrylate" represents both or both of acrylate and methacrylate, and "(meth) acryl" represents both or both of acryl and methacryl, "(Meth) allyl" represents both or all of allyl and metallyl, and "(meth) acryloyl" represents both or both of acryloyl and methacryloyl.

In the present specification, the term "process" is included in the term when not only an independent process but also a desired action of the process is achieved even when it cannot be clearly distinguished from other processes.

In this specification, a weight average molecular weight and a number average molecular weight are defined as polystyrene conversion value in a gel permeation chromatography (GPC) measurement.

<Manufacturing Method of Cured Film>

The manufacturing method of the cured film of this invention includes the process of irradiating the electron beam of the acceleration voltage of 10 kV or more and less than 100 kV to the layer of active energy ray curable composition (henceforth an active energy ray curable composition layer) which has on a base material. It is a manufacturing method of the cured film mentioned above, and the manufacturing method of a cured film is performed at the temperature of 100 degrees C or less through all the processes.

According to the present invention, even if the active energy ray-curable composition layer is irradiated with an electron beam of an accelerating voltage of 10 kV or more and less than 100 kV, reliability is achieved even at a low temperature (hereinafter referred to as a low temperature process) of 100 ° C or lower through the entire process. Excellent cured film can be manufactured.

In addition, in this invention, "to carry out at the temperature of 100 degrees C or less through the whole process" means performing the whole process of hardening | curing an active-energy-ray-curable composition layer and forming a cured film at the temperature of 100 degrees C or less, and hardening it. Each step of the film production step is performed at a temperature of 100 ° C. or less, respectively. That is, when the manufacturing process of a cured film contains another process other than the process of irradiating an said electron beam, another process is also performed at the temperature of 100 degrees C or less. For example, when it has a process of forming an active energy ray curable composition layer further on a base material, the process of forming an active energy ray curable composition layer is also performed at 100 degrees C or less. Moreover, when it has a process to expose further about the active energy ray curable composition layer on a base material, the process of exposing is also performed at 100 degrees C or less. Moreover, when it has a process of forming a pattern with respect to the active energy ray curable composition layer on a base material, the process of forming a pattern is also performed at the temperature of 100 degrees C or less. Moreover, when it has further the process of performing post-processing, such as heat processing, with respect to the active energy ray curable composition layer after electron beam irradiation, post-processing is also performed at the temperature of 100 degrees C or less.

Moreover, after forming a cured film, dicing (dividing into a chip | tip), bonding, etc. may be performed further, but the process after cured film formation is not included in the "all process" in this invention. That is, you may perform the process after forming a cured film at the temperature exceeding 100 degreeC. For example, when a thin glass substrate is used as the substrate, cracking or warping may occur in the substrate when the cured film is formed at a temperature exceeding 100 ° C, even if heated to a temperature exceeding 100 ° C after dicing. This is because cracking, warping, or the like is unlikely to occur.

Hereinafter, each process is demonstrated in order about the manufacturing method of the cured film of this invention.

An active energy ray curable composition layer is formed on a base material using an active energy ray curable composition. In addition, an active energy ray curable composition is mentioned later.

As a base material, the base material comprised from glass, silicone, resin, etc. are mentioned, for example. As glass, the glass used for optical instruments and display apparatuses, such as the Eagle series of the alkali free glass of Corning Corporation, 1737, the glass in which the organic layer which disperse | distributed or knead | mixed or kneaded the pigment | dye which has UV blocking function or infrared rays blocking function is also formed Inclusive). As the resin, for example, polyethylene, polypropylene, vinyl chloride, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, acryl, polyvinyl alcohol, Vinylidene chloride, polycarbonate, polyamide, polyacetal, polybutylene terephthalate, a fluororesin, and the like, and one or two or more thereof can be used in combination. On these base materials, organic semiconductor layers, such as an organic light emitting layer and an organic photoelectric conversion layer, etc. may be formed. As an organic semiconductor, an organic electroluminescent (OLED), an organic field effect transistor (OFET), an organic solar cell (OPV), etc. are mentioned. Moreover, in this invention, an organic semiconductor layer can also be used as a base material.

Although the film thickness of a base material changes with a use and a material, the thickness of a general base material can be applied.

According to the present invention, since a cured film can be formed even with respect to a substrate having poor heat resistance, the substrate is particularly effective for a substrate having low heat resistance. As a base material with low heat resistance, the glass base material with a thickness of 0.5 mm or less, a thermoplastic resin base material, the base material (preferably the base material which has an organic semiconductor layer on the surface), etc. are mentioned, for example.

Also in the said thermoplastic resin base material, the effect of this invention is remarkable in the case of the base material comprised from the thermoplastic resin whose glass transition temperature is 95 degrees C or less, for example. In particular, in a flexible substrate, the thermoplastic resin whose glass transition temperature is 90 degrees C or less is used more. Especially recently, it is especially preferable that it is 70 degrees C or less whose glass transition temperature is lower. The lower limit of the glass transition temperature of the thermoplastic resin is not particularly limited. For example, it can also be above normal temperature (23 degreeC). Moreover, the temperature below normal temperature can also be made into a lower limit. For example, it may be 0 degreeC or more, may be -50 degreeC or more, may be -100 degreeC or more, and may be -150 degreeC or more.

In addition, in this invention, when a thermoplastic resin has a glass transition temperature of 2 or more, let the lower temperature be the value of the glass transition temperature in this invention.

0.5 mm or less is preferable and, as for the film thickness of the said glass base material, 0.3 mm or less is more preferable. The lower limit is not particularly limited, but may be 0.1 mm or more.

As a method of applying the active energy ray-curable composition to the substrate, various methods such as slit coating, ink jet method, rotary coating, cast coating, roll coating, screen printing, spray coating and the like can be used. It is preferable to adjust the application amount of an active energy ray curable composition so that the film thickness after drying may be 0.1-45 micrometers. 44 micrometers or less are more preferable, as for an upper limit, 43 micrometers or less are more preferable, and 40 micrometers or less are especially preferable. As for a minimum, 0.2 micrometer or more is more preferable, for example.

In this invention, you may dry about the active energy ray curable composition layer formed on the base material. Drying includes normal temperature drying, heat drying, vacuum drying, and the like, and vacuum drying is preferable for the reasons of drying speed and drying at low temperature.

It is preferable to perform the said vacuum drying on the conditions of 0.02 PaG or more of vacuum degrees, and the temperature of 100 degrees C or less. The vacuum degree is more preferably 0.05 PaG or more, and even more preferably 0.09 PaG or more. The higher the degree of vacuum, the faster the drying rate and the shorter the drying time. As for temperature conditions, 70 degrees C or less is more preferable. A minimum may be 23 degreeC or more, for example, and it may be 30 degreeC or more. 30 second-1 hour are preferable, as for drying time, 1 minute-30 minutes are more preferable, and 2 minutes-20 minutes are more preferable.

It is preferable to perform the said heat drying at 100 degrees C or less, 80 degrees C or less is more preferable, and 70 degrees C or less is more preferable. The lower limit can be 23 degreeC or more, for example. 30 second-1 hour are preferable, as for a heat time, 1 minute-30 minutes are more preferable, and 2 minutes-20 minutes are more preferable.

Moreover, drying may be performed just before the process of irradiating an electron beam mentioned later, and may be performed after the process of irradiating an electron beam. Moreover, you may perform before the image development process mentioned later, and you may carry out after image development process.

In this invention, you may expose to the active energy ray curable composition layer formed on the base material. Exposure may be whole-surface exposure, and you may expose in pattern shape through a mask.

For example, pattern exposure can be performed by exposing the active energy ray curable composition layer formed on the base material through the mask which has a predetermined | prescribed mask pattern using exposure apparatuses, such as a stepper. Thereby, an exposure part can be hardened.

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

When exposing an active energy ray curable composition layer to a pattern shape, it is preferable to develop and remove an unexposed part, and to form a pattern. The development removal of an unexposed part can be performed using a developing solution. Thereby, the active energy ray curable composition layer of an unexposed part elutes to a developing solution, and only the photocured part remains.

As a developing solution, alkaline developing solution which does not damage a base material is preferable.

As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. As for image development time, 20 to 180 second is preferable.

As an alkali agent used for a developing solution, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide And organic alkaline compounds such as benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo [5.4.0] -7-undecene.

Moreover, you may use an inorganic alkaline compound as an alkali chemicals used for a developing solution. As an inorganic alkaline compound, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, etc. are preferable, for example.

The alkaline aqueous solution which diluted these alkaline agents with the pure water so that a density | concentration may be 0.001-10 mass%, Preferably 0.01-1 mass% is used suitably as a developing solution.

Moreover, you may use surfactant for a developing solution. As an example of surfactant, surfactant demonstrated by the active energy ray curable composition mentioned later is mentioned, A nonionic surfactant is preferable. When a developing solution contains surfactant, 0.001-2.0 mass% is preferable with respect to the total mass of a developing solution, and its 0.01-1.0 mass% is more preferable.

When using the developing solution which consists of such alkaline aqueous solution, it is generally preferable to wash (rinse) with pure water after image development.

After washing, for example, after spin drying, the drying is preferably performed.

Next, an electron beam is irradiated to the active energy ray curable composition layer on a base material. When only the said exposure is performed and the said image development is not performed with respect to an active energy ray curable composition layer, it is preferable to irradiate an electron beam after exposure. Moreover, when pattern formation is performed (in the case of exposure and image development) with respect to an active energy ray curable composition layer, it is preferable to irradiate an electron beam after pattern formation of an active energy ray curable composition layer.

The acceleration voltage of an electron beam is 10 kV or more and less than 100 kV. 15 kV or more is preferable, 20 kV or more is more preferable, and 30 kV or more of a minimum is more preferable. 99 kV or less is preferable, as for an upper limit, 98 kV or less is more preferable, and 97 kV or less is more preferable. If the acceleration voltage of an electron beam is the said range, the cured film excellent in reliability can be manufactured. Furthermore, the external appearance and spectral characteristics of the cured film obtained are also favorable.

As for the tube current of an electron beam, 0.01-10 mA is preferable. If the tube current of an electron beam is the said range, the electron beam density emitted from a filament will fully be maintained, and the cured film excellent in reliability can be manufactured. Furthermore, the external appearance and spectral characteristics of the cured film obtained are also favorable. It is preferable that the tube current of an electron beam is 0.01 mA or more, 0.1 mA or more is more preferable, and 1 mA or more is more preferable. It is preferable that an upper limit is 10 mA or less, 9 mA or less is more preferable, 8 mA or less is more preferable. It is preferable that the setting of the tube current is larger as long as the durability of the filament is maintained.

It is preferable to irradiate an electron beam in the range in which the absorbed dose of the electron beam of a cured film becomes 10 kGy or more. If the absorbed radiation amount of an electron beam is the said range, the cured film excellent in reliability can be manufactured. As for the absorbed dose of an electron beam, 15 kGy or more is more preferable, and 20 kGy or more is more preferable.

In the process of irradiating an electron beam, processing temperature (temperature in an apparatus) is 100 degrees C or less, 80 degrees C or less is preferable, and 70 degrees C or less is more preferable. The lower limit may be, for example, 10 ° C or higher, may be 15 ° C or higher, or may be 20 ° C or higher.

Moreover, it is preferable to perform irradiation of an electron beam in the atmosphere whose oxygen concentration is 3000 volume ppm or less. As for oxygen concentration, 1000 volume ppm or less is more preferable.

Moreover, 1-30 mm is preferable and, as for the clearance of a base material and an electron irradiation source, 5-10 mm is more preferable.

In the manufacturing method of the cured film of this invention, you may heat-process at the temperature of 100 degrees C or less with respect to the active energy ray curable composition layer which irradiated the electron beam. By heat processing, drying of a cured film can be accelerated | stimulated and the curability of a cured film can be stabilized.

As for heat processing temperature, the temperature which exceeds 23 degreeC-100 degrees C or less are preferable, for example. 80 degrees C or less is more preferable, and 70 degrees C or less of an upper limit is more preferable. Moreover, when a thermoplastic resin base material is used as a base material, the upper limit of heat processing temperature is 100 degrees C or less temperature, and the temperature below the glass transition of a thermoplastic resin base material is preferable. In addition, when the glass transition temperature of a thermoplastic resin base material exceeds 100 degreeC, the upper limit of heat processing temperature is 100 degreeC.

The heat treatment is a continuous or batch method using the heating means such as a hot plate, a convection oven (hot air circulation dryer), a high frequency heater, and the like to form the active energy ray curable composition layer after electron beam irradiation under the above conditions. I can do it.

Moreover, you may vacuum-dry instead of heat processing. Moreover, you may use together heat processing and vacuum drying.

<Active energy ray curable composition>

Next, the active energy ray curable composition used by the manufacturing method of the cured film of this invention is demonstrated.

In the present invention, any of the active energy ray curable compositions can be preferably used as long as the composition is cured by irradiation of active energy rays. Here, an active energy ray means what can give the energy which can generate a starting species in a composition by the irradiation, For example, (alpha) rays, (gamma) rays, X rays, an ultraviolet-ray, a visible ray, an electron beam Etc. can be mentioned.

<< resin >>

It is preferable that an active energy ray curable composition contains resin. Resin is mix | blended with the use which disperse | distributes a pigment etc. in a composition, and the use of a binder, for example. In addition, resin mainly used in order to disperse a pigment etc. is also called a dispersing agent. However, such a use of resin is an example and can also be used for purposes other than such a use.

As for the weight average molecular weight (Mw) of resin, 2,000-2,000,000 are preferable. 1,000,000 or less are more preferable, and, as for an upper limit, 500,000 or less are more preferable. As for a minimum, 3,000 or more are more preferable, and 5,000 or more are more preferable.

As the resin, (meth) acrylic resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyaryl And ethylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and siloxane resins. You may use individually by 1 type from these resin, and may mix and use 2 or more types.

In an active energy ray curable composition, it is preferable that it is 10-80 mass% of the total solid of an active energy ray curable composition, and, as for content of resin, it is more preferable that it is 20-60 mass%. The active energy ray curable composition may include only one type of resin, or may include two or more types. When it contains two or more types, it is preferable that the total amount exists in said range.

<<< alkali soluble resin >>>

It is preferable that an active energy ray curable composition contains alkali-soluble resin as resin. By containing alkali-soluble resin, developability and pattern formation property improve. Moreover, alkali-soluble resin can also be used as a dispersing agent and a binder.

Although it does not specifically determine as molecular weight of alkali-soluble resin, It is preferable that weight average molecular weights (Mw) are 5000-100,000. Moreover, it is preferable that number average molecular weight (Mn) is 1000-20,000.

As alkali-soluble resin, a linear organic high molecular polymer may be sufficient and it can select suitably from resin which has group which promotes alkali dissolution in a molecule | numerator (preferably an acryl-type copolymer and the molecule which has a styrene-type copolymer as a main chain).

As alkali-soluble resin, from a heat resistant viewpoint, polyhydroxy styrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acryl / acrylamide copolymer resin are preferable, and acrylic resin is preferable from a developability control viewpoint. , Acrylamide resins and acryl / acrylamide copolymer resins are preferred.

Examples of the group that promotes alkali dissolution (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, but are soluble in an organic solvent and developable by a weak alkaline aqueous solution. It is preferable and (meth) acrylic acid is mentioned as a especially preferable thing. 1 type of these acid groups may be sufficient, and 2 or more types may be sufficient as them.

A well-known radical polymerization method can be applied to manufacture of alkali-soluble resin, for example. The polymerization conditions such as the temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and conditions can also be determined experimentally.

As alkali-soluble resin, the polymer which has a carboxylic acid in a side chain is preferable, A methacrylic acid copolymer, an acrylic acid copolymer, itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, a novolak Alkali-soluble phenol resins, such as a mold resin, Acidic cellulose derivative which has a carboxyl group in a side chain, resin which added an acid anhydride to the polymer which has a hydroxyl group, etc. are mentioned. In particular, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is suitable as alkali-soluble resin. As another monomer copolymerizable with (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , Pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate And cyclohexyl (meth) acrylate. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, and N-vinylpyrroly. DON, tetrahydrofurfuryl methacrylate, a polystyrene macromonomer, a polymethyl methacrylate macromonomer, etc. are mentioned. As another monomer, the N-position substituted maleimide monomer of Unexamined-Japanese-Patent No. 10-300922, for example, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

Moreover, in order to improve the crosslinking efficiency of an active energy ray curable composition layer, you may use alkali-soluble resin which has a polymeric group. As a polymerizable group, a (meth) allyl group, a (meth) acryloyl group, etc. are mentioned. As alkali-soluble resin which has a polymeric group, alkali-soluble resin etc. which contained the polymeric group in the side chain are useful. The alkali-soluble resin having a polymerizable group may be a thermosetting resin or a photocurable resin.

As alkali-soluble resin containing a polymeric group, Diamond NR series (made by Mitsubishi Rayon Co., Ltd.), Photomer6173 (COOH containing polyurethane acrylic acid oligomer, Diamond Shamrock Co., Ltd. make), biscot R-264, KS resist 106 (all made by Osaka Yuki Chemical Co., Ltd.), cyclomer P series (e.g. ACA230AA, thermosetting resin), Plascel CF200 series (all made by Daicel Co., Ltd.), Ebecryl3800 (Diesel Yushibi ( Ltd.) and Acrycure RD-F8 (made by Nippon Shokubai Co., Ltd.) etc. are mentioned.

Benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / as alkali-soluble resin The multicomponent copolymer which consists of (meth) acrylic acid / another monomer can be used preferably. Moreover, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacryl which copolymerized 2-hydroxyethyl (meth) acrylate and is described in Unexamined-Japanese-Patent No. 7-140654. Acid Copolymer, 2-hydroxy-3-phenoxypropylacrylate / polymethylmethacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl Methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

Moreover, as a commercial item, FF-426 (made by Fujikura Kasei Co., Ltd.) etc. can also be used, for example.

Alkali-soluble resin is a polymer obtained by polymerizing a monomer component containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable to include.

[Formula 1]

In formula (ED1), R <^1> and R <^2> respectively independently represents the hydrogen atom or the C1-C25 hydrocarbon group which may have a substituent.

[Formula 2]

In formula (ED2), R represents a hydrogen atom or a C1-C30 organic group. As a specific example of Formula (ED2), description of Unexamined-Japanese-Patent No. 2010-168539 can be referred.

Although there is no restriction | limiting in particular as C1-C25 hydrocarbon group which may have substituents represented by R <^1> and R <^2> in formula (ED1), For example, methyl, ethyl, n-propyl, isopropyl, n-butyl Linear or branched alkyl groups such as isobutyl, tert-butyl, tert-amyl, stearyl, lauryl and 2-ethylhexyl; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecaneyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; Alkyl group substituted by alkoxy, such as 1-methoxyethyl and 1-ethoxyethyl; Alkyl groups substituted by aryl groups, such as benzyl, etc. are mentioned. Among these, substituents of primary or secondary carbon, which are difficult to be released by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl, etc., are preferable in terms of heat resistance.

As a specific example of an ether dimer, Paragraph No. 0317 of Unexamined-Japanese-Patent No. 2013-29760 can be referred, for example, This content is integrated in this specification. One type of ether dimer may be sufficient and 2 or more types may be sufficient as it.

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

[Formula 3]

In formula (X), R <_1> represents a hydrogen atom or a methyl group, R <_2> represents a C2-C10 alkylene group, R <_3> has a C1-C20 which may contain a hydrogen atom or a benzene ring. An alkyl group is shown. n represents the integer of 1-15.

In said Formula (X), 2-3 are preferable as carbon number of the alkylene group of R <_2> . Moreover, although carbon number of the alkyl group of R <_3> is 1-20, Preferably it is 1-10, and the alkyl group of R <_3> may also contain a benzene ring. As an alkyl group containing the benzene ring represented by R <_3> , a benzyl group, 2-phenyl (iso) propyl group, etc. are mentioned.

As a specific example of alkali-soluble resin, the following is mentioned.

[Formula 4]

As alkali-soluble resin, Paragraph No. 0558 of Unexamined-Japanese-Patent No. 2012-208494-description of 071 (paragraph No. 0685 of the corresponding US patent application publication 2012/0235099) can refer to description, These content is referred to this specification. It is used for.

Furthermore, Paragraph No. 0029 of Unexamined-Japanese-Patent No. 2012-32767-the copolymer (B) of 0063, and alkali-soluble resin used by the Example, Paragraph No. 0088 of Unexamined-Japanese-Patent No. 2012-208474, and the binder resin of 0098, and Binder resins used in Examples, Paragraph Nos. 0022 to 0032 of JP-A-2012-137531, Binder resins used in Examples, and Paragraph Nos. 0132 to 0431 of JP-A-2013-024934 Paragraph No. 0092-0098 of Unexamined-Japanese-Patent No. 2011-242752, Binder Resin used by the Example, and Paragraph No. 0030-00072 of Unexamined-Japanese-Patent No. 2012-032770 in the described binder resin and the binder resin used by the Example The binder resin described can also be used. These contents are incorporated in this specification.

As for the acid value of alkali-soluble resin, 30-500 mgKOH / g is preferable. As for a minimum, 50 mgKOH / g or more is more preferable, and 70 mgKOH / g or more is more preferable. 400 mgKOH / g or less is more preferable, 200 mgKOH / g or less is more preferable, 150 mgKOH / g or less is still more preferable, and 120 mgKOH / g or less is still more preferable.

As for content of alkali-soluble resin, 0.1-20 mass% is preferable with respect to the total solid of an active energy ray curable composition. 0.5 mass% or more is more preferable, 1 mass% or more is more preferable, 2 mass% or more is still more preferable, 3 mass% or more is especially preferable. 12 mass% or less is more preferable, and, as for an upper limit, 10 mass% or less is more preferable. The active energy ray curable composition may include only one type of alkali-soluble resin or may include two or more types. When it contains two or more types, it is preferable that the total amount exists in said range.

<<< dispersant >>>

An active energy ray curable composition can contain a dispersing agent as resin.

It is preferable that resin used as a dispersing agent contains the repeating unit which has an acidic radical. By containing the repeating unit which has an acidic radical, when the pattern is formed by photolithography, the residue which generate | occur | produces on a base can be reduced more.

The repeating unit which has an acidic radical can be comprised using the monomer which has an acidic radical. As a monomer which has an acidic radical, the vinyl monomer which has a carboxyl group, the vinyl monomer which has a sulfonic acid group, the vinyl monomer which has a phosphoric acid group, etc. are mentioned.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimers, and the like. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride, succinic anhydride and cyclohexanedicarboxylic acid anhydride, ω-carboxy-poly Caprolactone mono (meth) acrylate etc. can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, a citraconic acid anhydride, as a precursor of a carboxyl group. Especially, from the viewpoint of the image development removal property of an unexposed part, monomers which have hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and cyclic | annulars, such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexane dicarboxylic acid anhydride, etc. Addition reactants with anhydrides are preferred.

2-acrylamide-2-methylpropane sulfonic acid etc. are mentioned as a vinyl monomer which has a sulfonic acid group.

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

Moreover, as a repeating unit which has an acidic radical, description of Paragraph No. 0067-0069 of Unexamined-Japanese-Patent No. 2008-165059 can be referred, and this content is integrated in this specification.

Moreover, it is preferable that resin used as a dispersing agent is a graft copolymer. Since the graft copolymer has affinity with the solvent by the graft chain, it is excellent in dispersibility of the pigment and dispersion stability after aging. Moreover, since a composition has affinity with polymeric compound, alkali-soluble resin, etc. by presence of a graft chain, it can make it hard to produce a residue by alkali image development.

In addition, in this invention, a graft copolymer means resin which has a graft chain. In addition, a graft chain shows from the origin of the main chain of a polymer to the terminal of the group branching from a 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 excluding the hydrogen atom.

Moreover, it is preferable that the number of atoms except the hydrogen atom per graft chain is 40-10,000, 50-2,000 are more preferable, and 60-500 are more preferable.

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. Especially, (meth) acrylic resin is preferable.

As a graft chain of a graft copolymer, in order to improve the interaction property of a graft site and a solvent, and to improve dispersibility by this, it is preferable that it is a graft chain which has poly (meth) acryl, polyester, or a polyether, and is poly It is more preferable that it is a graft chain which has an ester or a polyether.

It is preferable that a graft copolymer contains the repeating unit which has a graft chain in mass conversion in 2 to 90 mass% with respect to the gross copolymer mass, and it contains in the range of 5 to 30 mass%. More preferred. If content of the repeating unit which has a graft chain is in this range, the dispersibility of a coloring agent is favorable.

As a macromonomer used when producing a graft copolymer by radical polymerization, a well-known macromonomer can be used, Macromonomer AA-6 (Methyl polymethacrylate whose terminal group is a methacryloyl group) by Toagosei Co., Ltd. , AS-6 (polystyrene having terminal methacryloyl group), AN-6S (copolymer of styrene having terminal methacryloyl group and acrylonitrile), AB-6 (poly terminal having end methacryloyl group) Butyl acrylate), Plascel FM5 (ε-caprolactone 5 molar equivalents adduct of 2-hydroxyethyl methacrylate) made by Daicel, FA10L (ε-caprolactone 10 molar equivalents of 2-hydroxyethyl acrylate) Additives), and polyester macromonomers described in JP-A 2-272009.

In this invention, the graft copolymer containing the repeating unit represented by either of following formula (1)-formula (4) can also be used as resin. These graft copolymers can be used particularly suitably as a dispersing agent of a black pigment.

[Formula 5]

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

In Formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ preferably each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each independently represent a hydrogen atom or a methyl group from the viewpoint of synthetic restrictions. More preferably, a methyl group is especially preferable.

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

[Formula 6]

In Formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. Although the structure of an organic group is not specifically limited, Specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group, etc. are mentioned. Can be mentioned. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , in particular, from the viewpoint of improving dispersibility, one having a three-dimensional repulsion effect is preferable, and each independently an alkyl group or alkoxy group having 5 to 24 carbon atoms Especially, especially, a C5-C24 branched alkyl group, a C5-C24 cyclic alkyl group, or a C5-C24 alkoxy group are especially preferable especially especially. In addition, the alkyl group contained in the alkoxy group may be any of linear, branched or cyclic.

In Formula (1)-Formula (4), n, m, p, and q are the integers of 1-500 each independently.

In addition, in Formula (1) and Formula (2), j and k represent the integer of 2-8 each independently. In j and k in Formula (1) and Formula (2), the integer of 4-6 is preferable from a viewpoint of dispersion stability and developability, and 5 is the most preferable.

In formula (3), R <^3> represents a branched or linear alkylene group, a C1-C10 alkylene group is preferable, and a C2-C3 alkylene group is more preferable. When p is 2-500, two or more R <^3> may mutually be same or different.

In formula (4), R <^4> represents a hydrogen atom or monovalent organic group, and it does not have a structural limitation in particular as this monovalent organic group. As R ⁴ , Preferably, a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group are mentioned, More preferably, they are a hydrogen atom or an alkyl group. When R <^4> is an alkyl group, as an alkyl group, a C1-C20 linear alkyl group, a C3-C20 branched alkyl group, or a C5-C20 cyclic alkyl group is preferable, A C1-C20 linear alkyl group is more preferable, More preferably, a C1-C6 linear alkyl group. In Formula (4), when q is 2-500, X <^5> and R <^4> which exists in multiple in a graft copolymer may be mutually same or different.

As a repeating unit represented by Formula (1), it is more preferable that it is a repeating unit represented by following formula (1A) from a viewpoint of dispersion stability and developability.

Moreover, as a repeating unit represented by Formula (2), it is more preferable that it is a repeating unit represented by following formula (2A) from a viewpoint of dispersion stability and developability.

Moreover, as a repeating unit represented by Formula (3), it is more preferable that it is a repeating unit represented by following formula (3A) or formula (3B) from a viewpoint of dispersion stability and developability.

[Formula 7]

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

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

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

Moreover, it is also preferable that the graft copolymer mentioned above has a hydrophobic repeating unit other than the repeating unit represented by Formula (1)-(4) mentioned above. However, in this invention, a hydrophobic repeating unit is a repeating unit which does not have an acidic radical (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

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

The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides a value of "calculated logP" calculated by Hansch, Leo's fragment approach (see literature below). The fragment approach is based on the chemical structure of the compound, and the logP value of the compound is estimated by dividing the chemical structure into partial structures (fragments) and summing the logP contributions assigned 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.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., P. 295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP means the common logarithm of the partition coefficient P (Partition Coefficient), and is a physical property value indicating quantitatively how an organic compound is distributed in the equilibrium of an oil (generally 1-octanol) and water, It is represented by the following formula.

logP = log (Coil / Cwater)

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

When the value of logP is positively greater with 0 between them, the usefulness increases, and when the negative value increases, the water solubility increases, which has a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for evaluating the hydrophilicity of.

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

[Formula 8]

In said formula (i)-(iii), R <^1> , R <^2> and R <^3> respectively independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or carbon number 1-; The alkyl group which is 6 (for example, methyl group, an ethyl group, a propyl group, etc.) is shown.

R ¹ , R ² , and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. It is particularly preferable that R ² and R ³ are hydrogen atoms.

X represents an oxygen atom (-O-) or an imino group (-NH-), and it is preferable that it is an oxygen atom.

L is a single bond or a divalent linking group. As a bivalent coupling group, a bivalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a bivalent aromatic group (for example, aryl Benzene group, substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ^31- , where R ³¹ is Aliphatic group, aromatic group or heterocyclic group), carbonyl group (-CO-), or a combination thereof.

L is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. As for the oxyalkylene structure, it is more preferable that it is an oxyethylene structure or an oxypropylene structure. In addition, L may include the polyoxyalkylene structure which repeats two or more oxyalkylene structures. As a polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) _n- , and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

As Z, an aliphatic group (for example, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (for example, arylene group, substituted arylene group), heterocyclic group, oxygen atom (-O-), sulfur atom ( -S-), imino group (-NH-), substituted imino group (-NR ^31- , wherein R ³¹ is an aliphatic group, aromatic group or heterocyclic group), carbonyl group (-CO-), or a combination thereof Can be mentioned.

The aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are more preferable. The aliphatic group further includes a ring-assembled hydrocarbon group and a temporarily exchangeable hydrocarbon group, and examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, a 4-cyclohexylphenyl group, and the like. As a crosslinkable hydrocarbon ring, for example, pinene, bonane, nopineine, norbornene, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring Tricyclic hydrocarbons such as bicyclic hydrocarbon rings, homobledine, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, etc. And tetracyclic hydrocarbon rings such as tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like. . Moreover, as a temporary exchange type hydrocarbon ring, a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenal Condensed rings in which a plurality of 5- to 8-membered cycloalkane rings such as len rings are condensed are also included. The aliphatic group is more preferably a saturated aliphatic group than the unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

6-20 are preferable, as for the carbon atom number of an aromatic group, 6-15 are more preferable, and 6-10 are more preferable. Moreover, the aromatic group may have a substituent. As an example of a substituent, a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group are mentioned. However, the aromatic group does not have an acid group as a substituent.

It is preferable that a heterocyclic group has a 5-membered ring or a 6-membered ring as a heterocyclic ring. Other heterocycles, aliphatic rings or aromatic rings may be condensed on the heterocycles. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), a substituted imino group (= NR ³² , wherein R ³² is an aliphatic group, Aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups. However, the heterocyclic group does not have an acid group as a substituent.

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

The monomer represented by the said general formula (i) is R <^1> , R <^2> and R <^3> is a hydrogen atom or a methyl group, L is a bivalent coupling group containing a single bond or an alkylene group, or an oxyalkylene structure, X is oxygen Preference is given to compounds which are atoms or imino groups and Z is an aliphatic group, a heterocyclic group or an aromatic group. As for the monomer represented by the said Formula (ii), the compound whose 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 is preferable. As for the monomer represented by said formula (iii), the compound in which R <^4> , R <^5> and R <^6> is a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.

As an example of the typical compound represented by Formula (i)-(iii), the radically polymerizable compound chosen from acrylic acid ester, methacrylic acid ester, styrene, etc. is mentioned. Moreover, as an example of a compound represented by Formula (i)-(iii), Paragraph No. 0089 of Unexamined-Japanese-Patent No. 2013-249417-the compound of 0093 can be referred to, and this content is integrated in this specification.

In the graft copolymer, the hydrophobic repeating unit is preferably contained in the range of 10 to 90% by mass with respect to the total mass of the graft copolymer in terms of mass, and more preferably contained in the range of 20 to 80% by mass. desirable. When content is the said range, sufficient pattern formation is obtained.

The above-mentioned graft copolymer is a functional group (for example, an acid group, a basic group, a coordinating group, a reactive group, etc.) capable of forming an interaction with a pigment or the like, in addition to the repeating units represented by the formulas (1) to (4) described above. It is preferable to include the repeating unit having a).

As said acid group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group etc. are mentioned, for example, Preferably it is at least 1 sort (s) of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, Especially preferably, coloring agents, such as a black pigment, It is a carboxylic acid group with good adsorption power to and high dispersibility.

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

Although the graft copolymer may or may not contain the repeating unit which has an acidic radical, when it contains, content of the repeating unit which has an acidic radical is 5-80 mass% with respect to the gross mass of a graft copolymer in mass conversion. It is preferable, More preferably, it is 10-60 mass%.

As said basic group, a primary amino group, a secondary amino group, a tertiary amino group, the heterocyclic ring containing an N atom, an amide group, etc. are mentioned, for example, The adsorption | suction power with respect to a coloring agent is especially preferable, and also It is a tertiary amino group with high dispersibility. The graft copolymer may have one kind or two or more kinds of these basic groups.

Although the graft copolymer may or may not contain the repeating unit which has a basic group, When it contains, content of the repeating unit which has a basic group is a mass conversion, Preferably it is 0.01-50 with respect to the gross mass of a graft copolymer. It is mass%, More preferably, it is 0.01-30 mass% from a viewpoint of developability inhibition suppression.

As said coordination group and reactive functional group, an acetylacetoxy group, a trialkoxy silyl group, an isocyanate group, an acid anhydride, an acid chloride, etc. are mentioned, for example. Especially preferred is an acetylacetoxy group having good adsorption power to the colorant and high dispersibility. The graft copolymer may have one kind or two or more kinds of these groups.

The graft copolymer may or may not contain a repeating unit having a coordinating group or a repeating unit having a reactive group, but when it is contained, the content of these repeating units is, in terms of mass, the total mass of the graft copolymer. It is 10-80 mass% with respect to, More preferably, it is 20-60 mass% from a viewpoint of developability inhibition suppression.

When the graft copolymer has a functional group capable of forming an interaction with the pigment other than the graft chain, how these functional groups are introduced is not particularly limited, but the graft copolymer is represented by the following formulas (iv) to (vi) It is preferable to have 1 or more types of repeating units chosen from the repeating unit derived from the monomer represented by these.

[Formula 9]

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like), or a carbon atom The alkyl group whose number is 1-6 (for example, a methyl group, an ethyl group, a propyl group, etc.) is shown.

In formula (iv)-formula (vi), R <^11> , R <^12> and R <^13> , Preferably, they are each independently a hydrogen atom or the alkyl group of 1-3 carbon atoms, More preferably, they are each independently It is a hydrogen atom or a methyl group. In General Formula (iv), R ¹² and R ¹³ are each particularly preferably a hydrogen atom.

X <_1> in Formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and it is preferable that it is an oxygen atom.

Y in Formula (v) represents a metaine group or a nitrogen atom.

L <_1> in Formula (iv)-Formula (v) represents a single bond or a bivalent coupling group. As an example of a bivalent coupling group, a bivalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a bivalent aromatic group (for example, Arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino bond (-NR ³¹ '-, Herein, R ³¹ ′ may include an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), or a combination thereof.

It is preferable that L <_1> is a bivalent coupling group containing a single bond, an alkylene group, or an oxyalkylene structure. As for the oxyalkylene structure, it is more preferable that it is an oxyethylene structure or an oxypropylene structure. In addition, L ₁ may include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As a polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) _n- , and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

In formula (vi), R <^14> , R <^15> and R <^16> are respectively independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine etc.), the alkyl group of 1-6 carbon atoms (For example, Methyl group, ethyl group, propyl group, or the like), -Z ₁ , or -L ₁ -Z ₁ . Here, L ₁ and Z ₁ is, and L ₁ and Z ₁ and copper in the above, preferred examples are the same. As R <^14> , R <^15> and R <^16> , a hydrogen atom or the C1-C3 alkyl group each independently is preferable, and a hydrogen atom is more preferable.

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

As an example of the specific example of the said graft copolymer, the following is mentioned. In addition, Paragraph No. 0127 of Unexamined-Japanese-Patent No. 2013-249417-the high molecular compound of 0129 can be referred to, and this content is integrated in this specification.

[Formula 10]

A dispersing agent can also be obtained as a commercial item, As such a specific example, "DA-7301" by the Kusumoto Kasei Co., Ltd. "DISPERBYK-101 (polyamide amine phosphate) by BYK Chemie", 107 (carboxylic acid ester), 110 (acid group) Copolymer comprising a), 111 (phosphate dispersant), 130 (polyamide), 140, 142, 145, 161, 162, 163, 164, 165, 166, 170, 180, 187, 190, 191, 2001, 2001, 2010, 2012, 2025 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), 9076 "," EFKA4047, 4050-4165 (polyurethane system) by EFKA, EFKA4330-443 ( Block copolymer), 4400-4440 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo Pigment derivative) "," Azisper PB821, PB822, PB880, PB881 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Florene TG-710 (urethane oligo) manufactured by Kyoeisha Chemical Co., Ltd. Mer) "," Polyflo No. 50E, No. 300 (acrylic copolymer) "," Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyhydric carboxylic acid) made by Kusumoto Kasei Co., Ltd., # 7004 (poly Ether ester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin) Polycondensates) "," homogenol L-18 (polymeric polycarboxylic acid) "," emulgen 920, 930, 935, 985 (polyoxyethylenenonylphenylether) "," acetamine 86 (stearylamine acetate) " Nippon Lubrizol Co., Ltd. "solsperpers 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (having functional part at the end) Polymer), 24000, 28000, 32000, 38500 (graft copolymer), "Nikko T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" by Nikko Chemicals, Kawaken Fine Chemical Co., Ltd. " Noact T-8000E "," organosiloxane polymer KP341 "by Shin-Etsu Chemical Co., Ltd.," EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer "by Morishita Sangyo Co., Ltd. 400, EFKA Polymer 401, EFKA Polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 ", manufactured by Sanofco Co., Ltd. Nick L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ", and Sanyo Kasei Co., Ltd." Ionet (Brand name) S-20 "etc. are mentioned. Acribase FFS-6752, Acribase FFS-187, Acricure RD-F8, and Cyclomer P can also be used.

<< radically polymerizable compound >>

An active energy ray curable composition can contain a radically polymerizable compound. The radically polymerizable compound is preferably a polymerizable compound having an ethylenically unsaturated bond. The radically polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more, and even more preferably three or more. For example, 15 or less are preferable and, as for an upper limit, 6 or less are more preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and the like.

The radically polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. Monomers are preferred.

It is preferable that it is 100-3,000, and, as for the molecular weight of a radically polymerizable compound, 250-1, 500 are more preferable.

It is preferable that it is a 3-15 functional (meth) acrylate compound, and, as for a radically polymerizable compound, it is more preferable that it is a 3-6 functional (meth) acrylate compound.

As an example of a monomer and a prepolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its esters, amides, and these multimers are mentioned, Preferably, they are ester of unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, the amide of unsaturated carboxylic acid and an aliphatic polyhydric amine compound, and these multimers. Moreover, the addition reaction product of the unsaturated carboxylic acid ester or amide which has nucleophilic substituents, such as a hydroxyl group, an amino group, and a mercapto group, with monofunctional or polyfunctional isocyanate or epoxy, or monofunctional or polyfunctional Dehydration condensation reaction products with carboxylic acid, etc. are also used suitably. And desorption products such as unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups, monofunctional or polyfunctional alcohols, amines and thiols, halogenated groups and tosyloxy groups Also suitable are reactants of unsaturated carboxylic acid esters or amides having a substituent with monofunctional or polyfunctional alcohols, amines and thiols. In addition, it is also possible to use the compound group substituted by vinylbenzene derivatives, such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, etc. instead of the said unsaturated carboxylic acid.

As these specific compounds, Paragraph No. 0095 of Unexamined-Japanese-Patent No. 2009-288705-the compound of 0108 can also be used suitably also in this invention.

As a radically polymerizable compound, the compound which has a boiling point of 100 degreeC or more under normal pressure which has one or more groups which have an ethylenically unsaturated bond is also preferable. As an example, Paragraph No. 0227 of Unexamined-Japanese-Patent No. 2013-29760, Paragraph No. 0254 of Unexamined-Japanese-Patent No. 2008-292970-0257 can be referred, for example, These content is integrated in this specification.

A radically polymerizable compound is a dipentaerythritol triacrylate (KAYARAD D-330 as a commercial item; the product made by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial item; Nippon Kayaku Co., Ltd.). Kaisha), dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; made by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; Nippon Kayaku Co., Ltd .; A-DPH-12E manufactured by Kabushiki Kaisha, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd., and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (eg, For example, SR454 and SR499 which are commercially available from Sartomer Co., Ltd. are preferable. These oligomer types can also be used. Moreover, NK ester A-TMMT (pentaerythritol tetraacrylate, the product made by Shin-Nakamura Kagaku Kogyo Co., Ltd.), KAYARAD RP-1040 (made by Nippon Kayaku Co., Ltd.), etc. can also be used.

The aspect of a preferable radically polymerizable compound is shown below.

The radically polymerizable compound may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. As the radical polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a radical polymerizable compound having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. The compound is more preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. As a commercial item, Toroni Seiko Corporation Aronix TO-2349, M-305, M-510, M-520 etc. are mentioned, for example.

Preferable acid value of a radically polymerizable compound is 0.1-40 mgKOH / g, Especially preferably, it is 5-30 mgKOH / g. If the acid value of a radically polymerizable compound is 0.1 mgKOH / g or more, image development melt | dissolution characteristic is favorable, and if it is 40 mgKOH / g or less, it is advantageous in manufacture and handling. Furthermore, photopolymerization performance is good and it is excellent in sclerosis | hardenability.

As a radically polymerizable compound, the compound which has a caprolactone structure is also a preferable aspect.

The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, but for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone-modified polyfunctional obtained by esterifying polyhydric alcohols such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, and (meth) acrylic acid and ε-caprolactone (Meth) acrylate is mentioned. Especially, the compound which has a caprolactone structure represented by a following formula (Z-1) is preferable.

[Formula 11]

In formula (Z-1), all 6 R's are groups represented by following formula (Z-2), or 1-5 of 6 R's are group represented by following formula (Z-2), and remainder is the following It is group represented by Formula (Z-3).

[Formula 12]

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

[Formula 13]

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

The radically polymerizable compound which has a caprolactone structure is marketed as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., for example, and m = in DPCA-20 (formula (Z-1)-(Z-3) above). 1, the number of groups represented by formula (Z-2) = 2, the compound in which R ¹ is all hydrogen atoms), DPCA-30 (same formula, m = 1, the number of groups represented by formula (Z-2) = 3 , A compound in which R ¹ is all a hydrogen atom), DPCA-60 (the number of groups represented by the same formula, m = 1, formula (Z-2) = 6, a compound in which R ¹ is all hydrogen atoms), DPCA-120 ( In the same formula, m = 2, the number of groups represented by Formula (Z-2) = 6, and R <^1> are all hydrogen atoms), etc. are mentioned.

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

[Formula 14]

In formulas (Z-4) and (Z-5), each E independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-. Y respectively independently represents the integer of 0-10, and X respectively independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.

In formula (Z-4), the sum total of a (meth) acryloyl group is three or four, m respectively independently represents the integer of 0-10, and the sum of each m is an integer of 0-40.

In formula (Z-5), the sum total of (meth) acryloyl groups is five or six, n respectively independently represents the integer of 0-10, and the sum of each n is an integer of 0-60.

In formula (Z-4), the integer of 0-6 is preferable and, as for m, the integer of 0-4 is more preferable.

Moreover, the integer of 2-40 is preferable, as for the sum total of each m, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In formula (Z-5), the integer of 0-6 is preferable and, as for n, the integer of 0-4 is more preferable.

Moreover, the integer of 3-60 is preferable, as for the sum total of each n, the integer of 3-24 is more preferable, and the integer of 6-12 is more preferable.

In formula (Z-4) or a group represented by the formula (Z-5) of _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - is, an end portion of an oxygen atom The form which couple | bonds with this X is preferable.

The compound represented by a formula (Z-4) or a formula (Z-5) may be used individually by 1 type, and may use 2 or more types together. In particular, in the formula (Z-5), all 6 X is an acryloyl group, and in a formula (Z-5), all 6 X is a compound which is acryloyl group, and at least 6 X Preferred is an embodiment in which one is a mixture with a compound that is a hydrogen atom. According to this aspect, developability can be further improved.

Moreover, 20 mass% or more is preferable and, as for content of the compound represented by a formula (Z-4) or a formula (Z-5) in a radically polymerizable compound, 50 mass% or more is more preferable.

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

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

Specifically, the compound (henceforth a "exemplary compound (a)-(f)" shown by following formula (a)-(f)) is mentioned, Especially, exemplary compound (a), (b) , (e) and (f) are preferred.

[Formula 15]

[Formula 16]

As a commercial item of the radically polymerizable compound represented by Formula (Z-4) and (Z-5), SR-494 and Nippon Kayaku Co., Ltd. which are tetrafunctional acrylates which have four ethyleneoxy chains made by Satomer, for example. DPCA-60 which is a 6-functional acrylate which has six pentylene oxy chains, and TPA-330 which is a trifunctional acrylate which has three isobutylene oxy chains, etc. are mentioned.

As for content of a radically polymerizable compound, 0.1-40 mass% is preferable with respect to the total solid of an active energy ray curable composition. 0.5 mass% or more is more preferable, and, as for a minimum, 1 mass% or more is more preferable. For example, 30 mass% or less is more preferable, and, as for an upper limit, 20 mass% or less is more preferable. A radically polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that the total amount exists in said range.

<< cationically polymerizable compound >>

The active energy ray curable composition may contain a cationically polymerizable compound. As a cationically polymerizable compound, the compound which has a cyclic ether group is mentioned. As a cyclic ether group, an epoxy group and an oxetanyl group are mentioned, An epoxy group is preferable.

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

The cationically polymerizable compound may be a low molecular weight compound (e.g., a molecular weight of less than 2,000, and even a molecular weight of less than 1,000), and a macromolecular compound (e.g., a molecular weight of 2,000 or more, in the case of a polymer, a weight average molecular weight of 2,000 or more) Any of these may be sufficient. It is preferable that it is 200-100,000, and, as for the weight average molecular weight of a cationically polymerizable compound, 500-50,000 are more preferable.

As an example of the compound which has two or more epoxy groups in a molecule | numerator, an aliphatic epoxy compound etc. are mentioned. Reference may be made to the descriptions of paragraphs 0021 to 0031 of WO2012 / 093591, which are incorporated herein by reference.

These can be obtained as a commercial item. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX -321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941 , EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC -301, DLC-402 (above Nagase Chemtex), Celoxide 2021P, 2081, 3000, EHPE3150, Epolyd GT400, Celbinas B0134, B0177 (made by Daicel Corporation), etc. are mentioned.

These can be used individually by 1 type or in combination of 2 or more types.

As a specific example of the compound which has two or more oxetanyl groups in a molecule | numerator, Aaron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd. product) can be used.

Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

As for content of a cationically polymerizable compound, 0.1-40 mass% is preferable with respect to the total solid of an active energy ray curable composition. 0.5 mass% or more is more preferable, and, as for a minimum, 1 mass% or more is more preferable. For example, 30 mass% or less is more preferable, and, as for an upper limit, 20 mass% or less is more preferable. 1 type may be sufficient as a cationically polymerizable compound, and may use 2 or more types together. When using 2 or more types together, it is preferable that the total amount exists in said range.

<< photoinitiator >>

An active energy ray curable composition can contain a photoinitiator. When an active energy ray curable composition contains a radically polymerizable compound, it is preferable to contain a photoinitiator.

As a photoinitiator, there is no restriction | limiting in particular as long as it has the ability to start superposition | polymerization of a radically polymerizable compound, It can select suitably from well-known photoinitiators. For example, it is preferable to have photosensitivity to visible light from an ultraviolet range. Moreover, the active agent which produces | generates some action with a photoexcited sensitizer and produces | generates an active radical may be sufficient, and the initiator which starts cationic polymerization according to the kind of monomer may be sufficient.

Moreover, it is preferable that the photoinitiator contains at least 1 sort (s) of the compound which has a molar extinction coefficient of at least about 50 in the range of about 300 nm-800 nm (330 nm-500 nm are more preferable).

As a photoinitiator, For example, acyl phosphine compounds, such as a halogenated hydrocarbon derivative (for example, a triazine skeleton, an oxadiazole skeleton), an acyl phosphine oxide, and hexaaryl biimidazole And oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like. As a halogenated hydrocarbon compound which has a triazine skeleton, For example, Wakabayashi etc., Bull. Chem. Soc. J. Org by the compounds described in Japan, 42, 2924 (1969), the compounds described in British Patent Publication No. 1388492, the compounds described in JP-A-53-133428, the compounds described in JP 3337024, FC Schaefer and the like. . Chem .; 29, 1527 (1964), the compound of JP-A-62-58241, the compound of JP-A-5-281728, the compound of JP-A-5-34920, United States The compound of patent publication 4212976, etc. are mentioned.

Moreover, from a viewpoint of exposure sensitivity, a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime Compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyloxadiazole compound, 3- Preferred are compounds selected from the group consisting of aryl substituted coumarin compounds.

More preferably, the trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound At least 1 sort (s) of compound chosen from the group which consists of a trihalomethyl triazine compound, the (alpha)-amino ketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is more preferable.

As a specific example of a photoinitiator, Paragraph No. 0265 of Unexamined-Japanese-Patent No. 2013-29760-0268 can be referred, for example, This content is integrated in this specification.

As a photoinitiator, a hydroxy acetophenone compound, an amino acetophenone compound, and an acyl phosphine compound can also be used suitably. More specifically, the amino acetophenone series initiator of Unexamined-Japanese-Patent No. 10-291969 and the acyl phosphine type initiator of Unexamined-Japanese-Patent No. 4225898 can also be used, for example.

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

As an aminoacetophenone type initiator, IRGACURE-907 which is a commercial item, IRGACURE-369, and IRGACURE-379EG (all are brand name: BASF Corporation make) can be used. The aminoacetophenone series initiator can also use the compound of Unexamined-Japanese-Patent No. 2009-191179 by which absorption wavelength was matched with longwave light sources, such as 365 nm or 405 nm.

As an acyl phosphine type initiator, IRGACURE-819 which is a commercial item, and Lucirin-TPO (all are brand name: BASF Corporation make) can be used.

As a photoinitiator, More preferably, an oxime compound is mentioned.

As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

In the present invention, as the oxime compound which can be suitably used, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one and 3-propionyloxyiminobutan-2-one , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyl jade C) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Unexamined-Japanese-Patent No. 2000-66385, Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2004-534797, Unexamined-Japanese-Patent No. 2006-342166, etc. are mentioned.

As a commercial item, IRGACURE-OXE01 (made by BASF Corporation) and IRGACURE-OXE02 (made by BASF Corporation) are used suitably. In addition, TR-PBG-304 (made by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Ackles NCI-831 and Adeka Ackles NCI-930 (made by ADEKA) It is available.

Moreover, as an oxime compound other than the above-mentioned, the compound of Unexamined-Japanese-Patent No. 2009-519904 with an oxime connected to the N-position of a carbazole ring, The compound of the US Patent No.7626957 with a hetero substituent introduced into the benzophenone site, and a pigment | dye site | part The compounds described in Japanese Unexamined Patent Publication No. 2010-15025 and U.S. Patent Publication No. 2009-292039, ketoxime compounds described in International Publication No. WO2009 / 131189, triazine skeleton and oxime skeleton having the same nitro group introduced therein You may use the compound of Unexamined-Japanese-Patent No. 7556910, the compound of Unexamined-Japanese-Patent No. 2009-221114 which has an absorption maximum in 405 nm, and has favorable sensitivity with respect to a g-ray light source.

Preferably, Paragraph No. 0274 of Unexamined-Japanese-Patent No. 2013-29760-0275 can be referred, for example, This content is integrated in this specification.

Specifically, as an oxime compound, the compound represented by a following formula (OX-1) is preferable. Moreover, the oxime compound of (E) body may be sufficient as N-O bond of oxime, the oxime compound of (Z) body may be sufficient, and the mixture of (E) body and (Z) body may be sufficient as it.

[Formula 17]

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

In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atom group.

Examples of the monovalent nonmetallic atom group include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be substituted by the other substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, acyloxy group, acyl group, alkyl group, aryl group and the like.

As a monovalent substituent represented by B in Formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is preferable. These groups may have one or more substituents. As a substituent, the substituent mentioned above is mentioned.

As a divalent organic group represented by A in Formula (OX-1), a C1-C12 alkylene group, a cycloalkylene group, and an alkynylene group is preferable. These groups may have one or more substituents. As a substituent, the substituent mentioned above is mentioned.

In this invention, the oxime compound which has a fluorine atom can also be used as a photoinitiator. As a specific example of the oxime compound which has a fluorine atom, the compound of Unexamined-Japanese-Patent No. 2010-262028, the compound of Unexamined-Japanese-Patent No. 2014-500852, the compound 24, 36-40, and the compound of Unexamined-Japanese-Patent No. 2013-164471 (C-3) etc. are mentioned. These contents are incorporated in this specification.

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

[Formula 18]

In Formula (1), R <^1> and R <^2> respectively independently represents a C1-C20 linear alkyl group, a C4-C20 alicyclic hydrocarbon group, a C6-C30 aryl group, or a C7-30 When an arylalkyl group is represented and R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and having 6 to 6 carbon atoms. An aryl group of 30, an arylalkyl group of 7 to 30 carbon atoms, or a heterocyclic group of 4 to 20 carbon atoms is represented, and X represents a direct bond or a carbonyl group.

In the formula (2), R ^1, R ^2, R ³ and R ^4, and R ^1, R ^2, R ³ and R ⁴ with the consent of the formula (1), R ⁵ is -R ^6, -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN , A halogen atom or a hydroxyl group, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond Or a carbonyl group is represented, a shows the integer of 0-4.

In said Formula (1) and Formula (2), R <^1> and R <^2> is respectively independently a methyl group, an ethyl group, n-propyl group, i-propyl group, a cyclohexyl group, or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. X is preferably a direct bond.

As a specific example of a compound represented by Formula (1) and Formula (2), Paragraph No. 0076 of Unexamined-Japanese-Patent No. 2014-137466-the compound of 0079 are mentioned, for example. This content is incorporated herein by reference.

Although the specific example of the oxime compound used preferably in this invention is shown below, this invention is not limited to these.

[Formula 19]

It is preferable that an oxime compound has a maximum absorption wavelength in the wavelength range of 350 nm-500 nm, It is more preferable to have an absorption wavelength in the wavelength range of 360 nm-480 nm, It is especially preferable that the absorbance of 365 nm and 405 nm is high.

It is preferable that the molar extinction coefficient in 365 nm or 405 nm is 1,000-300,000, as for an oxime compound, it is more preferable that it is 2,000-300,000, and it is more preferable that it is 5,000-200,000.

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

You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

As for content of a photoinitiator, 0.1-50 mass% is preferable with respect to the total solid of an active energy ray curable composition, More preferably, it is 0.5-30 mass%, More preferably, it is 1-20 mass%. The active energy ray curable composition may include only one type of photopolymerization initiator or may include two or more types. When it contains two or more types, it is preferable that the total amount exists in said 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 cationically polymerizable compound, it is preferable to contain an acid generator.

The acid generator is preferably a compound which generates an acid by irradiation with an active energy ray (radiation). As an acid generator, the light (400-200 nm ultraviolet-ray, far ultraviolet rays, especially preferably g-ray, h-ray, i-ray) used for a photocationic polymerization initiator, the pigment | dye coloring agent, a photochromic agent, or a microresist etc. , KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam can be used to select a compound that generates acid appropriately, and to select an acid generator sensitive to ultraviolet rays desirable.

Examples of the acid generator include onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, which are decomposed by irradiation with radiation, imidosulfonates, oxime sulfonates, and diazodisulfones. And sulfonate compounds such as disulfone and ortho-nitrobenzyl sulfonate. As a kind of acid generator, a specific compound, and a preferable example, Paragraph No. 0066 of Unexamined-Japanese-Patent No. 2008-13646-the compound of 0222 can be mentioned, These can also be applied to this invention.

As a compound which is preferable as an acid generator which can be used for this invention, the compound represented by following formula (b1), (b2), (b3) is mentioned.

[Formula 20]

In formula (b1), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent an organic group. X ^- is, represents a non-nucleophilic anion, preferably a sulfonic acid anion, carboxylic acid anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide _{^{anion, BF 4 -, PF 6 -}} , SbF 6 - and the like or groups shown in the following, and preferably _{^{BF 4 -, PF 6 -,}} SbF 6 - a.

As a commercial item of an acid generator, WPAG-469 (made by Wako Junyaku Kogyo Co., Ltd.) etc. is mentioned.

As for content of an acid generator, 0.1-50 mass% is preferable with respect to the total solid of an active energy ray curable composition, More preferably, it is 0.5-30 mass%, More preferably, it is 1-20 mass%. The active energy ray curable composition may include only one type of acid generator or may include two or more types. When it contains two or more types, it is preferable that the total amount exists in said range.

<< silane coupling agent >>

In an active energy ray curable composition, you may contain a silane coupling agent for the purpose of improving adhesiveness with a base material. In particular, when the active energy ray-curable composition contains a thermosetting resin, it is preferable to further contain a silane coupling agent. Even when a cured film is manufactured by a low temperature process of 100 degrees C or less using the active energy ray curable composition containing a thermosetting resin, adhesiveness with a base material can be fully ensured by containing a silane coupling agent further.

In the present invention, the silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. It is preferable that hydrolysable groups, such as an alkoxy group, couple | bond with the silicon atom. The hydrolyzable group refers to a substituent which can be directly connected to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and / or a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group, an alkenyloxy group is mentioned, for example. When the hydrolyzable group has a carbon atom, the carbon number is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group of 4 or less carbon atoms or an alkenyloxy group of 4 or less carbon atoms is preferable.

In the present invention, in order to improve the adhesion of the cured film, the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (except for the silicon atom to which the hydrolyzable group is bonded), and the fluorine atom and the silicon atom ( However, it is preferable not to include the silicon atom to which a hydrolyzable group couple | bonded), the alkylene group substituted by the silicon atom, the C8 or more linear alkyl group, and the C3 or more branched alkyl group.

It is preferable that a silane coupling agent has group represented by the following formula (Z). * Indicates a bonding position.

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

R ^z1 represents an alkyl group, R ^z2 represents a hydrolyzable group, and m represents an integer of 1 to 3. It is preferable that it is 1-5, and, as for carbon number of the alkyl group which R ^z1 represents, 1-3 are more preferable. The definition of the hydrolyzable group represented by R ^z2 is as described above.

It is preferable that a silane coupling agent has a curable functional group. Examples of the curable functional group include (meth) acryloyloxy groups, epoxy groups, oxetanyl groups, isocyanate groups, hydroxyl groups, amino groups, carboxyl groups, thiol groups, alkoxysilyl groups, methylol groups, vinyl groups, and (meth) acryl It is preferable that it is at least 1 sort (s) chosen from the group which consists of an amide group, a styryl group, and a maleimide group, and it is more preferable that it is at least 1 sort (s) chosen from the group which consists of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.

The molecular weight of the silane coupling agent is not particularly limited, and from the viewpoint of handleability, 100 to 1,000 are preferable, 270 or more are preferable, and 270 to 1,000 are more preferable at the point which the effect of this invention is more excellent.

As one of the suitable aspects of a silane coupling agent, the silane coupling agent X represented by Formula (W) is mentioned.

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 suitable range is also as described above.

Lz represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene group, arylene group, -NR ^12- , -CONR ^12- , -CO-, -CO _2- , -SO ₂ NR ^12- , -O-, -S-, -SO _2- , Or a combination thereof.

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

Lz is at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms and an arylene group having 6 to 12 carbon atoms, or these groups and -NR ^12- , -CONR ^12- , -CO-, -CO _2- , A group consisting of a combination with at least one group selected from the group consisting of -SO ₂ NR ^12- , -O-, -S-, and -SO ₂ -is preferably an alkylene group having 2 to 10 carbon atoms, -CO ₂ - is more preferably a group consisting of or a combination of these groups ^{-, -O-, -CO-, -CONR 12} . Here, said R <^12> represents a hydrogen atom or a methyl group.

m represents 1-3, 2-3 are preferable and 3 is more preferable.

As the silane coupling agent X, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl trime Toxysilane (brand name KBM-603 by Shin-Etsu Chemical Co., Ltd.), N- (beta) -aminoethyl- (gamma) -aminopropyl- triethoxysilane (brand name KBE-602 by Shin-Etsu Chemical Co., Ltd.), gamma-aminopropyl Trimethoxysilane (brand name KBM-903 made by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl triethoxysilane (brand name KBE-903 made by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl trimethoxy silane Phosphorus (brand name KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), glycidoxy octyl trimethoxysilane (trade name KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

The silane coupling agent Y which has a silicon atom, a nitrogen atom, a curable functional group, and has a hydrolysable group couple | bonded with the silicon atom in a molecule | numerator is also preferable.

The silane coupling agent Y may have at least one silicon atom in a molecule | numerator, and a silicon atom can couple | bond with the following atoms and substituents. They may be the same atom, substituent, or may differ. The atom and substituent which can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an amino group which can be substituted with an aryl group, an alkyl group and / or an aryl group, a silyl group, or 1 carbon atom. An alkoxy group, an aryloxy group, etc. of -20 are mentioned. These substituents also include silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amino groups which can be substituted with alkyl groups and / or aryl groups, halogen atoms, sulfonamide groups, alkoxycarbonyl groups May be substituted with an amide group, urea group, ammonium group, alkylammonium group, carboxyl group or salt thereof, sulfo group or salt thereof.

At least one hydrolyzable group is bonded to the silicon atom. The definition of a hydrolyzable group is as above-mentioned.

The group represented by Formula (Z) may be contained in the silane coupling agent Y.

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom has at least one organic group as a substituent. desirable. Moreover, as an amino group structure, it may exist in a molecule | numerator in the form of the partial structure of a nitrogen-containing heterocycle, and may exist as a substituted amino group, such as aniline. Here, as an organic group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof is mentioned. These may further have a substituent and as a substituent which can be introduced, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, a sulfonamide group, an alkoxy carbo And a vinyl group, a carbonyloxy group, an amide group, a urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group or salts thereof, and a sulfo group.

Moreover, it is preferable that a nitrogen atom is couple | bonded with the curable functional group through arbitrary organic coupling groups. As a preferable organic coupling group, the substituent which can introduce | transduce the above-mentioned nitrogen atom and the organic group couple | bonded with it is mentioned.

The definition of the curable functional group contained in the silane coupling agent Y is as above-mentioned, and the suitable range is also as above-mentioned.

Although the silane coupling agent Y should have at least 1 or more of curable functional groups in 1 molecule, it is also possible to have 2 or more of curable functional groups in 1 molecule. From a viewpoint of a sensitivity and stability, it is preferable to have 2-20 curable functional groups in 1 molecule, It is more preferable to have 4-15, It is more preferable to have 6-10.

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 the integer of 1-3, n represents the integer of 1 or more.

R ^y1 , R ^y2 , R ^y3 and m in the formula (Y) are synonymous with R ^z1 , R ^z2 , R ^z3 and m in the formula (W), respectively, and the preferred range thereof is also the same.

N in Formula (Y) represents an integer of 1 or more. For example, 20 or less are preferable, 15 or less are more preferable, and 10 or less of an upper limit is more preferable. For example, 2 or more are preferable, as for a minimum, 4 or more are more preferable, and 6 or more are more preferable. N may be set to 1.

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

And to, as a group having nitrogen formula (LN-1) ~ at least one type of, or the formula is selected from (LN-4) (LN- 1) ~ (LN-4), -CO-, -CO 2 - there may be mentioned a group comprising a combination of at least one kind selected from -, -O-, -S-, and -SO _2. The alkylene group may be either linear or branched. The alkylene group and the arylene group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.

[Formula 21]

In formula, * represents a connection hand.

As a specific example of the silane coupling agent Y, the following compound is mentioned, for example. In the formula, Et represents an ethyl group. Moreover, Paragraph No. 0018 of Unexamined-Japanese-Patent No. 2009-288703-the compound of 0036 are mentioned, This content is integrated in this specification.

[Formula 22]

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

<< colored coloring agent >>

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

In this invention, a pigment | dye may be sufficient as a chromatic coloring agent. Preferably it is a pigment.

The pigment has an average particle diameter r of preferably 20 nm ≤ r ≤ 300 nm, more preferably 25 nm ≤ r ≤ 250 nm, more preferably 30 nm ≤ r ≤ 200 nm. The "average particle diameter" here means the average particle diameter with respect to the secondary particle which the primary particle of a pigment aggregated.

Moreover, it is preferable that the particle size distribution (henceforth simply called "particle size distribution") of the secondary particle of the pigment which can be used is 70 mass% or more of the whole secondary particle which enters (average particle diameter +/- 100) nm, 80 It is more preferable that it is mass% or more. In addition, the particle size distribution of a secondary particle can be measured using a scattering intensity distribution.

In addition, the average particle diameter of a primary particle can be calculated | required by observing with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring 100 particle sizes in the part which particle | grains are not aggregated, and calculating an average value. .

It is preferable that a pigment is an organic pigment, and the following are mentioned. However, this invention is not limited to these.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35 : 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94 , 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137 , 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 , 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 and so on (yellow pigment),

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

CI 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. Red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc.

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

There is no restriction | limiting in particular in dye, A well-known dye can be used. Examples of the chemical structure include pyrazole azo, anilinoazo, triaryl methane, anthraquinone, azomethine, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, and cyanine. Dyes such as phenoxyazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo and pyrromethene. Moreover, you may use the multimer of these dyes. Moreover, the dye of Unexamined-Japanese-Patent No. 2015-028144 and Unexamined-Japanese-Patent No. 2015-34966 can also be used.

Moreover, as a dye, an acid dye and / or its derivative may be used suitably.

In addition, direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes, and / or derivatives thereof, and the like can also be usefully used.

Although the specific example of an acid dye is given to the following, it is not limited to these. For example, the following dyes and derivatives of these dyes are mentioned.

Acid alizarin violet N,

Acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40-45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1,

Acid chrome violet K,

Acid Fuchsin; Acid green 1, 3, 5, 9, 16, 25, 27, 50,

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

Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274,

Acid violet 6B, 7, 9, 17, 19,

Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243,

Food Yellow 3

Moreover, azo, xanthene, and phthalocyanine acid dyes other than the above are also preferable, and C. I. Solvent Blue 44, 38; C. I. Solvent orange 45; Acid dyes such as Rhodamine B and Rhodamine 110 and derivatives of these dyes are also preferably used.

Especially, as dye, a triaryl methane type, anthraquinone type, an azomethine type, a benzylidene type, an oxonol type, a cyanine type, a phenothiazine type, a pyrrolopyrazole azomethine type, a xanthene type, a phthalocyanine It is preferable that it is a coloring agent chosen from a system, a benzopyran system, an indigo system, a pyrazole azo system, an anilino azo system, a pyrazolo triazole azo system, a pyridone azo system, an anth pyridone system, and a pyrromethene system.

Moreover, you may use combining a pigment and dye.

When an active energy ray curable composition contains a chromatic colorant, 1-80 mass% is preferable with respect to the total solid of an active energy ray curable composition, content of a chromatic colorant. 5 mass% or more is more preferable, 10 mass% or more is more preferable, and 20 mass% or more of a minimum is more preferable. 75 mass% or less is more preferable, and, as for an upper limit, 70 mass% or less is more preferable.

<< black colorant >>

The active energy ray curable composition may contain a black colorant. As the black colorant, any of an organic black colorant and an inorganic black colorant may be used. Moreover, both can also be used together. Although the composition containing a black coloring agent is low in sclerosis | hardenability by exposure, and was heat-processing at high temperature conventionally, even if it is an active energy ray curable composition containing a black coloring agent by the low-temperature process, according to the method of this invention, it is reliable. This excellent cured film can be produced, and the effect of the present invention is particularly remarkable.

(Organic black colorant)

As an organic type black coloring agent, a bisbenzofuranone compound, an azomethine compound, a perylene compound, an azo compound, etc. are mentioned, for example. As a bisbenzofuranone compound, the thing of Unexamined-Japanese-Patent No. 2010-534726, Unexamined-Japanese-Patent No. 2012-515233, Unexamined-Japanese-Patent No. 2012-515234, etc. is mentioned, For example, "IRGAPHOR Black" by BASF Corporation. It is available as. As a perylene compound, C. I. Pigment Black 31, 32, etc. are mentioned. As an azomethine compound, what was described in Unexamined-Japanese-Patent No. 1-170601, Unexamined-Japanese-Patent No. 2-34664, etc. can be mentioned, For example, it can obtain as "Chromopine black A1103" by Dainichi Seika Co., Ltd. Can be. Although an azo compound is not specifically limited, The compound etc. which are represented by a following formula (A-1) are mentioned suitably.

[Formula 23]

(Inorganic black colorant)

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

Titanium black is a black particle containing a titanium atom. Preferably, it is low titanium oxide, titanium oxynitride, etc. Titanium black particles can modify the surface as needed for the purpose of improving dispersibility, suppressing cohesiveness, and the like. It is possible to coat with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water repellent substance such as that shown in JP-A-2007-302836 is also possible.

Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of the individual particles are small.

Specifically, the average primary particle size is preferably in the range of 10 nm to 45 nm. In addition, the particle diameter in this invention, ie, a particle diameter, is a diameter of the circle which has the same area as the projection area of the outer surface of particle | grains. The projection area of the particles is obtained by measuring the area obtained by imaging with an electron micrograph and correcting the imaging magnification.

Although the specific surface area of titanium black is not restrict | limited, The value measured by Brunauer, Emmett, Teller (BET) method is a thing in order that the water repellency after surface treatment of titanium black with a water repellent agent may become predetermined performance. 5 and preferably from 150m ² / g, more preferably 20 ~ 120m ² / g.

As an example of the commercial item of titanium black, titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (brand name: Mitsubishi Material, Inc.), Tilack D (brand name: Acco) Kasei Co., Ltd.) etc. are mentioned.

Moreover, it is also preferable to contain titanium black as a to-be-dispersed thing containing titanium black and Si atom.

In this aspect, the titanium black is contained in the composition as a dispersion, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is preferably 0.05 or more, and more preferably 0.05 to 0.5 in terms of mass. 0.07-0.4 are more preferable.

Here, the said to-be-dispersed body contains both a thing of the titanium black in a primary particle state, and an aggregate (secondary particle) state.

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

First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C), whereby titanium black particles are the main component, and Si and Ti are The to-be-dispersed object containing can be obtained. The reduction treatment may be performed in an atmosphere of reducing gas such as ammonia. Examples of titanium oxide include TTO-51N (trade name: Ishihara Sangyo Co., Ltd.). As a commercial item of a silica particle, AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (brand name: Evonik make) etc. are mentioned.

You may use a dispersing agent for dispersion of a titanium oxide and a silica particle. As a dispersing agent, what is demonstrated in the column of the dispersing agent mentioned above is mentioned.

The above dispersion may be performed in a solvent. Examples of the solvent include water and an organic solvent. As a specific example, what is demonstrated in the column of the organic solvent mentioned later is mentioned.

Titanium black in which Si / Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the methods described in paragraph No. 0005 and paragraph No. 0016 to 0021 of JP2008-266045A.

In the to-be-dispersed product containing titanium black and Si atom, the above-mentioned thing can be used for titanium black.

Moreover, in this to-be-dispersed body, it consists of complex oxides, such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc. with the objective of adjusting dispersibility, coloring property, etc. with titanium black. You may use it 1 type or in combination or 2 or more types of black pigment.

In this case, it is preferable that the to-be-dispersed body which consists of titanium black occupies 50 mass% or more in all the to-be-dispersed body.

In addition, in this to-be-dispersed body, you may use together other colorants (organic pigment, dye, etc.) according to the objective with titanium black, unless the effect of this invention is impaired for the purpose of adjustment of light-shielding property, etc. .

Hereinafter, the material used when introducing Si atom into a to-be-dispersed body is demonstrated. When introducing Si atom into a to-be-dispersed body, Si containing substance, such as a silica, may be used.

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

In addition, when the particle diameter of the silica particles forms the light shielding film, if the particle size is smaller than the film thickness, the light shielding property is better, it is preferable to use fine particle type silica as the silica particles. Moreover, as an example of the particulate-type silica, the silica of Paragraph No. 0039 of Unexamined-Japanese-Patent No. 2013-249417 is mentioned, for example, This content is integrated in this specification.

When an active energy ray curable composition contains a black coloring agent, 1-80 mass% is preferable with respect to the total solid of an active energy ray curable composition, content of a black coloring agent. 5 mass% or more is more preferable, 10 mass% or more is more preferable, and 20 mass% or more of a minimum is more preferable. 75 mass% or less is more preferable, and, as for an upper limit, 70 mass% or less is more preferable.

Moreover, it is preferable that the total content of a black coloring agent and a chromatic coloring agent is 1-80 mass% with respect to the total solid of an active energy ray curable composition. 5 mass% or more is more preferable, 10 mass% or more is more preferable, and 20 mass% or more of a minimum is more preferable. 75 mass% or less is more preferable, and, as for an upper limit, 70 mass% or less is more preferable.

<< infrared absorber >>

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

In this invention, an infrared absorber means the compound which has maximum absorption in the wavelength range of an infrared region (preferably wavelength 800-1300 nm).

As an infrared absorber, a pyrrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an iminium compound, a thiol complex system compound, a transition metal oxide type compound, a squarylium compound, a naphthalocyanine, for example A compound, a quaterylene compound, a dithiol metal complex system compound, a croconium compound, etc. are mentioned.

As a pyrrolopyrrole compound, Paragraph No. 0049 of Unexamined-Japanese-Patent No. 2009-263614-the compound of 0058 may be used, and this content is integrated in this specification. As the phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanine compound, the squarylium compound, and the croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP2010-111750A may be used. This content is incorporated herein by reference. In addition, a cyanine compound can be referred to, for example, "functional dye, Makoto Ogawara / Masaru Matsuoka / Kitao Daisyro / Hirashima Tsuneaki, Godansha Scientific", and this content is incorporated herein by reference. .

Moreover, as an infrared absorber, the compound disclosed by Paragraph No. 0004-0016 of Unexamined-Japanese-Patent No. 07-164729, the compound disclosed by Paragraph No. 0027-0062 of Unexamined-Japanese-Patent No. 2002-146254, and Paragraph No. of Unexamined-Japanese-Patent No. 2011-164583 The near-infrared absorbing particle which consists of crystallites of the oxide containing Cu and / or P disclosed by 0034-0067 and whose number average aggregate particle diameter is 5-200 nm may be used, These content is integrated in this specification. FD-25 (manufactured by Yamada Kagaku Co., Ltd.), IRA842 (manufactured by Exiton Co., Ltd.) and the like can also be used.

When an active energy ray curable composition contains an infrared absorber, it is preferable that content of an infrared ray absorber is 1-80 mass% with respect to the total solid of an active energy ray curable composition. 5 mass% or more is more preferable, 10 mass% or more is more preferable, and 20 mass% or more of a minimum is more preferable. 75 mass% or less is more preferable, and, as for an upper limit, 70 mass% or less is more preferable.

Moreover, it is preferable that the sum total content of an infrared absorber, a black coloring agent, and a chromatic coloring agent is 1-80 mass% with respect to the total solid of an active energy ray curable composition. 5 mass% or more is more preferable, 10 mass% or more is more preferable, and 20 mass% or more of a minimum is more preferable. 75 mass% or less is more preferable, and, as for an upper limit, 70 mass% or less is more preferable.

<< pigment derivative >>

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

<< organic solvent >>

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

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

As the organic solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, ammonium formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, alkyl oxyacetates (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.) (e.g. methoxyacetate, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxy 3-oxypropionate alkyl esters (e.g. methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.) (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy) Methyl propionate, ethyl 3-ethoxypropionate, etc.), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionate) Ethyl onion, 2-oxypropionic acid propyl, and the like (e.g., 2-methoxypropionate methyl, 2-methoxypropionate propyl, 2-methoxypropionic acid propyl, 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) , Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like, for example, diethylene glycol dimethyl ether, tetrahydrofuran , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Die ethylene Lycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and the like, for example, as ketones. Methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc., and aromatic hydrocarbons are mentioned suitably, for example, toluene, xylene, etc.

It is also preferable to use these organic solvents in mixture of 2 or more types from a viewpoint of solubility, such as polymeric compound, alkali-soluble resin, improvement of a coating surface shape, etc. In this case, Especially preferably, said 3-ethoxy propionate methyl, 3-ethoxy propionate ethyl, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy Mixed solution composed of two or more selected from methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate to be.

In this invention, it is preferable that the content rate of a peroxide is 0.8 mmol / L or less, and it is more preferable that an organic solvent does not contain a peroxide substantially.

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

The active energy ray curable composition may include only one type of organic solvent or may include two or more types. When it contains two or more types, it is preferable that the total amount exists in said range.

<< polymerization inhibitor >>

It is preferable that an active energy ray curable composition adds a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of a polymeric compound during manufacture or storage of a composition.

As the polymerization inhibitor, hydroquinone, para-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6 -tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine 1st cerium salt, etc. are mentioned.

When an active energy ray curable composition contains a polymerization inhibitor, as for content of a polymerization inhibitor, 0.01-5 mass% is preferable with respect to the total solid of an active energy ray curable composition.

The active energy ray curable composition may include only one type of polymerization inhibitor or may include two or more types. When it contains two or more types, it is preferable that the total amount exists in said range.

<< surfactant >>

You may add various surfactant to an active energy ray curable composition from a viewpoint of further improving applicability | paintability. As surfactant, various surfactant, such as a fluorochemical surfactant, nonionic surfactant, cationic surfactant, anionic surfactant, silicone type surfactant, can be used.

For example, by containing a fluorochemical surfactant, the liquid characteristic (particularly fluidity) at the time of preparing as a coating liquid improves more. That is, when forming a cured film using the coloring composition containing a fluorine-type surfactant, by reducing the interface tension of a to-be-coated surface and a coating liquid, the wettability to a to-be-coated surface is improved and the applicability | paintability to a to-be-coated surface is improved. do. For this reason, even when a thin film of about several micrometers is formed with a small amount of liquid, it is effective at the point which can form the film of uniform thickness with a small thickness variation more suitably.

It is suitable that the fluorine content rate in a fluorine-type surfactant is 3-40 mass%, More preferably, it is 5-30 mass%, More preferably, it is 7-25 mass%. The fluorine-type surfactant whose fluorine content rate exists in this range is effective at the point of the uniformity of the thickness of a coating film, or liquid-liquid solution, and the solubility in a coloring composition is also favorable.

As a fluorine type surfactant, Megapak F171, copper F172, copper F173, copper F176, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437, copper F475, copper F479, copper F482 , Copper F554, copper F780, copper F781 (above, made by DIC Corporation), fluoride FC430, copper FC431, copper FC171 (or more, manufactured by Sumitomo 3M, Inc.), surflon S-382, copper SC-101, East SC-103, East SC-104, East SC-105, East SC-1068, East SC-381, East SC-383, East S-393, East KH-40 (above, made by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA), etc. are mentioned.

A block polymer can also be used as a fluorine-type surfactant, As a specific example, the compound of Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example.

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

[Formula 24]

The weight average molecular weight of the said compound becomes like this. Preferably it is 3,000-50,000, for example, 14,000.

Moreover, the fluorine-containing polymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. As a specific example, Paragraph No. 0050 of Unexamined-Japanese-Patent No. 2010-164965, and the compound of 0090 and 0289-0295, for example, Megapak RS-101, RS-102, RS-718K by DIC Corporation, etc. are mentioned. In addition, the fluorine-containing polymer which has an ethylenically unsaturated group in a side chain is a compound different from the radically polymerizable compound mentioned above.

Specific examples of the nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (for example, glycerol propoxylate and glycerin ethoxylate) and polyoxyethylene. Lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol die Stearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 made by BASF), Solsper 20000 (Nihon Lubri Sol) etc. are mentioned. Moreover, the pionein D-6112-W by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001, NCW-1002 by Wako Junyaku High School Co., Ltd. can also be used.

Specifically as a cationic surfactant, a phthalocyanine derivative (brand name: EFKA-745, the Morishita Sangyo Co., Ltd. product), organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), (meth) Acrylic acid (co) polymer polyflo no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Corporation), and the like.

As anionic surfactant, W004, W005, W017 (made by Yusho Corporation) etc. are mentioned specifically ,.

As a silicone type surfactant, Toray Dow Corning Co., Ltd. "Toray Silicon DC3PA", "Toray Silicon SH7PA", "Toray Silicon DC11PA", "Toray Silicon SH28PA", "Toray Silicon SH28PA", "Toray Silicon SH29PA" "," Toray Silicon SH30PA "," Toray Silicon SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "," TSF-4452 "made by Momentive Performance Materials "KP341", "KF6001", "KF6002", "BYK307", "BYK323", "BYK330" by the company made from Shin-Etsu Silicone Co., Ltd., etc. are mentioned.

When an active energy ray curable composition contains surfactant, it is preferable that content of surfactant is 0.001-2.0 mass% with respect to the total solid of an active energy ray curable composition, More preferably, it is 0.005-1.0 mass%. .

The active energy ray curable composition may include only one type of surfactant or may include two or more types. When it contains two or more types, it is preferable that the total amount exists in said range.

<< other additive >>

An active energy ray curable composition can mix | blend various additives, for example, a filler, adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. as needed. As these additives, Paragraph No. 0155 of Unexamined-Japanese-Patent No. 2004-295116-the thing of 0156 are mentioned, This content is integrated in this specification.

In an active energy ray curable composition, the sensitizer and light stabilizer of Paragraph No. 0078 of Unexamined-Japanese-Patent No. 2004-295116, and the thermal polymerization inhibitor of Paragraph No. 0081 of this publication can be contained.

<Example of active energy ray curable composition>

In the manufacturing method of this invention, when an active energy ray curable composition forms the cured film whose thickness is 0.5 micrometer, the optical density with respect to any wavelength in the range of wavelength 260-440 nm is 1 or more (preferably 2 or more). , More preferably 3 or more), is effective.

Moreover, when an active energy ray curable composition formed the cured film with a thickness of 0.5 micrometer, it is preferable that the minimum value of the optical density in the range of wavelength 260-440 nm is 1 or more, 2 or more are more preferable, and 3 or more are more desirable.

Moreover, when an active energy ray curable composition formed the cured film with a thickness of 0.5 micrometer, it is preferable that the optical density in wavelength 365nm is 1 or more, 2 or more are more preferable, and 3 or more are more preferable.

In addition, an optical density is a value which expressed the absorption degree in logarithm, and is a value defined by a following formula. In this invention, the optical density of a cured film is a value which measured the light transmittance with the spectrometer (UV4100 (brand name)) by Hitachi High-Technologies Corporation, and let the light transmit the light of wavelength 365nm.

OD (λ) = Log ₁₀ [T (λ) / I (λ)]

λ represents a wavelength, OD (λ) represents an optical concentration at a wavelength λ, T (λ) represents an amount of transmitted light at a wavelength λ, and I (λ) represents an incident light amount at a wavelength λ. .

In order to make the minimum value of the optical density in the said wavelength range of a cured film into 1 or more, it can achieve by containing the coloring agent which absorbs the light of the wavelength range of 260-440 nm, adjusting content of the coloring agent in all solid content, etc. suitably. Can be.

As an active energy ray curable composition which has the said optical density, the active energy ray curable composition containing a black coloring agent (preferably inorganic black coloring agent) is mentioned, for example.

Moreover, as another example of the active energy ray curable composition which has the said optical density | concentration, the ratio A / of the minimum value A of the absorbance in the range of wavelength 400 nm or more and less than 580 nm, and the minimum value B of the absorbance in the range of wavelength 580 nm or more and 750 nm or less. Active energy ray in which B is 0.3-3, and ratio C / D of the minimum value C of the absorbance in the range of wavelength 400nm or more and 750nm or less, and the maximum value D of the absorbance in the range of wavelength 1000nm or more and 1300nm or less becomes 5 or more. A curable composition is also mentioned. By using the composition which has this spectral characteristic, the maximum value of the transmittance | permeability in the range of wavelength 400-700 nm is 20% or less, and the cured film which has the spectral characteristic whose minimum value in any specific range of wavelength 850-1300 nm is 80% or more suitably is suitable. Can be formed.

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

Aλ = -log (Tλ)... (One)

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

In the present invention, the value of absorbance may be a value measured in a solution state, or may be a value in a film state formed into a film using the composition. In the case where the absorbance is measured in a film state, the composition is coated on a glass substrate so as to have a predetermined film thickness after drying by a method such as spin coating, and dried at 100 ° C. for 120 seconds using a hot plate. It is preferable to use the prepared membrane. The film thickness of a film | membrane measures the board | substrate which has a film | membrane using a stylus type surface shape measuring instrument (DEKTAK150 by ULVAC company).

In addition, absorbance can be measured using a conventionally well-known spectrophotometer. Although the measurement conditions of absorbance are not specifically limited, The minimum value B of the absorbance in the range of 580 nm or more and 750 nm or less on the conditions adjusted so that the minimum value A of the absorbance in the range of wavelength 400 nm or more and less than 580 nm may be 0.1-3.0. It is preferable to measure the minimum value C of the absorbance in the range of wavelength 400 nm or more and 750 nm or less, and the maximum value D of the absorbance in the range of wavelength 1000 nm or more and 1300 nm or less. By measuring the absorbance under such conditions, the measurement error can be made smaller. There is no restriction | limiting in particular as a method of adjusting so that the minimum value A of the light absorbency in the range of wavelength 400nm or more and less than 580nm may be 0.1-3.0. For example, when measuring absorbance in a composition (solution) state, the method of adjusting the optical path length of a sample cell is mentioned. Moreover, when measuring absorbance in a film | membrane state, the method of adjusting film thickness, etc. are mentioned.

The measuring method of the spectral characteristic of a film | membrane, a film thickness, etc. is shown below.

The composition was applied onto a glass substrate by a method such as spin coating so that the film thickness after drying became the predetermined film thickness described above, and dried at 100 ° C. for 120 seconds using a hot plate. The film thickness of the film | membrane measured the board | substrate after drying which has a film | membrane using the stylus type surface shape measuring device (DEKTAK150 by ULVAC company). The transmittance | permeability in the range of 300-1300 nm was measured for the board | substrate after drying which has this film | membrane using the ultraviolet visible near-infrared spectrophotometer (U-4100 by Hitachi High-Technologies Corporation).

The active energy ray curable composition which has the said spectral characteristic can mention the composition containing the color material which shields visible light. It is preferable that the color material which shields visible light is a material which absorbs light of a wavelength range of purple to red. It is preferable that the color material which shields visible light meets at least one of the following (A) and (B).

(A): Two or more types of chromatic colorants are included and black is formed by the combination of two or more kinds of chromatic colorants.

(B): The organic type black coloring agent is included.

The above-mentioned thing is mentioned as a chromatic coloring agent and an organic type black coloring agent.

In this invention, the color material which shields visible light has A / B 4.5 which is ratio of the minimum value A of the absorbance in the range of 450-650 nm, and the minimum value B of the absorbance in the range of 900-1300 nm, for example. It is preferable that it is above. The above characteristics may be satisfied by one type of material or may be satisfied by a combination of a plurality of materials.

In the case of said aspect (A), it is preferable to contain 2 or more types of coloring agents chosen from a red coloring agent, a yellow coloring agent, a blue coloring agent, and a purple coloring agent. Moreover, it is preferable to contain at least 1 sort (s) chosen from a red coloring agent, a yellow coloring agent, and a purple coloring agent, and a blue coloring agent. Especially, the aspect in any one of the following (1)-(3) is preferable.

(1) The aspect containing a red colorant, a yellow colorant, a blue colorant, and a purple colorant.

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

(3) The aspect containing a yellow coloring agent, a blue coloring agent, and a purple coloring agent.

As a chromatic coloring agent, when it contains a red coloring agent, a yellow coloring agent, a blue coloring agent, and a purple coloring agent, the mass ratio of a red coloring agent is 0.1-0.6, and the mass ratio of a yellow coloring agent is 0.1-0.6 in the mass ratio with respect to the whole coloring colorant. It is preferable that it is 0.4, the mass ratio of a blue coloring agent is 0.1-0.6, and the mass ratio of a purple coloring agent is 0.01-0.3. More preferably, the mass ratio of the red colorant is 0.2-0.5, the mass ratio of the yellow colorant is 0.1-0.3, the mass ratio of the blue colorant is 0.2-0.5, and the mass ratio of the purple colorant is 0.05-0.25.

Moreover, when it contains a red colorant, a yellow colorant, and a blue colorant as a chromatic colorant, the mass ratio of a red colorant is 0.2-0.7, the mass ratio of a yellow colorant is 0.1-0.4, in the mass ratio with respect to the chromatic colorant whole quantity, It is preferable that the mass ratio of a blue coloring agent is 0.1-0.6. More preferably, the mass ratio of a red colorant is 0.3-0.6, the mass ratio of a yellow colorant is 0.1-0.3, and the mass ratio of a blue colorant is 0.2-0.5.

Moreover, when it contains a yellow coloring agent, a blue coloring agent, and a purple coloring agent as a chromatic coloring agent, the mass ratio of a yellow coloring agent is 0.1-0.4, and the mass ratio of a blue coloring agent is 0.1-0.6 in the mass ratio with respect to the whole coloring colorant. It is preferable that the mass ratio of a coloring agent is 0.2-0.7. More preferably, the mass ratio of the yellow colorant is 0.1-0.3, the mass ratio of the blue colorant is 0.2-0.5, and the mass ratio of the purple colorant is 0.3-0.6.

Moreover, in the active energy ray curable composition which has the said spectral characteristic, you may further contain an infrared absorber (preferably, the infrared absorber which has an absorption maximum in the range of wavelength 800-900 nm). Thereby, the cured film which has the spectral characteristic whose maximum value of the transmittance in the range of wavelength 400-830 nm is 20% or less, and the minimum value of the transmittance in the range of wavelength 1000-1300 nm is 80% or more can be formed suitably.

In this aspect, it is preferable that an infrared absorber contains 10-200 mass parts with respect to 100 mass parts of color materials which light-shield visible light. Moreover, it is preferable that it is 1-60 mass% of the total solid of a composition, and, as for content of an infrared absorber, it is more preferable that it is 10-40 mass%. It is preferable that it is 10-60 mass% of the total solid of a composition, and, as for content of the color material which shields visible light, it is more preferable that it is 30-50 mass%. It is preferable that it is 1-80 mass% with respect to the total solid of a composition, and, as for the total amount of the infrared absorber and the color material which shields visible light, it is more preferable that it is 20-70 mass%, and it is more preferable that it is 30-70 mass%. .

<Preparation method of an active energy ray curable composition>

An active energy ray curable composition can mix and prepare the above-mentioned component.

At the time of preparation of an active energy ray curable composition, you may mix | blend each component collectively, and you may mix | blend sequentially, after melt | dissolving and disperse | distributing each component to a solvent. In addition, the addition order and working conditions at the time of compounding are not restrict | limited. For example, a composition may be prepared by dissolving and dispersing all the components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions and dispersions. You may prepare.

In preparation of an active energy ray curable composition, it is preferable to filter by a filter for the purpose of removal of a foreign material, reduction of a defect, etc. As a filter, if it is conventionally used for a filtration use etc., it can use without being specifically limited. For example, fluorine resins 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) (high density And / or ultra high molecular weight polyolefin resins). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

As for the pore diameter of a filter, about 0.01-7.0 micrometers is suitable, Preferably it is about 0.01-3.0 micrometers, More preferably, it is about 0.05-0.5 micrometer. By setting it as this range, it becomes possible to reliably remove the fine foreign material which inhibits preparation of a uniform and smooth composition in a later process. Moreover, it is also preferable to use a fiber-shaped filter medium, As a filter medium, polypropylene fiber, nylon fiber, glass fiber, etc. are mentioned, for example, SBP type series (SBP008 etc.) and TPR type series by Rocky Techno Co., Ltd. are mentioned, for example. (TPR002, TPR005, etc.) and filter cartridges of the SHPX type series (SHPX003, etc.) can be used.

When using a filter, you may combine another filter. In that case, the filtering by a 1st filter may be only once, and may be performed twice or more.

Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The hole diameter here can refer to the nominal value of a filter manufacturer. Examples of commercially available filters include Nippon-Paul Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.) You can choose from the various filters provided.

As the second filter, one formed of the same material as that of the first filter described above can be used.

For example, filtering by a 1st filter may be performed only by a dispersion liquid, and after mixing another component, you may perform 2nd filtering.

<Curing film>

The cured film of this invention is obtained by the manufacturing method of the cured film of the said invention.

It is preferable that the optical density with respect to any wavelength in the range of wavelength 260-440 nm of the cured film of this invention is 1 or more, 2 or more are more preferable, and 3 or more are more preferable.

Moreover, it is preferable that the minimum value of the optical density in the range of wavelength 260-440 nm is 1 or more, 2 or more are more preferable, and 3 or more are more preferable.

Moreover, it is preferable that the optical density in wavelength 365nm is 1 or more, 2 or more are more preferable, and 3 or more are more preferable.

According to this invention, even if it is a cured film with a high optical density in the said wavelength range, it can manufacture by a low temperature process. For this reason, the higher the optical density is, the more significant the effect of the present invention is.

It is preferable that the said optical density is the value in thickness of 0.5 micrometer or more of cured film.

It is preferable that the thickness of the cured film of this invention is 0.1-45 micrometers. 44 micrometers or less are more preferable, as for an upper limit, 43 micrometers or less are more preferable, and 40 micrometers or less are further more preferable. As for a minimum, 0.2 micrometer or more is more preferable, for example. If the thickness of a cured film is the said range, the reliability of a cured film and adhesiveness with a base material are favorable.

The cured film of this invention can be used suitably for a color filter, an infrared transmission filter, an infrared cut filter, a light shielding film, a transparent film, a band pass filter, etc. Moreover, a printed matter can also be formed using an active energy ray curable composition as a printing ink.

In addition, in this invention, a color filter means the filter which passes | blocks the light of a specific wavelength, and transmits the light of a specific wavelength among the light of the wavelength of a visible range. In addition, an infrared transmission filter means the filter which light-shields the light of the wavelength of a visible range, and transmits the light (infrared ray) of the wavelength of a specific infrared region. In addition, an infrared cut-off filter means the filter which permeate | transmits the light (visible light) of the wavelength of a visible range, and shields at least one part of the light (infrared) of the wavelength of an infrared range. In addition, a light shielding film means the film | membrane which shields the light of the wavelength of a visible range at least. In addition, a transparent film means the film | membrane which permeate | transmits light of the wavelength of a visible range at least.

A color filter, an infrared transmission filter, and an infrared cut filter are solid-state imaging elements, such as CCD (charge coupling element) and CMOS (complementary metal oxide film semiconductor), image display apparatuses, such as a liquid crystal display device, organic electro luminescence (organic EL) element etc. can be used preferably.

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

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

Although it will not specifically limit, if it is a structure provided with the cured film of this invention and functioning as a solid-state image sensor as a solid-state image sensor, For example, the following structures are mentioned.

On the support, it has a transfer electrode which consists of several photodiodes and polysilicon etc. which comprise the light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.), and only the light receiving part of a photodiode on a photodiode and a transfer electrode It has an open light shielding film, has a device protective film which consists of silicon nitride etc. formed on the light shielding film so that the light shielding film whole surface and a photodiode light-receiving part may be covered, and a color filter is provided on a device protective film.

Moreover, the structure which has light concentrating means (for example, a micro lens etc .. same below) on a device protective film and under a color filter (side close to a support body), the structure which has light concentrating means on a color filter, etc. may be sufficient.

As an image display apparatus, a liquid crystal display device, an organic electroluminescent display apparatus, etc. are mentioned. For the definition of the display device and the details of each display device, for example, "Electronic display device (Aki Sasaki by Co., Ltd., Kosago Co., Ltd., 1990)", "Display device (by Ibuki Sumiaki, by Sangyo Tosho (Note) ) Issued in the first year of Heisei). Moreover, about a liquid crystal display device, it describes in the "next-generation liquid crystal display technology (Datsuo Uchida Editing, Kosago Co., Ltd., 1994)." There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

The image display device may have a white organic EL element. As the white organic EL device, one having a tandem structure is preferable. Regarding the tandem structure of the organic EL device, Japanese Laid-Open Patent Publication No. 2003-45676, supervised by Mikami Akiyoshi, "A front line of organic EL technology development-high brightness, high precision, long life, know-how collection", Kijutsu Joho Kykai, 326 -328 pages, 2008. It is preferable that the spectrum of the white light which organic electroluminescent element emits has a strong maximum emission peak in blue region (430nm-485nm), green region (530nm-580nm), and yellow region (580nm-620nm). In addition to these emission peaks, it is more preferable to further have a maximum emission peak in the red region (650 nm-700 nm).

Example

An Example is given to the following and this invention is demonstrated to it further more concretely. The material, the amount of use, the ratio, the treatment content, the treatment sequence, and the like, which are shown in the following examples, can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below. In addition, "part" and "%" are mass references | standards unless there is particular notice.

<Test Example 1>

[Production of Titanium Black A-1]

120 g of titanium oxide having a BET specific surface area of 110 m ² / g ("TTO-51N" (trade name: Ishihara Sangyo Co., Ltd.), 25 g of silica particles having a BET surface area of 300 m ² / g ("AEROSIL 300", manufactured by Evonic), And 100 g of a dispersant ("DISPERBYK-190", manufactured by BYKChemie) was added, and 71 g of ion electro-exchange water was added and uniformly treated by using a MAZERSTAR KK-400W manufactured by KURABO at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm for 30 minutes. One mixture aqueous solution was obtained. The aqueous solution was filled into a quartz vessel, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama, KK), and then the atmosphere was replaced with nitrogen. The nitriding reduction process was performed by passing time. The powder collected after completion was pulverized in a mortar, and contained titanium atoms (A-1) having a specific surface area of 85 m ² / g in powder form (a dispersion of titanium black particles and Si atoms). Got.

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

The component shown in the following composition 1 was mixed for 15 minutes using the stirrer (EUROSTAR by IKA Corporation), and the dispersion a was obtained.

The obtained dispersion a was subjected to dispersion treatment under the following conditions using an ultra-apex mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd., and a nylon filter (made by Nippon Pole Co., Ltd., DFA4201NXEY) having a pore diameter of 0.45 μm was used. Filtration was carried out to obtain a titanium black dispersion (hereinafter, referred to as TB dispersion 1).

(Composition 1)

Titanium black (A-1) obtained as mentioned above. 25 parts by mass

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

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

Resin 1: The following structure. It synthesize | combined with reference to description of Unexamined-Japanese-Patent No. 2013-249417. In addition, in the formula of Resin 1, x was 43 mass%, y was 49 mass%, and z was 8 mass%. Moreover, the weight average molecular weight of resin 1 was 30,000, the acid value was 60 mgKOH / g, and the number of atoms (except hydrogen atoms) of the graft chain was 117.

[Formula 25]

(Dispersion condition)

Bead diameter: 0.05mm in diameter

Bead filling rate: 75% by volume

Mill circumference: 8 m / s

Mixed liquid amount to be dispersed: 500 g

Circulating flow rate (pump supply): 13 kg / hr

Treatment liquid temperature: 25 ~ 30 ℃

Cooling water: tap water

Volume in bead mill annular passage: 0.15L

Number of passes: 90 passes

[Preparation of active energy ray curable composition]

After mixing the following composition, it filtered using the nylon filter (made by Nippon Pole Co., Ltd., DFA4201NXEY) of 0.45 micrometer of pore diameters, and prepared the 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

Photoinitiator (IRGACURE-OXE02 (made by BASF)). 1.81 parts by mass

Radically polymerizable compound (KAYARAD DPHA (brand name: Nippon Kayaku Co., Ltd.))… 6.29 parts by mass

Surfactant 1... 0.02 parts by mass

Solvent (cyclohexanone) 4.66 parts by mass

Fluorine-type surfactant (Megapak RS-72-K, a fluorine-containing polymer which has an ethylenically unsaturated group in a side chain (DIC Corporation make, 30% of solid content, a solvent: propylene glycol monomethyl ether acetate)): 10.65 mass parts

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

Alkali-soluble resin 1: The following structure. It synthesize | combined according to the manufacturing method of Paragraph No. 0338 of Unexamined-Japanese-Patent No. 2010-106268-0340. In addition, in the following formula, x was 90 mass%, and z was 10 mass%. Moreover, the weight average molecular weight of alkali-soluble resin 1 was 40,000, the acid value was 100 mgKOH / g, and the number of atoms of a graft chain (except hydrogen atom) was 117.

[Formula 26]

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

[Formula 27]

[Production of Cured Film]

The thing which performed the hexamethyldisilazane (HMDS) process about the glass base material (diameter 200mm (8 inches), thickness 0.7mm, 1737 (made by brand name Corning Corporation)) was used as a base material. HMDS process was performed at 100 degreeC for 60 second using ACT8 (brand name) by Tokyo Electron.

After apply | coating the active energy ray curable composition produced above to the glass base material which performed the HMDS process by the spin coat method, it heat-processed (prebaked) for 100 second using the 65 degreeC hotplate. The coating film thickness of an active energy ray curable composition was adjusted so that the film thickness after prebaking might be set to 4.0 micrometers.

Subsequently, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Corporation, NA / σ = 0.63 / 0.65, Focus offset = 0 μm), the transfer pattern (10 μm × 10 μm island, pitch 20 μm) was used. It exposed at the exposure amount of 8,000 J / m <^2> through the mask.

Subsequently, 0.3 mass% and 0.01 mass of tetramethylammonium hydroxide (TMAH) of surfactant NCW-101 (nonionic surfactant) by Wako Junyaku Kogyo Co., Ltd. were made using AD-1200 (made by Mikasa Co., Ltd.). In the developing solution containing%, the puddle was developed for 40 seconds.

Next, the rinse process was performed using pure water, and it dried at high speed rotation of 200 rpm for 30 second after that.

Next, electron beam irradiation was performed on the following conditions and the cured film was manufactured.

Electron beam irradiation conditions

Device: Electron beam irradiation device made by Hamamatsu Photonics

Acceleration voltage: 5.0kV ~ 200kV, Tube voltage: 4.0mA

Absorbed Dose: 145kGy

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scan speed at the time of processing): 100mm / second (in substrate of diameter 200mm, two pieces / second)

Treatment temperature: 23 ℃ or 50 ℃

(Measurement of Optical Density (OD Value) of Cured Film)

The light of wavelength 260-440 nm is made to enter into the obtained cured film (4 micrometers in thickness), and the transmittance is measured using the Hitachi High-Technologies spectrometer UV4100 (brand name), and the minimum value of the optical density in the range of wavelength 260-440 nm. Was measured.

(Evaluation of Adhesiveness of Cured Film)

After immersing the obtained cured film in the cyclohexanone solution for 10 minutes, adhesiveness was evaluated on the following references | standards.

A: No pattern peeling

B: Pattern Peeling Occurs

(Appearance Evaluation of Curing Film)

The external appearance of the obtained cured film was evaluated.

A: good

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

C: A lot of turbidity arises on the surface, and it is not practical.

(Evaluation of Reliability of Curing Film)

Temperature cycle test immunity

The temperature cycle test of the cured film was done on condition of the following.

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

Test conditions: It was left to stand for 15 minutes in the atmosphere of -45 degreeC and 85 degreeC, 50 cycles were carried out using this as 1 cycle, and the temperature cycling test tolerance was evaluated based on the following references | standards.

A: There is no pattern peeling.

B: Although turbidity arose on the surface, there is no problem. There is no pattern peeling.

C: A lot of turbidity arises on the surface, and it is not practical. Pattern peeling is also mixed.

Constant temperature and humidity test resistance

The constant temperature and humidity test of the cured film was done on condition of the following.

After standing for 100 hours in an environment of 85 ° C and 85% relative humidity, the constant temperature and humidity test resistance was evaluated based on the following criteria.

A: There is no pattern peeling.

B: Although turbidity arose on the surface, there is no problem. There is no pattern peeling.

C: A lot of turbidity arises on the surface, and it is not practical. Pattern peeling is also mixed.

TABLE 1

As shown in the table above, the test No. 1, which was irradiated with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV. 101-108 was able to manufacture the cured film excellent in reliability. Moreover, adhesiveness and an external appearance of the obtained cured film were also favorable.

On the other hand, test No. whose acceleration voltage is less than 10 kV. C11, Test No. of which the acceleration voltage is 100 kV or more. C12 and 13 were inferior in the reliability of the obtained cured film.

<Test Example 2>

[Preparation of active energy ray curable composition]

After mixing the following composition, it filtered using the nylon filter (made by Nippon Pole Co., Ltd., DFA4201NXEY) of 0.45 micrometer of pore diameters, and prepared the active energy ray curable composition.

(Furtherance)

Thermosetting resin (cyclomer P (ACA) 230AA, manufactured by Daicel Co., Ltd.) 10.96 mass%

Propylene Glycol Monomethyl Ether Acetate… 89.03 mass%

Surfactant 1... 0.01 mass%

Silane coupling agent (KBM-602, Shin-Etsu Chemical Co., Ltd.)… The ratio (mass% with respect to solid content in a composition) shown in Table 2

In addition, surfactant 1 used the same thing as surfactant 1 of the active energy ray curable composition of Test Example 1.

[Production of Cured Film]

After apply | coating the active energy ray curable composition produced above to the glass base material which performed the HMDS process by the spin coat method, it heat-processed (prebaked) for 100 second using the 65 degreeC hotplate. The coating film thickness of an active energy ray curable composition was adjusted so that the film thickness after prebaking might be 0.3 micrometer.

Next, electron beam irradiation was performed on the following conditions and the cured film was manufactured.

Electron beam irradiation conditions

Device: Electron beam irradiation device made by Hamamatsu Photonics

Acceleration voltage: 70 kV, tube voltage: 4.0 mA

Absorbed Dose: 145kGy

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scan speed at the time of processing): 100mm / second (in substrate of diameter 200mm, two pieces / second)

Treatment 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 (film thickness of 0.3 μm) was measured.

(Evaluation of adhesiveness (cross cut))

The adhesiveness of the cured film produced above was evaluated by the cross cut test (according to JIS K5600. However, it performed by the grid pattern which consists of 100 film pieces). In the cross-cut test, cutting of the depth until reaching a base material was carried out 11 places in the longitudinal direction and the transverse direction with respect to the cured film.

The number of the peeled film pieces among 100 film pieces was evaluated in accordance with the following evaluation criteria, and the result obtained is shown in Table 2 below.

A: 0

B: 1 or more but less than 100

C: 100

(Appearance Evaluation of Curing Film)

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

(Evaluation of Reliability of Curing Film)

Temperature cycle test immunity

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

Constant temperature and humidity test resistance

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

TABLE 2

As shown in the table above, the test No. 1, which was irradiated with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV. 201-206 were able to manufacture the cured film excellent in reliability.

<Test Example 3>

[Preparation of active energy ray curable composition]

After mixing the following composition, it filtered using the nylon filter (made by Nippon Pole Co., Ltd., DFA4201NXEY) of 0.45 micrometer of pore diameters, and prepared the active energy ray curable composition.

(Furtherance)

Resin (Acrylic RD-F8, made by Nippon Shokubai Co., Ltd.) 19.08 parts by mass

Radically polymerizable compound (Aronix TO-2349, product of Toagosei Co., Ltd.) 47.7 parts by mass

Photoinitiator (IRGACURE-184, made by BASF Corporation)... 4.10 parts by mass

Photopolymerization initiator (Lucirin-TPO, manufactured by BASF)... 0.57 parts by mass

Silane coupling agent (KBM-602, Shin-Etsu Chemical Co., Ltd.)… 0.05 parts by mass

Surfactant (NCW-101, Wako Junyaku Kogyo Co., Ltd.) 0.01 parts by mass

Propylene Glycol Monomethyl Ether Acetate… 28.62 parts by mass

[Production of Cured Film]

After apply | coating the active energy ray curable composition produced above to the glass base material (diameter 200mm (8 inches), thickness 0.7mm, 1737 (brand name Corning Corporation)) on condition of the following, using a 65 degreeC hotplate, Heat processing (prebaking) was performed for 100 second.

Application: Spray coating method

Atomization pressure: 450Pa

Flow rate: 3.0 cm ³ / min

Distance between nozzle and substrate: 30mm

Coating scan speed: 200mm / second (in base material of diameter 200mm, two pieces / second)

Scan Pitch: 5.0mm

Coating film thickness: 10.0μm-50.0μm (film thickness after prebaking, the film thickness is defined by the number of scans)

Subsequently, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Corporation, NA / σ = 0.63 / 0.65, Focus offset = 0 μm), the transfer pattern (500 μm × 500 μm island, pitch is 1000 μm) was used. It exposed at the exposure amount of 8000 J / m <^2> through the mask.

Subsequently, it developed for 60 second in the puddle in alkaline developing solution (0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH)) using AD-1200 (made by Mikasa Corporation).

Next, the rinse process was performed using pure water, and it dried at high speed rotation of 200 rpm for 30 second after that.

Next, electron beam irradiation was performed on the following conditions and the cured film was manufactured.

Electron beam irradiation conditions

Device: Electron beam irradiation device made by Hamamatsu Photonics

Acceleration voltage: 95 kV, tube voltage: 4.0 mA

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scan speed at the time of processing): 100mm / second (in substrate of diameter 200mm, two pieces / second)

Treatment 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 (film thickness shown in Table 3) was measured.

(Evaluation of Reliability of Curing Film)

Temperature cycle test immunity

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

Constant temperature and humidity test resistance

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

TABLE 3

As shown in the table above, the test No. 1, which was irradiated with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV. 301-306 could manufacture the cured film excellent in reliability.

<Test Example 4>

As a base material, the glass base material which performed the HMDS process used in the test example 1 was used.

After apply | coating a red resist (SR2000, Fujifilm Electronic Materials Co., Ltd.) by the spin coat method, heat processing (prebaking) was performed for 150 second using the 65 degreeC hotplate. The coating film thickness of an active energy ray curable composition was adjusted so that the film thickness after prebaking might be set to 2 micrometers.

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

Subsequently, it developed for 60 second in the puddle in alkaline developing solution (0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH)) using AD-1200 (made by Mikasa Corporation).

Next, the rinse process was performed using pure water, and it dried at high speed rotation of 200 rpm for 30 second after that.

Next, hardening process was performed on either of the following conditions, and the cured film (red colored pattern) was manufactured.

(EB Curing 1)

Device: Electron beam irradiation device made by Hamamatsu Photonics

Acceleration voltage: 70 kV, tube voltage: 4.0 mA

Absorbed Dose: 145kGy

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scan speed at the time of processing): 100mm / second (in substrate of diameter 200mm, two pieces / second)

Treatment temperature: 23 ℃

(EB Curing 2)

Device: Electron beam irradiation device made by Hamamatsu Photonics

Acceleration voltage: 120 kV, tube voltage: 4.0 mA

Absorbed Dose: 145kGy

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scan speed at the time of processing): 100mm / second (in substrate of diameter 200mm, two pieces / second)

Treatment temperature: 23 ℃

(UV curing)

Exposure amount (ultraviolet rays): 3,000mJ / cm ²

Temperature: 35 ℃

(Spectral evaluation)

The spectra of the film before the curing treatment and the spectroscopy of the film after the curing treatment under the conditions of EB curing 1 were measured using a spectrometer (MCPD3000, manufactured by Otsuka Denshi Co., Ltd.).

(Reliability of hard film)

The cured film cured under the conditions of EB Curing 1 was subjected to temperature cycle test resistance and constant temperature and humidity test resistance in the same manner as in Test Example 1, and the reliability of the cured film was evaluated. .

(Evaluation of mixed colors)

The maximum transmittance T0 in the wavelength range of 600-700 nm was measured using the spectrometer (MCPD3000, Otsuka Denshi Corporation) for the spectroscopy of the film | membrane before a hardening process.

Next, a blue resist (SB2000, manufactured by FUJIFILM Materials) for blending color evaluation was spin-coated so that the film thickness after drying might be set to 2 micrometers on the red colored pattern manufactured by performing each hardening process, and it is 150 second at 65 degreeC. Heat treatment (prebaking) was performed.

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

Subsequently, it developed for 60 second in the puddle in alkaline developing solution (0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH)) using AD-1200 (made by Mikasa Corporation).

Next, the rinse process was performed using pure water, and it dried at high speed rotation of 200 rpm for 30 second after that, and formed the blue coloring pattern.

Next, the maximum transmittance | permeability T1 in the wavelength range of 600-700 nm is measured with the spectrometer (MCPD3000, Otsuka Denshi Co., Ltd.) about the cured film (red coloring pattern) after forming a blue coloring pattern, and maximum transmittance | permeability The change (ΔT = T0-T1) was calculated.

Moreover, the spectrum after the hardening of the red coloring pattern after hardening on the conditions of the hardening process of the red coloring pattern, EB hardening 1, and UV hardening is shown in FIG.

TABLE 4

Test No. which hardened | cured on condition of EB hardening 1 from said result. 401 was able to effectively suppress mixed color of other colors.

<Test Example 5>

About the base material shown in the following table | surface, heat processing for 5 minutes (hotplate) or 1 hour (oven) was performed at electron beam irradiation or 220 degreeC, and the damage of a base material was evaluated with the following references | standards.

Electron beam irradiation was performed on condition of the following.

Electron beam irradiation conditions

Device: Electron beam irradiation device made by Hamamatsu Photonics

Acceleration voltage: 95 kV, tube voltage: 4.0 mA

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scan speed at the time of processing): 100mm / second (in substrate of diameter 200mm, two pieces / second)

Treatment temperature: 23 ℃

Five substrates were used for each treatment condition. In addition, the numerical value in parentheses in a table | surface is a defective rate.

A: The base material after the treatment is free from warpage, damage, cracks, and discoloration.

B: Part of the substrate had cracks or damage.

C: The base material of 1-3 sheets had a crack or curvature.

D: The four or more base materials had cracks or warpage.

A 220 degreeC hotplate / oven and an electron beam irradiation are mentioned as a method of hardening of a composition. The damage of the base material by these hardening methods was evaluated (5 base materials used).

TABLE 5

As is clear from the above results, even if the base material generated warpage, damage, cracks, or the like in the heat treatment, warpage, damage, and cracks did not occur in the electron beam irradiation.

<Test Example 6>

[Preparation of Pigment Dispersion B-1]

The mixed solution of the following composition was mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) with a pressure reduction mechanism) using 0.3 mm diameter zirconia beads to obtain a pigment. Dispersion B-1 was prepared.

A mixed pigment consisting of a red pigment (C. I. Pigment Red 254) and a yellow pigment (C. I. Pigment Yellow 139) (C. I. Pigment Red 254: C. I. Pigment Yellow 139 = 4: 1 (mass ratio)). 11.8 parts by mass

Resin 1 (dispersant) (manufactured by BYK Chemie, DISPERBYK-111)... 9.1 parts by mass

Propylene glycol methyl ether acetate... 79.1 parts by mass

[Preparation of Pigment Dispersion B-2]

The mixed solution of the following composition was mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) with a pressure reduction mechanism) using 0.3 mm diameter zirconia beads to obtain a pigment. Dispersion B-2 was prepared.

A mixed pigment (C. I. pigment blue 15: 6: C. I. pigment violet 23 = 9: 4 (mass ratio)) consisting of a blue pigment (C. I. pigment blue 15: 6) and a purple pigment (C. I. pigment violet 23). 12.6 parts by mass

Resin 1 (dispersant) (manufactured by BYK Chemie, DISPERBYK-111)... 2.0 parts by mass

Resin 2 (dispersant). 3.3 parts by mass

Cyclohexanone 31.2 parts by mass

Propylene glycol methyl ether acetate... 50 parts by mass

Resin 2: The following structure (ratio in repeat unit is molar ratio, Mw = 14,000)

Resin 2 is also an alkali-soluble resin.

[Formula 28]

[Preparation of active energy ray curable composition]

After mixing the following composition, it filtered using the nylon filter (made by Nippon Pole Co., Ltd., DFA4201NXEY) of 0.45 micrometer of pore diameters, and prepared the active energy ray curable composition.

(Furtherance)

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

Pigment dispersion B-2... 37.1 parts by mass

Alkali-soluble resin 1... 1.1 parts by mass

Radically polymerizable compound 1... 1.8 parts by mass

Silane coupling agent 1... 0.6 parts by mass

Photopolymerization initiator 1... 0.9 parts by mass

Surfactant 1:... 4.2 parts by mass

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

PGMEA…. 7.8 parts by mass

Alkali-soluble resin 1: The following structure (ratio in recurring unit is molar ratio, Mw = 11,000)

[Formula 29]

Radical polymerizable compound 1: the following structure (mixture in which the molar ratio of the left compound and the right compound is 7: 3)

[Formula 30]

·

·

Silane coupling agent 1: the following structure

[Formula 31]

Photopolymerization initiator 1: the following structure

[Formula 32]

In addition, surfactant 1 used the same thing as surfactant 1 of the active energy ray curable composition of Test Example 1.

[Production of Cured Film]

After apply | coating the active energy ray curable composition produced above to the glass base material (diameter 200mm (8 inches), thickness 0.7mm, 1737 (brand name Corning Corporation)), heat-process for 120 second using a 65 degreeC hotplate ( Prebaking). The coating film thickness of an active energy ray curable composition was adjusted so that the film thickness after prebaking might be set to 2 micrometers.

Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Corporation, NA / σ = 0.63 / 0.65, Focus offset = 0 μm), through a mask having a transfer pattern (pattern size: 100 μm × 100 μm) It exposed at the exposure amount of 500mJ / cm <^2> .

Subsequently, it developed for 60 second in the puddle in alkaline developing solution (0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH)) using AD-1200 (made by Mikasa Corporation).

Subsequently, rinse treatment was performed using pure water, followed by drying at high speed of 200 rpm for 30 seconds.

Subsequently, after hardening process was performed on either of the following conditions, the baking process was further performed at 240 degreeC for 5 minutes using a hotplate.

(EB Curing)

Device: Electron beam irradiation device made by Hamamatsu Photonics

Acceleration voltage: 70 kV, tube voltage: 4.0 mA

Absorbed Dose: 145kGy

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scan speed at the time of processing): 100mm / second (in substrate of diameter 200mm, two pieces / second)

Treatment temperature: 23 ℃

(UV curing)

Exposure amount (ultraviolet rays): 3,000mJ / cm ²

Temperature: 35 ℃

(Heat curing)

In oven, 1 hour at 220 ° C

(Measurement of optical density (OD value))

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

(Evaluation of Reliability of Curing Film)

Temperature cycle test immunity

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

Constant temperature and humidity test resistance

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

(Exterior)

The external appearance of the film | membrane after further baking after hardening processing and after hardening processing was evaluated.

A: No problem

B: wrinkles on the surface

TABLE 6

As shown in the table above, the test No. 1, which was irradiated with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV. 601 is No. which performed heat-hardening. The cured film which was excellent in reliability similar to 603 was able to be manufactured. Moreover, after hardening, the film | membrane after further baking did not have a wrinkle, and the external appearance was favorable.

On the other hand, test No. which performed UV hardening. 602 was inferior in reliability. In addition, wrinkles occurred in the film after further baking. Since the hardening was accelerated only on the surface of the exposure pattern and the polymerization inside the pattern was insufficient, it is presumed that wrinkles occurred on the surface due to the surface shrinkage difference between the surface and the inside due to the treatment at a high temperature.

<Test Example 7>

[Preparation of active energy ray curable composition]

After mixing the following composition, it filtered using the nylon filter (made by Nippon Pole Co., Ltd., DFA4201NXEY) of 0.45 micrometer of pore diameters, and prepared the active energy ray curable composition.

(Furtherance)

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

Acid generator (WPAG-469, manufactured by Wako Junyaku Kogyo Co., Ltd., 20% propylene glycol monomethyl ether acetate solution); 1.0 mass%

Surfactant 1... 0.1 mass%

Propylene glycol monomethyl ether acetate (PGMEA); 94.9 mass%

In addition, surfactant 1 used the same thing as surfactant 1 of the active energy ray curable composition of Test Example 1.

[Production of Cured Film]

After apply | coating the active energy ray curable composition produced above to the glass base material (diameter 200 mm (8 inches), thickness 0.7 mm, 1737 (brand name Corning Corporation make)) by the spin coat method, it uses a 65 degreeC hotplate. The heat treatment (prebaking) was performed for 120 seconds. The coating film thickness of an active energy ray curable composition was adjusted so that the film thickness after prebaking might be 0.1 micrometer.

Next, electron beam irradiation (made by Hamamatsu Photonics Co., Ltd.) was performed on condition of the following, and the cured film was manufactured.

(EB condition 1)

Acceleration voltage: 70 kV, tube voltage: 4.0 mA

Absorbed Dose: 145kGy

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scanning speed during processing): 100 mm / sec x 1 scan

Treatment temperature: 23 ℃

(EB condition 2)

Acceleration voltage: 50 kV, tube voltage: 2.6 mA

Absorbed dose: 15kGy

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scanning speed during processing): 100 mm / sec x 1 scan

Treatment temperature: 23 ℃

(EB condition 3)

Acceleration voltage: 50 kV, tube voltage: 2.6 mA

Absorbed dose: 30kGy

Clearance of substrate and electron source: 10mm

Oxygen concentration ≤ 1000 volume ppm

Carrying speed (scanning speed during processing): 100 mm / sec x 2 scans

Treatment 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 on the following references | standards.

A: No abnormality in the membrane surface and no change in the membrane thickness

B: There is an abnormality in the membrane surface or there is a variation in the membrane thickness.

(Evaluation of Reliability of Curing Film)

Temperature cycle test immunity

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

Constant temperature and humidity test resistance

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

TABLE 7

As shown in the table above, the test No. 1, which was irradiated with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV. 701-703 were able to manufacture the cured film excellent in reliability.

Claims (26)

As a manufacturing method of the cured film containing the process of irradiating the layer of the active energy ray curable composition on a base material with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV,
Exposing the layer of the active energy ray curable composition, and after the exposing step, developing the layer of the active energy ray curable composition to form a pattern,
The step of irradiating the electron beam is performed after the step of forming the pattern,
The manufacturing method of the cured film performed at the temperature of 100 degrees C or less through all the processes. As a manufacturing method of the cured film containing the process of irradiating the layer of the active energy ray curable composition on a base material with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV,
The said base material is a thermoplastic resin base material comprised from the thermoplastic resin whose glass transition temperature is 100 degrees C or less,
The manufacturing method of the cured film performed at the temperature of 100 degrees C or less through all the processes. As a manufacturing method of the cured film containing the process of irradiating the layer of the active energy ray curable composition on a base material with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV,
The said cured film is the optical density with respect to any wavelength in the range of wavelength 260-440 nm, 1 or more,
The manufacturing method of the cured film performed at the temperature of 100 degrees C or less through all the processes. As a manufacturing method of the cured film containing the process of irradiating the layer of the active energy ray curable composition on a base material with an electron beam of an acceleration voltage of 10 kV or more and less than 100 kV,
The substrate includes an organic semiconductor layer,
The manufacturing method of the cured film performed at the temperature of 100 degrees C or less through all the processes. The method according to any one of claims 1 to 4,
The said active energy ray curable composition is a manufacturing method of the cured film containing alkali-soluble resin. The method according to any one of claims 1, 3 and 4,
The said base material is a manufacturing method of the cured film containing the thermoplastic resin base material comprised from the thermoplastic resin whose glass transition temperature is 100 degrees C or less. The method according to any one of claims 1, 3 and 4,
The said base material is a manufacturing method of the cured film containing the glass base material of thickness 0.5mm or less. The method according to claim 1 or 3,
The said base material is a manufacturing method of the cured film containing an organic semiconductor layer. The method according to any one of claims 1 to 4,
The said base material is a manufacturing method of the cured film which has an organic-semiconductor layer on the surface. The method according to any one of claims 2 to 4,
Further comprising exposing the layer of the active energy ray curable composition,
The manufacturing method of the cured film which performs the process of irradiating the said electron beam after the said process of exposing. The method according to any one of claims 2 to 4,
Exposing the layer of the active energy ray curable composition, and after the exposing step, developing the layer of the active energy ray curable composition to form a pattern,
The manufacturing method of the cured film which performs the process of irradiating the said electron beam after the process of forming the said pattern. The method according to claim 10,
The manufacturing method of the cured film which performs the said process to expose using ultraviolet-ray. The method according to any one of claims 1 to 4,
The said active energy ray curable composition is a manufacturing method of the cured film containing 0.01-5.0 mass% of silane coupling agents in solid content of the said active energy ray curable composition. The method according to claim 13,
The said active energy ray curable composition is a manufacturing method of the cured film containing a thermosetting resin. The method according to any one of claims 1 to 4,
The said active energy ray curable composition is a manufacturing method of the cured film containing at least 1 sort (s) chosen from a chromatic coloring agent and a black coloring agent. The method according to any one of claims 1, 2 and 4,
The said cured film is a manufacturing method of the cured film whose optical density with respect to any wavelength in the range of wavelength 260-440 nm is 1 or more. The method according to claim 16,
The said cured film is a manufacturing method of the cured film whose minimum value of the optical density in the range of wavelength 260-440 nm is 1 or more. The method according to claim 16,
The said cured film is a manufacturing method of the cured film whose optical density with respect to wavelength 365nm is 1 or more. The method according to any one of claims 1 to 4,
The said active energy ray curable composition is a manufacturing method of the cured film containing a photoinitiator and a radically polymerizable compound. The method according to any one of claims 1 to 4,
The said active energy ray curable composition is a manufacturing method of the cured film containing an acid generator and a cationically polymerizable compound. The method according to any one of claims 1 to 4,
The film thickness of the said cured film is a manufacturing method of the cured film which is 0.1-45 micrometers. The method according to any one of claims 1 to 4,
After applying the said active energy ray curable composition on the said base material, The manufacturing method of the cured film further includes the process of drying and forming the layer of the said active energy ray curable composition. The method according to any one of claims 1 to 4,
The manufacturing method of the cured film further including the process of performing vacuum drying. The method according to any one of claims 1 to 4,
The manufacturing method of the cured film which further includes the process of heat-processing at the temperature of 100 degrees C or less with respect to the layer which irradiated the said electron beam. The method according to any one of claims 1, 3 and 4,
The process of heat-processing at the temperature of 100 degrees C or less with respect to the layer which irradiated the said electron beam further,
The said base material contains a thermoplastic resin base material, The process of the said heat processing is a manufacturing method of the cured film which is performed at the temperature below the glass transition temperature of the said thermoplastic resin base material, and at the temperature of 100 degrees C or less. The cured film obtained by the manufacturing method of the cured film of any one of Claims 1-4.

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