JPWO2020059374A1 - Black ink composition, light-shielding film and its manufacturing method, and optical members - Google Patents

Abstract

It contains a black dye, titanium dioxide particles, and a photopolymerizable monomer, and the content of the titanium dioxide particles is 15% by mass or more and 45% by mass or less with respect to the total amount of the black ink composition, and the black dye is contained. A black ink composition in which the mass ratio of the content of titanium dioxide particles to the amount is 2.0 or more and 15.0 or less, a light-shielding film, a method for producing the light-shielding film, and an optical member.

Description

The present disclosure relates to a black ink composition, a light-shielding film and a method for producing the same, and an optical member.

Conventionally, various studies have been made on light-shielding films containing dyes or pigments.
For example, in Patent Document 1 below, as a light-shielding film for an optical element that is a thin film and has little internal reflection, it is a light-shielding film for an optical element that contains at least a resin and a colorant, and has a wavelength from 400 nm to the wavelength of the entire light-shielding film. A light-shielding film for an optical element having an average extinction coefficient of 0.03 or more and 0.15 or less, which is an average value of an extinction coefficient at 700 nm, is disclosed.
In Patent Document 1, it is said that the colorant is preferably composed of a dye or a dye and a pigment, and the resin is preferably an epoxy resin.
In the example of Patent Document 1, a light-shielding film is formed by using a thermosetting light-shielding paint containing an epoxy resin, a dye, non-black particles, propylene glycol monomethyl ether (solvent), and a curing agent.

Patent Document 1: Japanese Unexamined Patent Publication No. 2011-186437

It goes without saying that the light-shielding film is required to have a light-shielding property, but it may also be required to have a high refractive index.
For example, in recent years, as a lens which is an example of an optical member, a high refractive index lens may be used from the viewpoint of thinning, high resolution, and the like. When a light-shielding film is provided on the side surface of the high-refractive index lens (that is, the outer peripheral surface of the lens when the incident direction of light is the axis), the light-shielding film is used in order to effectively exert the performance of the high-refractive index lens. It is effective to reduce the difference in the refractive index between the light-shielding film and the high-refractive-index lens by increasing the refractive index of the lens. By reducing the difference in refractive index between the light-shielding film and the high-refractive index lens, it is possible to reduce internal reflection of incident light incident from an angle, and as a result, flare or ghost can be prevented.

Further, the material for forming a light-shielding film (for example, a paint) may be required to have excellent patterning property.
Here, the patterning property means a performance for forming a film having a desired pattern shape (for example, a light-shielding film).
For example, when a light-shielding film is provided on at least a part of the side surface of the high-refractive index lens described above, the material for forming the light-shielding film is used from the viewpoint of suppressing the protrusion of the light-shielding film into a region where the light-shielding film should not be formed. On the other hand, excellent patterning property is required.

Regarding the above points, the light-shielding film described in Patent Document 1 may have a insufficient refractive index.
For example, in the light-shielding film described in Patent Document 1, if the content mass ratio [non-black particles / black dye] is too small, the refractive index may be insufficient.

Further, the light-shielding paint containing an epoxy resin, a dye, non-black particles, propylene glycol monomethyl ether (solvent), and a curing agent described in Patent Document 1 described above contains a large amount of solvent and is a thermosetting paint. Therefore, the patterning property of the light-shielding film may be insufficient.
Specifically, when a light-shielding film is formed using the light-shielding paint described in Patent Document 1, it takes a long time to dry the light-shielding paint applied on the base material (that is, to remove the solvent from the light-shielding material). It is necessary and it takes a long time to heat-cure the light-shielding paint, for example, as compared with the time for photo-curing. Therefore, the light-shielding material applied on the substrate spreads wet during these long periods of time, and as a result, a light-shielding film having a desired pattern shape cannot be obtained (that is, the patterning property of the light-shielding film is insufficient). ) In some cases.
On the other hand, when the amount of the solvent in the light-shielding paint is reduced in order to suppress the spread of wetness, the viscosity of the light-shielding paint increases, and the light-shielding paint is applied onto the base material to form a coating film. In some steps (ie, prior to drying and thermosetting), a coating with the desired pattern shape may not be obtained. Therefore, in this case as well, the patterning property of the light-shielding paint is insufficient.

The present disclosure has been made in view of the above.
The problem to be solved by one aspect of the present disclosure is to provide a black ink composition having excellent light-shielding properties, capable of forming a light-shielding film having a high refractive index (preferably 1.75 or more), and excellent patterning properties. It is to be.
The problem to be solved by another aspect of the present disclosure is to provide a light-shielding film having excellent light-shielding property and a high refractive index (preferably 1.75 or more), and an optical member provided with the light-shielding film. That is.
An object to be solved by yet another aspect of the present disclosure is to provide a method for producing a light-shielding film using the black ink composition.

Specific means for solving the problem include the following aspects.
<1> Containing a black dye, titanium dioxide particles, and a photopolymerizable monomer,
The content of the titanium dioxide particles is 15% by mass or more and 45% by mass or less with respect to the total amount of the black ink composition.
A black ink composition in which the mass ratio of the content of titanium dioxide particles to the content of black dye is 2.0 or more and 15.0 or less.
<2> The black ink composition according to <1>, wherein the content of the photopolymerizable monomer is 30% by mass or more with respect to the total amount of the black ink composition.
<3> The black ink composition according to <1> or <2>, wherein the average primary particle diameter of the titanium dioxide particles is 10 nm or more and 100 nm or less.
<4> The photopolymerizable monomer contains at least one of a compound having one photopolymerizable group and a compound having two photopolymerizable groups.
The total content of the compound having one photopolymerizable group and the compound having two photopolymerizable groups is 30% by mass or more based on the total amount of the black ink composition <1> to <3>. The black ink composition according to any one.
<5> The black ink composition according to any one of <1> to <4>, wherein the content of the organic solvent is 20% by mass or less with respect to the total amount of the black ink composition.
<6> The photopolymerizable monomer is 2- (2-ethoxyethoxy) ethyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. The black ink composition according to any one of <1> to <5>, which comprises at least one selected from the group consisting of.
<7> 2- (2-ethoxyethoxy) ethyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, and 2- (2-vinyloxyethoxy) ethyl ( The black ink composition according to <6>, wherein the total proportion of the meta) acrylate is 15% by mass or more.
<8> The black ink composition according to any one of <1> to <7> used as an inkjet ink.
<9> A light-shielding film which is a cured product of the black ink composition according to any one of <1> to <8>.
<10> Contains black dye, titanium dioxide particles, and acrylic resin.
A light-shielding film in which the mass ratio of the content of titanium dioxide particles to the content of black dye is 2.0 or more and 15.0 or less.
<11> The light-shielding film according to <9> or <10>, which is a light-shielding film for an optical member.
<12> With the base material
The light-shielding film according to any one of <9> to <11>
An optical member comprising.
<13> The base material is a glass base material or a resin base material.
The optical member according to <12>, wherein the light-shielding film is provided on at least a part of the outer peripheral surface of the base material when the light-shielding film is oriented in the thickness direction of the base material.
<14> A step of applying the black ink composition according to any one of <1> to <8> on a base material to form an ink film.
The process of irradiating the ink film with active energy rays to obtain a light-shielding film,
A method for producing a light-shielding film having a light-shielding film.

According to one aspect of the present disclosure, there is provided a black ink composition which is excellent in light-shielding property, can form a light-shielding film having a high refractive index (preferably 1.75 or more), and is excellent in patterning property.
According to another aspect of the present disclosure, the light-shielding film and the optical member provided with the light-shielding film are provided.
According to still another aspect of the present disclosure, there is provided a method for producing a light-shielding film using the black ink composition.

In the present disclosure, the numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. To do.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. , May be replaced with the values shown in the examples.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.

In the present disclosure, “black” means that the optical density (OD) per 1 μm of thickness is 0.1 or more (OD ≧ 0.1 / μm), and the ratio of the absorbance at 580 nm to the absorbance at 480 nm is 0.3. It means that it is ~ 3.
In the present disclosure, the term "light" in the terms "photopolymerization" and "photocuring" is a concept that includes active energy rays such as γ-rays, β-rays, electron beams, ultraviolet rays, and visible rays. ..
In the present disclosure, "(meth) acrylic" is a concept that includes both acrylic and methacrylic, and "(meth) acrylate" is a concept that includes both acrylate and methacrylate, and is a "(meth) acryloyl group." Is a concept that includes both acryloyl and methacryloyl groups.

The black ink composition of the present disclosure (hereinafter, also simply referred to as “ink”) is
Contains black dye, titanium dioxide particles and photopolymerizable monomer,
The content of titanium dioxide particles is 15% by mass or more and 45% by mass or less with respect to the total amount of ink.
Black ink composition in which the mass ratio of the content of titanium dioxide particles to the content of black dye (hereinafter, also referred to as "content mass ratio [titanium dioxide particles / black dye]") is 2.0 or more and 15.0 or less. It is a thing.

According to the ink of the present disclosure, it is possible to form a light-shielding film having excellent light-shielding property and a high refractive index (preferably 1.75 or more). The ink of the present disclosure is excellent in patterning property.
The reason why such an effect is achieved is presumed as follows.

The effect of forming a light-shielding film having excellent light-shielding properties is contributed by the fact that the ink contains a black dye and that the mass ratio [titanium dioxide particles / black dye] is 15.0 or less. Conceivable. That is, it is considered that when the ink satisfies these conditions, the optical density of the light-shielding film is secured and the light-shielding property of the light-shielding film is secured.

The effect of being able to form a light-shielding film having a high refractive index is that the ink contains titanium dioxide particles, the content of the titanium dioxide particles is 15% by mass or more, and the content mass ratio [titanium dioxide particles / It is considered that the fact that the black dye] is 2.0 or more contributes. That is, it is considered that when the ink satisfies these conditions, the action of increasing the refractive index of the light-shielding film by the titanium dioxide particles works effectively, and as a result, the refractive index of the light-shielding film can be increased.

It is considered that the ink contains a photopolymerizable monomer, which contributes to the effect of patterning property. This point will be described in detail below.
The ink of the present disclosure is a photocurable ink (that is, an active energy ray-curable ink) containing a photopolymerizable monomer.
The photopolymerizable monomer has a function of photocuring the ink film by photopolymerizing in the ink (hereinafter, also referred to as “ink film”) applied to the base material, and also emits light (that is, active energy rays). Before being irradiated, it also has a function of ensuring the liquid state of the ink (that is, a function as a liquid component). Since the photopolymerizable monomer has a function as a liquid component, the ink of the present disclosure can reduce the content of the organic solvent or have a composition that does not contain the organic solvent.
Therefore, in the formation of the light-shielding film using the ink of the present disclosure, the ink is applied onto the base material on which the light-shielding film is formed to form the ink film, and then the ink film is immediately photocured to form a pattern (? That is, a light-shielding film) can be formed. That is, it is possible to shorten the time for drying the ink film between the formation of the ink film and the light irradiation of the ink film. Therefore, in the formation of the light-shielding film using the ink of the present disclosure, it is possible to suppress the wetting and spreading of the ink film from the formation of the ink film to the curing of the ink film, so that the light-shielding film having excellent pattern accuracy can be suppressed. Can be formed.

Further, it is considered that the content of titanium dioxide particles of 45% by mass or less also contributes to the effect of patterning property.
The reason for this is that the content of the titanium dioxide particles is 45% by mass or less, so that the viscosity of the ink is reduced, and as a result, it is desired at the stage of applying the ink on the substrate to form the ink film. This is considered to be because an ink film having a pattern shape can be easily obtained.

Hereinafter, each component that can be contained in the ink of the present disclosure will be described.

<Black dye>
The ink of the present disclosure contains a black dye.
The black dye is a component that contributes to the light-shielding property of the light-shielding film.
The black dye contained in the ink of the present disclosure may be only one kind or two or more kinds.
The black dye is not particularly limited, and known ones can be used.

As the black dye, a commercially available product may be used.
Commercially available black dyes include BONJET BLACK AS-0850, VALIFAST BLACK 1821, VALRFAST BLACK 3810, Oil Black HBB (manufactured by Orient Chemical Industries, Ltd.), Aizen Spirit Black MHS-Liquid, AIZENSO. Black-5 (above, manufactured by Hodogaya Chemical Co., Ltd.), RESORN Black GSN 200%, RESOLIN BlackBS (above, manufactured by Bayer Japan), KAYASET Black AN (manufactured by Nippon Kayaku Co., Ltd.), DAIWA Black MSC (manufactured by Nippon Kayaku) , HSB-202 (manufactured by Mitsubishi Kasei Co., Ltd.), NEPTUNE Black X60, NEOPEN Black X58 (manufactured by BASF Japan, Inc.) and the like.

The content of the black dye in the ink of the present disclosure may be in the range where the content mass ratio [titanium dioxide particles / black dye] is 2.0 or more and 15.0 or less.
The content of the black dye in the ink of the present disclosure is, for example, 1% by mass to 20% by mass, preferably 1% by mass to 15% by mass, and more preferably 1% by mass or more 13 with respect to the total amount of the ink. It is less than mass%, more preferably 2% by mass to 12% by mass.
When the content of the black dye is 1% by mass or more, it is advantageous in terms of the light-shielding property of the light-shielding film.
When the content of the black dye is 20% by mass or less, the viscosity of the ink can be reduced, which is advantageous in terms of patterning property.

Further, the ink of the present disclosure may contain a dye of a color other than black (for example, red, blue, yellow, etc.).
However, from the viewpoint of further improving the light-shielding property of the formed light-shielding film, the ratio of the black dye to the total dye contained in the ink of the present disclosure is preferably 60% by mass or more, more preferably 80% by mass or more. , 90% by mass or more is more preferable.
The ratio of the black dye to the total dye may be 100% by mass. That is, the ink of the present disclosure does not have to contain a dye of a color other than black.

<Titanium dioxide particles>
The ink of the present disclosure contains titanium dioxide particles.
Titanium dioxide particles are components that contribute to improving the refractive index of the light-shielding film.
The titanium dioxide particles contained in the ink of the present disclosure may be only one kind or two or more kinds.
The shape of the titanium dioxide particles is not particularly limited, and may be granular or needle-shaped.

The crystal structure of titanium dioxide in the titanium dioxide particles includes rutile type (tetragonal crystal), anatase type (tetragonal crystal), brookite type (orthorhombic crystal) and the like, but is not particularly limited.
Among them, the preferable titanium dioxide particles are rutile-type titanium dioxide particles from the viewpoint of crystal stability and availability.
Titanium dioxide particles can be produced by a vapor phase method or a liquid phase method. Of these methods, the vapor phase method is preferable because a highly crystalline method can be easily obtained.
Further, as the titanium dioxide particles, either untreated particles or surface-treated particles can be used. When the titanium dioxide particles are surface-treated, the surface treatment includes; _{surface treatment with an inorganic substance such as alumina (Al 2} O ₃ ) and silica (SiO ₂ ); titanium coupling agent, silane coupling agent, silicone oil, etc. Surface treatment with organic substances; etc.

Titanium dioxide particles have organic matter decomposability due to photocatalytic activity. Therefore, as the titanium dioxide particles, those whose surface is surface-treated with an inorganic oxide such as alumina, or those whose surface is coated with an inorganic hydrate containing zinc, magnesium, zirconium or the like are preferable.
Further, from the viewpoint of adjusting the acidic or basic state of the particle surface and the durability, those in which alumina and silica are used in combination for surface treatment are also preferable.

As the titanium dioxide particles, commercially available products on the market may be used.
As an example of a commercial product of rutile-type titanium dioxide particles,
Taipaque (registered trademark) R series (rutile type; for example, R-550, R-630, R-680, R-820), Taipaque CR series (rutile type; for example, CR-50, CR) manufactured by Ishihara Sangyo Co., Ltd. -80), PF series, ultrafine titanium oxide TTO series (rutile type; for example, TTO-51 series (eg TTO-51A, TTO-51B, etc.), TTO-55 series (eg TTO-55A, TTO-) 55B etc.), TTO-S series (eg TTO-S-1 etc.), TTO-V series (eg TTO-V-3 etc.), TTO-F series, TTO-W-5 series),
R series manufactured by Sakai Chemical Industry Co., Ltd.,
JR series, MT series, fine particle titanium oxide MT series (for example, MT-01, MT-10EX, MT-05, MT-100S, MT-100SA, MT-500SA, MT-150EX, MT-150W) manufactured by TAYCA CORPORATION. ),
KURONOS KR series manufactured by Titan Kogyo Co., Ltd.,
TR series manufactured by Fuji Titanium Industry Co., Ltd.,
And so on.

The average primary particle size of the titanium dioxide particles is not particularly limited, but is preferably 10 nm or more and 300 nm or less.
When the average primary particle size of the titanium dioxide particles is 300 nm or less, the transparency of the titanium dioxide particles is excellent, so that the influence of the titanium dioxide particles on the blackish color tone of the ink of the present disclosure can be further reduced. Therefore, the light-shielding property of the formed light-shielding film is further improved. Further, when the average primary particle size of the titanium dioxide particles is 300 nm or less, the patterning property of the ink is further improved. The reason for this is considered to be that the dispersion stability of the titanium dioxide particles is further improved. From the viewpoint that these effects are more effectively exhibited, the average primary particle size of the titanium dioxide particles is more preferably 100 nm or less, further preferably 80 nm or less.
On the other hand, when the average primary particle size of the titanium dioxide particles is 10 nm or more, the refractive index of the light-shielding film formed is further improved. From the viewpoint that such an effect is more effectively exhibited, the average primary particle size of the titanium dioxide particles is more preferably 30 nm or more.
From the above viewpoint, the average primary particle size of the titanium dioxide particles is more preferably 10 nm or more and 100 nm or less, further preferably 10 nm or more and 80 nm or less, and further preferably 30 nm or more and 80 nm or less.

The average primary particle diameter of the titanium dioxide particles represents the arithmetic mean value of the area equivalent circle diameter of the titanium dioxide particles.
Specifically, the average primary particle size of the titanium dioxide particles is the particle size of 1000 primary particles of titanium dioxide (equivalent to an area circle) arbitrarily selected based on an image taken by a transmission electron microscope of the titanium dioxide particle group. It is obtained by measuring the diameter) and calculating the arithmetic mean value of the obtained measured value group.
As the transmission electron microscope, for example, TEM2010 (pressurized voltage 200 kV; manufactured by JEOL Ltd.) can be used.

The content of titanium dioxide particles in the ink of the present disclosure is 15% by mass or more and 45% by mass or less with respect to the total amount of the ink.
The content of the titanium dioxide particles of 15% by mass or more contributes to increasing the refractive index of the light-shielding film. From the viewpoint of further increasing the refractive index of the light-shielding film, the content of titanium dioxide particles is more preferably 20% by mass or more, further preferably 23% by mass or more.
The content of the titanium dioxide particles of 45% by mass or less contributes to the improvement of patterning property. The reason for this is considered to be that the viscosity of the ink is further reduced. From the viewpoint of further improving the patterning property, the content of the titanium dioxide particles is more preferably 35% by mass or less, further preferably 32% by mass or less.
From the above viewpoint, the content of the titanium dioxide particles is more preferably in the range of 20% by mass or more and 35% by mass or less, and further preferably in the range of 23% by mass or more and 32% by mass or less.

In the ink of the present disclosure, the content mass ratio [titanium dioxide particles / black dye] (that is, the mass ratio of the content of titanium dioxide particles to the content of the black dye) is 2.0 or more and 15.0 or less.
A mass ratio [titanium dioxide particles / black dye] of 2.0 or more contributes to increasing the refractive index of the light-shielding film. From the viewpoint of further increasing the refractive index of the light-shielding film, the content mass ratio [titanium dioxide particles / black dye] is preferably 3.0 or more.
The content mass ratio [titanium dioxide particles / black dye] of 15.0 or less contributes to improving the light-shielding property of the light-shielding film. From the viewpoint of further improving the light-shielding property of the light-shielding film, the content mass ratio [titanium dioxide particles / black dye] is preferably 13.0 or less, and more preferably 12.0 or less.
From the above viewpoint, the content mass ratio [titanium dioxide particles / black dye] is more preferably 3.0 or more and 13.0 or less, and further preferably 3.0 or more and 12.0 or less.

<Photopolymerizable monomer>
The ink of the present disclosure contains a photopolymerizable monomer.
The photopolymerizable monomer contained in the ink of the present disclosure may be only one kind or two or more kinds.
Here, the photopolymerizable monomer means a monomer compound containing a photopolymerizable group.
As the photopolymerizable group, a group containing an ethylenic double bond is preferable. Examples of the group containing an ethylenic double bond include a (meth) acryloyl group, a vinyl group, an allyl group, and the like.
The photopolymerizable monomer contained in the ink of the present disclosure may be only one kind or two or more kinds.

The molecular weight of the photopolymerizable monomer is preferably 100 or more and less than 1,000, more preferably 100 or more and 800 or less, and further preferably 150 or more and 700 or less.

The content of the photopolymerizable monomer with respect to the total amount of the ink is preferably 30% by mass or more.
When the content of the photopolymerizable monomer with respect to the total amount of the ink is 30% by mass or more, the patterning property of the ink is further improved.
From the viewpoint of further improving the patterning property of the ink, the content of the photopolymerizable monomer with respect to the total amount of the ink is more preferably 35% by mass or more, still more preferably 40% by mass or more.
The upper limit of the content of the photopolymerizable monomer with respect to the total amount of the ink depends on the content of other components in the ink, but is preferably 80% by mass, more preferably 70% by mass.

The photopolymerizable monomer preferably contains at least one of a compound containing one photopolymerizable group and a compound containing two photopolymerizable groups.
The compound containing two photopolymerizable groups may be a compound containing two identical photopolymerizable groups, or a compound containing one different photopolymerizable group (for example, 2- (2) described later. − Vinyloxyethoxy) ethyl (meth) acrylate) may be used.

When the photopolymerizable monomer contains at least one of a compound containing one photopolymerizable group and a compound containing two photopolymerizable groups, photopolymerization occupying the photopolymerizable monomer from the viewpoint of further improving the patterning property. The total ratio of the compound containing one sex group and the compound containing two photopolymerizable groups is preferably 80% by mass or more.
The ratio of the total may be 100% by mass or less than 100% by mass.

When the photopolymerizable monomer contains at least one of a compound containing one photopolymerizable group and a compound containing two photopolymerizable groups, one photopolymerizable group is used from the viewpoint of further improving the patterning property. The total content of the compound containing the compound and the compound containing two photopolymerizable groups is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, based on the total amount of the ink. Is.
Here, the term "total content of a compound containing one photopolymerizable group and a compound containing two photopolymerizable groups" does not necessarily mean a compound containing one photopolymerizable group and a photopolymerizable group. It does not mean that it contains both of the two-containing compounds. For example, when the ink contains only one of a compound containing one photopolymerizable group and a compound containing two photopolymerizable groups, "a compound containing one photopolymerizable group and a photopolymerizable group are used. "Total content of two compounds" means the content of only one of them.
The upper limit of the total content of the compound containing one photopolymerizable group and the compound containing two photopolymerizable groups depends on the content of other components in the ink, but is preferably 80 with respect to the total amount of the ink. It is mass%, more preferably 70 mass%.

Hereinafter, a compound containing one photopolymerizable group may be referred to as a monofunctional monomer, and a compound containing two photopolymerizable groups may be referred to as a bifunctional monomer.

As a monofunctional monomer (that is, a compound containing one photopolymerizable group),
2-Phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclic trimethylolpropaneformal (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl ( Meta) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, tridecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, caprolactone-modified (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene Monofunctional (meth) acrylate compounds such as glycol (meth) acrylate, polypropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate;
(Meta) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- Butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N-dodecyl (meth) acrylamide, N- (methoxymethyl) (meth) ) Monofunctional (meth) acrylamide compounds such as acrylamide, N- (butoxymethyl) (meth) acrylamide, N-phenyl (meth) acrylamide;
Monofunctional vinyl ether compounds such as normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether;
Monofunctional N-vinyl compounds such as N-vinylcaprolactam and N-vinylpyrrolidone;
And so on.

As a bifunctional monomer (that is, a compound containing two photopolymerizable groups),
Hexadiol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, nonanediol di (meth) acrylate, decandiol di (meth) acrylate, neo Bifunctionals such as pentyl glycol di (meth) acrylate, polyethylene glycol-modified bisphenol A di (meth) acrylate, dioxane glycol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate. (Meta) acrylate compound;
A (meth) acrylate compound having one (meth) acryloyl group and one photopolymerizable group other than the (meth) acryloyl group, such as 2- (2-vinyloxyethoxy) ethyl (meth) acrylate;
Bifunctional vinyl compounds such as 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether;
And so on.

As photopolymerizable monomers, in addition to the above-mentioned monofunctional monomers and bifunctional monomers, Shinzo Yamashita ed., "Crosslinking Agent Handbook" (1981 Taiseisha); Kiyomi Kato ed., "UV / EB Curing Handbook (UV / EB Curing Handbook) Raw Materials) ”(1985, Polymer Publishing Association); Radtech Study Group,“ Applications and Markets of UV / EB Curing Technology ”, p. 79, (1989, CMC); Eiichiro Takiyama,“ Polyester Resin Handbook , (1988, Nikkan Kogyo Shimbun), etc., or monofunctional or bifunctional photopolymerizable monomers known in the industry can be used.

From the viewpoint of further improving the patterning property of the ink, the photopolymerizable monomer contains at least one selected from the group consisting of a compound containing one (meth) acryloyl group and a compound containing two (meth) acryloyl groups. Is preferable.
Here, the compounds containing one (meth) acryloyl group include the monofunctional (meth) acrylate compound, the monofunctional (meth) acrylamide compound, and the one other than the (meth) acryloyl group and the (meth) acryloyl group. Examples of the (meth) acrylate compound having one photopolymerizable group of the above, the above monofunctional (meth) acrylate compound, or the above (meth) acryloyl group and one photopolymerizable group other than the (meth) acryloyl group. A (meth) acrylate compound having is preferable.
Examples of the compound containing two (meth) acryloyl groups include the above-mentioned bifunctional (meth) acrylate compound.

From the viewpoint of further improving the patterning property of the ink, the total ratio of the compound containing one (meth) acryloyl group and the compound containing two (meth) acryloyl groups in the photopolymerizable monomer is 70% by mass or more. It is preferably 80% by mass or more, and more preferably 80% by mass or more.
The ratio of the total may be 100% by mass or less than 100% by mass.

The photopolymerizable monomer is a group consisting of 2- (2-ethoxyethoxy) ethyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. It is preferable to contain at least one selected from the above (hereinafter, also referred to as “specific monomer A”).
When the photopolymerizable monomer contains the specific monomer A, the patterning property of the ink is further improved. The reason why such an effect is exhibited is not clear, but it is considered that the specific monomer A has a function of reducing the viscosity of the ink.

When the photopolymerizable monomer contains the specific monomer A, from the viewpoint of further improving the patterning property of the ink, the ratio of the specific monomer A to the photopolymerizable monomer (that is, 2- (2-ethoxyethoxy) ethyl (meth). ) Acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate (total ratio) is preferably 15% by mass or more, more preferably 20% by mass or more. Preferably, 25% by mass or more is more preferable, and 30% by mass or more is further preferable.
The ratio of the specific monomer A may be 100% by mass or less than 100% by mass.

<Photopolymerization initiator>
The ink of the present disclosure preferably contains a photopolymerization initiator.
When the ink of the present disclosure contains a photopolymerization initiator, the photopolymerization initiator contained may be only one kind or two or more kinds.
As the photopolymerization initiator, a known photopolymerization initiator that absorbs active energy rays to generate radicals that are polymerization initiators can be used.

Examples of the active energy ray include ultraviolet rays (UV), visible light, electron beam, and the like, and among them, ultraviolet rays are preferable from the viewpoint of versatility.

Examples of the photopolymerization initiator include (a) carbonyl compounds such as aromatic ketones, (b) acylphosphine oxide compounds, (c) aromatic onium salt compounds, (d) organic peroxides, and (e) thio compounds. It has (f) hexaarylbiimidazole compound, (g) ketooxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, (k) active ester compound, and (l) carbon halogen bond. Examples thereof include compounds, (m) alkylamine compounds and the like.
As the photopolymerization initiator, the above compounds (a) to (m) may be used alone or in combination of two or more.

Preferred examples of the (a) carbonyl compound, (b) acylphosphine oxide compound, and (e) thio compound include "RADITION CURING IN POLYMER SCIENCE AND TECHNOLOGY", J. Mol. P. FOUASSIER, J. Mol. F. RABEK (1993), pp. Examples thereof include the compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77 to 117.
More preferable examples include an α-thiobenzophenone compound described in Japanese Patent Publication No. 47-6416, a benzoin ether compound described in Japanese Patent Publication No. 47-3981, and an α-substituted benzoin compound described in Japanese Patent Publication No. 47-22326. The benzoin derivative described in JP-A-47-23664, the aloylphosphonic acid ester described in JP-A-57-30704, the dialkoxybenzophenone described in JP-A-60-26483, JP-A-60-26403, JP-A. Benzoin ethers described in Japanese Patent Application Laid-Open No. 62-81345, Japanese Patent Publication No. 1-32422, US Pat. No. 4,318,791 pamphlet, α-aminobenzophenones described in European Patent No. 0284561A1, JP-A-2-211452. P-di (dimethylaminobenzoyl) benzene described in JP-A, thio-substituted aromatic ketones described in JP-A-61-194062, acylphosphine sulfides described in JP-A-2-9597, JP-A-2-9596. Examples thereof include the acylphosphins described, the thioxanthones described in Japanese Patent Publication No. 63-61950, and the coumarins described in Japanese Patent Publication No. 59-42864.
Further, the polymerization initiators described in JP-A-2008-105379 and JP-A-2009-114290 are also preferable.

Among the photopolymerization initiators, (a) carbonyl compound or (b) acylphosphine oxide compound is more preferable, and specifically, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (for example, manufactured by BASF). IRGACURE® 819), 2- (dimethylamine) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (eg, IRGACURE® 369 manufactured by BASF), 2-methyl -1- (4-Methylthiophenyl) -2-morpholinopropane-1-one (eg, IRGACURE® 907, manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (eg, manufactured by BASF). IRGACURE® 184), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (eg, IRGACURE® from BASF) 2959), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (for example, DAROCUR® TPO, LUCIRIN® TPO (both manufactured by BASF)) and the like.
Among these, (b) acylphosphine oxide compounds are preferable as the photopolymerization initiator, and monoacylphosphine oxide compounds (particularly preferably 2,4) are preferable from the viewpoint of improving sensitivity and compatibility with LED light. , 6-trimethylbenzoyl-diphenyl-phosphine oxide) or bisacylphosphine oxide compound (particularly preferably bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide).

When the ink of the present disclosure contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.5% by mass to 25.0% by mass, preferably 0.5% by mass to 25.0% by mass, based on the total amount of the ink. 20.0% by mass is more preferable, and 1.0% by mass to 15.0% by mass is further preferable.

<Basic dispersant>
The ink of the present disclosure preferably contains a basic dispersant.
When the ink of the present disclosure contains a basic dispersant, the basic dispersant contained in the ink may be only one kind or two or more kinds.
When the ink of the present disclosure contains a basic dispersant, the basic polar functional groups of the basic dispersant easily act on the surface of the titanium dioxide particles, thereby improving the dispersion stability of the titanium dioxide particles. Can be kept better.

The basic dispersant is preferably a polymer having a basic polar functional group and having a weight average molecular weight (Mw) of 1000 or more.

In the present disclosure, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC).
For the measurement by gel permeation chromatography (GPC), for example, HLC (registered trademark) -8020 GPC (Tosoh Corporation) is used as a measuring device, and TSKgel (registered trademark) Super Multipore HZ-H (4. Three 6 mm ID x 15 cm, Tosoh Corporation are used, and THF (tetrahydrofuran) is used as the eluent. The measurement conditions are a sample concentration of 0.45% by mass, a flow rate of 0.35 ml / min, a sample injection amount of 10 μl, and a measurement temperature of 40 ° C., and the measurement is performed using an RI detector.
The calibration curve is "Standard sample TSK standard, polystyrene": "F-40", "F-20", "F-4", "F-1", "A-5000", "A" of Tosoh Corporation. It is made from 8 samples of "-2500", "A-1000", and "n-propylbenzene".

Examples of the basic polar functional group in the basic dispersant include an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group.
Of these, an amino group is preferable from the viewpoint of dispersion stability of titanium dioxide particles.

The amine value of the basic dispersant is preferably 10 mgKOH / g or more and 80 mgKOH / g or less.
When the amine value is 10 mgKOH / g or more, the dispersion stability of the titanium dioxide particles becomes better. Further, when the amine value is 80 mgKOH / g or less, the aggregation of titanium dioxide particles can be suppressed and the stability over time can be well maintained, which makes it easier to secure a high refractive index of the light-shielding film.
The amine value of the basic dispersant is more preferably 10 mgKOH / g or more and 50 mgKOH / g or less.

In the present disclosure, the amine value is a value indicating the total amount of free base and base, and specifically, it is represented by the number of mg of potassium hydroxide equivalent to the hydrochloric acid required to neutralize 1 g of the sample. The value.
The amine value is measured by a method according to JIS-K7237 (1995).

Examples of the basic dispersant include a salt of a long-chain polyaminoamide and a high-molecular-weight acid ester; a salt of a long-chain polyaminoamide and a polar acid ester; a polyester polyamine; a stearylamine acetate; an unsaturated carboxylic acid such as polyacrylic acid. (Partial) amine salt, (partial) ammonium salt or (partial) alkylamine salt of the (co) polymer; unsaturated polyamide; long-chain polyaminoamide phosphate; polyethyleneimine-based compound [eg with polylower alkyleneimine] Amide, which is a reaction product with a free carboxy group-containing polyester]; Polyallylamine-based compound [Example: Polyallylamine and polyester having a free carboxyl group, polyamide and polyesteramide (cocondensate of ester and amide) selected from three types Reaction products with at least one compound] and the like.
Among them, a compound having a polyester polyamine skeleton or a compound having a polyethyleneimine skeleton is preferable, and a compound having a polyethyleneimine skeleton is preferable.
Here, the "(co) polymer" means a polymer that may be a copolymer (that is, a homopolymer or a copolymer), and the "(partial) amine salt" means a partial amine. It means an amine salt which may be a salt, "(partial) ammonium salt" means an ammonium salt which may be a partial ammonium salt, and "(partial) alkylamine salt" means a partial alkylamine. It means an alkylamine salt which may be a salt.

As the basic dispersant, a commercially available product on the market may be used.
Examples of commercially available products include Solsperse (registered trademark) series manufactured by Nippon Louvre Resol Co., Ltd. [For example, trade name: Solsperse 24000 (amine value: 41.6 mgKOH / g), trade name: Solsperse 32000 (amine value: 31. 2 mgKOH / g), trade name: Solsperse 35100 (amine value: 14 mgKOH / g), trade name: Solsperse 39000 (amine value: 25.7 mgKOH / g), trade name: Solsperse 71000 (amine value: 78 mgKOH / g), product Name: Solsperse J100, Product name: Solsperse J200, etc.], DISPERBYK (registered trademark) series manufactured by Big Chemie Japan Co., Ltd. [Product name: DISPERBYK-162 (amine value: 13 mgKOH / g), Product name: DISPERBYK-163 (amine) Price: 10 mgKOH / g), Product name: DISPERBYK-168 (amine value: 11 mgKOH / g), Product name: DISPERBYK-2050 (amine value: 30.7 mgKOH / g), Product name: DISPERBYK-2200 (30.7 mgKOH / g) g), Product name: DISPERBYK-2150 (amine value: 56.7 mgKOH / g), etc.], BYKJET (registered trademark) series manufactured by Big Chemie Japan Co., Ltd. [Product name: BYKJET-9151 (amine value: 17.2 mgKOH / g) g), Product name: BYKJET-9152 (amine value: 27.3 mgKOH / g), etc.], Ajispar (registered trademark) series manufactured by Ajinomoto Fine Techno Co., Ltd. [Product name: Ajispar PB821 (amine value: 11.2 mgKOH / g) ), Product name: Ajispar PB-822 (amine value: 18.2 mgKOH / g), Product name: Ajisper PB-881 (amine value: 17.4 mgKOH / g), Product name: Ajisper PB-824 (amine value: 17 mgKOH) / G), etc.], EFKA PX4731 (amine value: 25 mgKOH / g) manufactured by BASF, etc. can be mentioned.

When the ink of the present disclosure contains a basic dispersant, the content of the basic dispersant is preferably 3% by mass or more and 20% by mass or less, and 5% by mass or more and 15% by mass or less, based on the total amount of the ink. Is more preferable.
When the content of the basic dispersant is 3% by mass or more, the dispersion stability of the titanium dioxide particles can be kept better. When the content of the basic dispersant is 20% by mass or less, it is advantageous in terms of patterning property.

<Polymerization inhibitor>
The ink of the present disclosure may contain a polymerization inhibitor.
When the ink of the present disclosure contains a polymerization inhibitor, the polymerization inhibitor contained may be only one kind or two or more kinds.
Polymerization inhibitors include p-methoxyphenol (MEHQ), quinones (eg, hydroquinone, benzoquinone, methoxybenzoquinone, etc.), phenothiazine, catechols, alkylphenols (eg, dibutylhydroxytoluene (BHT), etc.), alkylbisphenols. , Zinc dimethyl dithiocarbamate, copper dimethyl dithiocarbamate, copper dibutyl dithiocarbamate, copper salicylate, thiodipropionic acid esters, mercaptobenzimidazole, phosphites, 2,2,6,6-tetramethylpiperidin-1-oxyl ( TEMPO), 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl (TEMPOL), tris (N-nitroso-N-phenylhydroxylamine) aluminum salt (also known as cuperon Al) and the like. ..
Among them, at least one selected from p-methoxyphenol, catechols, quinones, alkylphenols, TEMPO, TEMPOL, and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt (also known as cuperon Al) is preferable.
When the ink of the present disclosure contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 2.0% by mass, preferably 0.02% by mass to 1.% by mass, based on the total amount of the ink. 5% by mass is more preferable.

<Organic solvent>
The ink of the present disclosure may contain at least one organic solvent as long as it does not interfere with the effect of patterning property.
When the ink of the present disclosure contains an organic solvent, examples of the contained organic solvent include organic solvents having a boiling point of 120 ° C. or higher.
Examples of the organic solvent having a boiling point of 120 ° C. or higher include ethylene glycol monomethyl ether (boiling point: 124 ° C.), ethylene glycol monomethyl ether acetate (boiling point: 143 ° C.), propylene glycol methyl ether acetate (boiling point: 146 ° C.), and diethylene glycol dimethyl ether. (Boiling point: 162 ° C.), Diethylene glycol diethyl ether (DEGdEE) (boiling point: 180 ° C.), Diethylene glycol ethylmethyl ether (boiling point: 179 ° C.), Diethylene glycol monobutyl ether (boiling point: 230 ° C.), Diethylene glycol dibutyl ether (boiling point: 255 ° C.) , Glycol ether-based solvent such as triethylene glycol dimethyl ether (boiling point: 216 ° C.); and the like.

However, from the viewpoint of further improving the patterning property, the content of the organic solvent with respect to the total amount of the ink is preferably 25% by mass or less. In this case, the lower limit of the content of the organic solvent may be 0% by mass. That is, the ink of the present disclosure does not have to contain an organic solvent.
In the ink of the present disclosure, when the content of the organic solvent with respect to the total amount of the ink is 25% by mass or less, the wet spread of the ink film until the ink film on the substrate is cured is further suppressed. , The patterning property is further improved.
From this point of view, the content of the organic solvent with respect to the total amount of the ink is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and 5% by mass. It is more preferably 2% by mass or less, further preferably 0% by mass (that is, the ink does not contain an organic solvent).

<Water>
The ink of the present disclosure may contain a small amount of water, but is preferably a non-water-based ink that does not substantially contain water. Specifically, the content of water with respect to the total amount of the ink of the present disclosure is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. The water content may be 0% by mass.

<Surfactant>
The ink of the present disclosure may contain a surfactant.
Examples of the surfactant include the surfactants described in JP-A-62-173463 and JP-A-62-183457. For example, anionic surfactants such as dialkyl sulfosuccinate, alkylnaphthalene sulfonate, fatty acid salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, acetylene glycol, polyoxyethylene / polyoxypropylene block copolymer, modified Examples thereof include nonionic surfactants such as siloxanes such as polydimethylsiloxane, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and betaine-based surfactants such as carbobetaine and sulfobetaine.

<Photopolymerizable resin>
The ink of the present disclosure may contain a photopolymerizable resin.
When the ink of the present disclosure contains a photopolymerizable resin, the contained photopolymerizable resin may be only one type or two or more types.
Here, the photopolymerizable resin means a resin having a photopolymerizable group (that is, an oligomer or a polymer).
The preferred embodiment of the photopolymerizable group in the photopolymerizable resin is the same as the preferred embodiment of the photopolymerizable group in the photopolymerizable monomer.

Examples of the resin that is the base of the photopolymerizable resin include acrylic resin, urethane resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, and polybutadiene resin.

The photopolymerizable group can be introduced into the resin by a polymer reaction or copolymerization.
The introduction of a polymerizable group into a resin is, for example, a reaction between a resin having a carboxy group in the side chain and glycidyl (meth) acrylate; a resin having an epoxy group and an ethylenically unsaturated group-containing carboxylic acid (for example, (meth) acrylic). Reaction with acid); etc. can be used.

As the photopolymerizable resin, a commercially available product on the market may be used.
Examples of commercially available acrylic resins having a photopolymerizable group include (ACA) Z200M, (ACA) Z230AA, (ACA) Z251, (ACA) Z254F (above, Daicel Ornex Co., Ltd.), and Hitaroid 7975D (Hitachi). Kasei Co., Ltd., etc. can be mentioned.

Examples of commercially available urethane resins having a photopolymerizable group include EBECRYL (registered trademark) 8402, EBECRYL8405, EBECRYL9270, EBECRYL8311, EBECRYL8701, KRM8667, KRM8528 (above, Daicel Ornex Co., Ltd.), CN964, CN90. , CN996, CN975, CN9782 (above, Sartmer), UV-6300B, UV-7600B, UV-7605B, UV-7620EA, UV-7630B, UV-1700B (above, Nippon Synthetic Chemical Co., Ltd.), U-6HA , U-15HA, U-108A, U-200PA, UA-4200 (above, Shin-Nakamura Chemical Industry Co., Ltd.), Tesslac 2300, Hitaroid 4863, Tesslac 2328, Tesslac 2350, Hitaroid 7902-1 (above, Hitachi Chemical Co., Ltd. Co., Ltd.), 8UA-017, 8UA-239, 8UA-239H, 8UA-140, 8UA-585H, 8UA-347H, 8UX-015A (above, Taisei Fine Chemicals Co., Ltd.) and the like.

Examples of commercially available polyester resins having a photopolymerizable group include CN294, CN2254, CN2260, CN2271E, CN2300, CN2301, CN2302, CN2303, CN2304 (hereinafter, Sartmer), EBECRYL436, EBECRYL438, EBECRYL546, EBECRYL524, EBECRYL524. EBECRYL811, EBECRYL812 (above, Daicel Ornex Co., Ltd.) and the like can be mentioned.
Examples of commercially available products of the polyether resin having a photopolymerizable group include Blemmer (registered trademark) ADE-400A, Blemmer ADP-400 (above, NOF CORPORATION) and the like.
Examples of commercially available products of polycarbonate resins having a photopolymerizable group include polycarbonate diol diacrylate (Ube Industries, Ltd.) and the like.
Examples of commercially available epoxy resins having photopolymerizable groups include EBECRYL3708 (Dycel Ornex Co., Ltd.), CN120, CN120B60, CN120B80, CN120E50 (above, Sartmer), Hitaroid (registered trademark) 7851 (Hitachi Kasei (Hitachi Kasei). Co., Ltd.) and the like.
Examples of commercially available products of the polybutadiene resin having a photopolymerizable group include CN301, CN303, CN307 (above, Sartmer) and the like.

The weight average molecular weight (Mw) of the photopolymerizable resin is preferably 1000 or more and 100,000 or less, more preferably 1000 or more and 40,000 or less, and further preferably 1000 or more and 10000 from the viewpoint of achieving both adhesion and dispersion stability. It is as follows.

<Binder>
The ink of the present disclosure may contain a binder.
When the ink of the present disclosure contains a binder, the binder contained may be only one kind or two or more kinds.
Here, the binder means a resin having no polymerizable group.
As the binder, known binders such as polyester resin, polyurethane resin, vinyl resin, acrylic resin, and rubber resin can be used. Among them, acrylic resin or polyester resin is preferable, and methyl methacrylate alone weight is inert. Combined and / or copolymers are more preferred.

As the binder, a commercially available product on the market may be used. For example, a polymethylmethacrylate manufactured by Aldrich (molecular weight 10,000, catalog number 81497; molecular weight 20,000, catalog number 81498; molecular weight 50,000, catalog) may be used. No. 81501), methyl methacrylate / n-butyl methacrylate copolymer (mass ratio 85/15, molecular weight 75,000; catalog number 474029), etc .; ELVACITE 2013 (methyl methacrylate / n-butyl methacrylate copolymer) manufactured by Lucite International Co., Ltd., Mass ratio 36/64, molecular weight 37,000), 2021, 2614, 4025, 4026, 4028, etc .; Paraloid DM55, B66, etc. manufactured by Rohmand Haas; BR113, 115, etc. manufactured by Mitsubishi Rayon Co., Ltd. can be mentioned.

The weight average molecular weight (Mw) of the binder is preferably 1000 or more, more preferably 1000 to 1000000, further preferably 5000 to 20000, and particularly preferably 800 to 100,000.
The glass transition temperature (Tg) of the binder is preferably 50 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C. Tg is a value measured by differential scanning calorimetry (DSC).

<Sensitizer>
The inks of the present disclosure may additionally contain a sensitizer.
A sensitizer is a substance that absorbs a specific active energy ray and becomes an electron-excited state. The sensitizer in the electron-excited state comes into contact with the photopolymerization initiator and causes actions such as electron transfer, energy transfer, and heat generation. This promotes chemical changes in the photopolymerization initiator, that is, decomposition, radicals, acid or base production, and the like.

Examples of the sensitizer include benzophenone (BP), thioxanthone, isopropylthioxanthone (ITX), ethyl 4- (dimethylamino) benzoate (EDB), anthraquinone, 3-acylcoumarin derivative, terphenyl, styrylketone, 3-. (Aloyl methylene) Thiazoline, ginseng quinone, eosin, rhodamine, erythrosin and the like can be mentioned.
Further, as the sensitizer, a compound represented by the general formula (i) described in JP-A-2010-24276 and a compound represented by the general formula (I) described in JP-A-6-107718. Can also be suitably used.
Among them, the sensitizer is selected from thioxanthone, isopropylthioxanthone, ethyl 4- (dimethylamino) benzoate, and benzophenone from the viewpoint of compatibility with light emitting diode (LED) light and reactivity with a photopolymerization initiator. At least one type is preferable.

<Other ingredients>
The ink of the present disclosure may contain other components other than the above.
Examples of other components include ultraviolet absorbers, co-sensitizers, antioxidants, anti-fading agents, conductive salts and the like.
For other components, publicly known documents such as Japanese Patent Application Laid-Open No. 2011-225884 and Japanese Patent Application Laid-Open No. 2009-209352 can be referred to as appropriate.

<Use of ink>
The ink of the present disclosure can be used for forming a light-shielding film by a coating method, a dipping method, a gravure method, a flexographic method, an inkjet method, or the like.
The ink of the present disclosure is particularly preferably used for forming a light-shielding film by an inkjet method (that is, as an inkjet ink).

<Physical characteristics of ink>
(viscosity)
The viscosity of the ink of the present disclosure is not particularly limited.
The viscosity of the ink of the present disclosure at 40 ° C. is preferably 10 mPa · s to 25 mPa · s, and more preferably 10 mPa · s to 20 mPa · s.
When the viscosity of the ink is in the above-mentioned preferable range, the ejection stability from the inkjet nozzle when used as an inkjet ink is further improved. As a result, the patterning property is further improved.
The viscosity of the ink can be adjusted, for example, by adjusting the composition ratio of each component contained.
Further, as described above, the specific monomer A contributes to the reduction of the viscosity of the ink, which in turn contributes to the further improvement of the patterning property.

In the present disclosure, the viscosity of the ink is a value measured using a viscometer (for example, VISCOMETER RE-85L of Toki Sangyo Co., Ltd.) with respect to the ink whose temperature has been adjusted to 40 ° C.

(surface tension)
The surface tension of the ink of the present disclosure is not particularly limited.
The surface tension of the ink of the present disclosure at 30 ° C. is, for example, 20 mN / m to 30 mN / m, preferably 23 mN / m to 28 mN / m.
In the present disclosure, the surface tension is a value measured using a surface tension meter (for example, DY-700 of Kyowa Surface Chemistry Co., Ltd.) for an ink whose temperature has been adjusted to 30 ° C.

[Manufacturing method of light-shielding film]
The method for producing a light-shielding film of the present disclosure is
A step of applying the above-mentioned ink of the present disclosure on a base material to obtain an ink film (hereinafter, also referred to as “applying step”).
A step of irradiating the ink film with active energy rays to obtain a light-shielding film (hereinafter, “irradiation step”), and
Have.
Since the method for producing a light-shielding film of the present disclosure uses the ink of the present disclosure, it is possible to form a light-shielding film having excellent light-shielding properties, a high refractive index (preferably 1.75 or more), and excellent patterning properties. ..

As described above, the method for producing a light-shielding film of the present disclosure is a method for forming a light-shielding film on a base material.
The light-shielding film manufacturing method of the present disclosure is also suitable as a manufacturing method for manufacturing an optical member including a base material and a light-shielding film, which will be described later.

<Base material>
Hereinafter, the base material in the method for producing a light-shielding film of the present disclosure will be described.
The base material is not particularly limited, and either a non-absorbent base material that does not absorb ink or an absorbable base material that absorbs ink can be used.
“Non-absorbable” refers to a property in which the water absorption rate (mass%, 24 hr.) Is less than 0.2 in ASTM D570 of the ASTM test method.

Examples of the non-absorbent base material include a glass base material, a resin (plastic) base material [eg, a polyvinyl chloride (PVC) base material, a polystyrene (PS) base material, a polycarbonate (PC) base material, and a polyester base material (for example, Polyethylene terephthalate (PET), polyethylene naphthalate), polyolefin base material (for example, polypropylene (PP)), acrylic resin base material, etc.] and the like.
Examples of the absorbent base material include paper and non-woven fabric.
A glass base material or a resin base material is preferable as the base material in the optical member provided with the base material and the light-shielding film, which will be described later.

<Granting process>
The applying step is a step of applying the above-mentioned ink of the present disclosure on a base material to obtain an ink film.
The method of applying ink in the applying step is not particularly limited, and known methods such as a coating method, a dipping method, a gravure method, a flexographic method, and an inkjet method can be applied.
Above all, the inkjet method is preferable from the viewpoint of easily forming a light-shielding film having a desired pattern shape, from the viewpoint of speeding up the formation of the light-shielding film, and the like.

Ink application by the inkjet method can be performed using a known inkjet recording device.
Examples of the inkjet recording device include a device including an ink supply system, a temperature sensor, and a heating means.
The ink supply system preferably includes, for example, a source tank containing ink, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo type inkjet head preferably has multi-size dots of 1 pl to 100 pl (more preferably 8 pl to 30 pl), preferably 320 dpi (dot per inch) × 320 dpi to 4000 dpi × 4000 dpi (more preferably 400 dpi × 400 dpi to 1600 dpi ×). Those that can be driven so as to be able to discharge at a resolution of 1600 dpi, more preferably 720 dpi × 720 dpi to 1600 dpi × 1600 dpi) are preferable.
In addition, dpi represents the number of dots per 2.54 cm (1 inch).

<Irradiation process>
The irradiation step is a step of irradiating the ink film with active energy rays to obtain a light-shielding film.
In the irradiation step, irradiation of the ink film with active energy rays (that is, light) causes the polymerization reaction of the photopolymerizable monomer to proceed in the ink film, thereby curing the ink film, resulting in film strength and substrate. A light-shielding film having excellent fixability to the surface is formed.

Examples of the active energy ray include ultraviolet rays (UV), visible light, electron beam, and the like, and among them, ultraviolet rays are preferable from the viewpoint of versatility.
The peak wavelength of the active energy ray is preferably 200 nm to 405 nm, more preferably 220 nm to 390 nm, and even more preferably 220 nm to 385 nm.
The peak wavelength of the active energy ray is preferably 200 nm to 310 nm, and preferably 200 n to 280 nm.

Exposure surface illuminance when active energy rays are irradiated, for example, ^{10mW / cm 2 ~2000mW / cm 2} , preferably ^{500mW / cm 2 ~2000mW / cm 2} , more ^preferably, 800mW / cm 2 ^~1500mW / It is cm ^2.
The exposure energy when the active energy ray (light) is irradiated is, for example, 10 mJ / cm ^{2 to} 20000 mJ / cm ² , preferably 500 mJ / cm ^{2 to} 20000 mJ / cm ² , and more preferably 800 mJ / cm ^{2 to} 15000 mJ. / Cm ² .

As an active energy radiation source (that is, a light source) for generating an active energy ray, a metal halide lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a UV fluorescent lamp, a gas laser, and a solid state laser are used. , LED (Light Emitting Diode), LD (Laser Diode) and the like.

In the irradiation step, the irradiation time of the active energy rays on the ink applied on the substrate is preferably 0.01 seconds to 30 seconds, more preferably 0.05 seconds to 10 seconds, and even more preferably. It is 0.1 seconds to 5 seconds.
As the irradiation conditions and the basic irradiation method, the irradiation conditions and the irradiation method disclosed in Japanese Patent Application Laid-Open No. 60-132767 can be similarly applied.
As the activation energy ray irradiation method, specifically, a method in which light sources are provided on both sides of the head unit including an ink ejection device and the head unit and the light source are scanned by a so-called shuttle method, or another light source that does not involve driving is used. A method of irradiating with active energy rays is preferable.

<Heat drying process>
The method for producing a light-shielding film of the present disclosure may further include a heat-drying step after the applying step and before the irradiation step, if necessary.
The heating means is not particularly limited, and examples thereof include a heat drum, hot air, an infrared lamp, a heat oven, and a heat plate.
The heating temperature is preferably 40 ° C. or higher, more preferably 40 ° C. to 150 ° C., and even more preferably 40 ° C. to 80 ° C.

[Light-shielding film]
<First Embodiment>
The first embodiment of the light-shielding film of the present disclosure is a cured product of the ink of the present disclosure described above.
Therefore, the light-shielding film according to the first embodiment contains a black dye, titanium dioxide particles, and a polymer of a photopolymerizable monomer, and has a content mass ratio [titanium dioxide particles / black dye] of 2.0. It is 15.0 or less.
Therefore, the light-shielding film according to the first embodiment has excellent light-shielding properties and a high refractive index (preferably 1.75 or more).

In the light-shielding film according to the first embodiment, the preferred embodiments of the black dye, the titanium dioxide particles, and the photopolymerizable monomer are the same as the preferred embodiments of these components in the ink of the present disclosure.
The light-shielding film according to the first embodiment may appropriately contain components that can be contained in the ink of the present disclosure, in addition to the polymer of the black dye, titanium dioxide particles, and the photopolymerizable monomer.
The preferable contents of the black dye, the titanium dioxide particles, and the photopolymerizable monomer (and other components contained as necessary) in the light-shielding film according to the first embodiment are preferable for each component in the ink of the present disclosure. It is the same as the content.
However, in the description of the preferable content in the ink of the present disclosure, "relative to the total amount of ink" shall be read as "relative to the total solid content of the light-shielding film".
Here, the total solid content of the light-shielding film corresponds to the total amount of the light-shielding film when the light-shielding film does not contain a liquid component (organic solvent, water, etc.), and when the light-shielding film contains a liquid component, It corresponds to the total amount of the light-shielding film excluding the liquid component (hereinafter, the same applies).
Further, in the description of the preferable content in the ink of the present disclosure, "content of photopolymerizable monomer" shall be read as "content of polymer of photopolymerizable monomer".

The light-shielding film according to the first embodiment is a film having a high refractive index, and the refractive index is preferably 1.75 or more, and more preferably 1.80 or more.
The refractive index is a value measured by ellipsometry at a wavelength of 590 nm.
The refractive index can be measured using, for example, a high-speed spectroscopic ellipsometer M-2000 (JA Woolam Japan Co., Ltd.).

The film thickness of the light-shielding film can be, for example, in the range of 0.5 μm to 100 μm, preferably in the range of 0.5 μm to 60 μm.
Further, from the viewpoint of light-shielding property, the film thickness of the light-shielding film may be thick, and may be 35 μm to 60 μm.
Hereinafter, a supplement will be given regarding a light-shielding film having a thick film thickness.
Usually, in an ink containing a certain amount of organic solvent, the film thickness is reduced (specifically, in the process from forming the ink film on the base material to drying the ink film to obtain a light-shielding film). The decrease in film thickness due to the removal of the organic solvent) may be remarkable.
On the other hand, the ink of the present disclosure is an ink containing a photopolymerizable monomer, and the content of the organic solvent can be reduced. Therefore, in the formation of the light-shielding film using the ink of the present disclosure, the decrease in the film thickness in the process from the formation of the ink film on the base material to the photo-curing of the ink film to obtain the light-shielding film is reduced. it can.
For this reason, the inks of the present disclosure are also suitable for applications of forming a light-shielding film having a thick film thickness (for example, a film thickness of 35 μm to 60 μm).

The light-shielding film according to the first embodiment can be used not only for blocking light, but also for absorbing light, providing a decorative function, and the like.
The light-shielding film according to the first embodiment is particularly suitable as a light-shielding film for optical members because it has excellent light-shielding properties and has a high refractive index (preferably 1.75 or more).
Details of the optical member will be described later.

The method for producing the light-shielding film according to the first embodiment is not particularly limited, but the above-mentioned method for producing the light-shielding film according to the present disclosure is preferable.

<Second Embodiment>
The second embodiment of the light-shielding film of the present disclosure contains a black dye, titanium dioxide particles, and an acrylic resin, and the mass ratio of the content of the titanium dioxide particles to the content of the black dye is 2.0 or more and 15.0. It is as follows.
The light-shielding film according to the second embodiment has excellent light-shielding properties and a high refractive index (preferably 1.75 or more).

In the light-shielding film according to the second embodiment, the preferred embodiment of the black dye and the titanium dioxide particles is the same as the preferred embodiment of these components in the ink of the present disclosure.

In the light-shielding film according to the second embodiment, the acrylic resin is at least one (co-) selected from the group consisting of compounds containing a (meth) acryloyl group (for example, (meth) acrylate, (meth) acrylamide, etc.). ) Polymers are preferred.
The acrylic resin is more preferably at least one selected from the group consisting of a compound containing one (meth) acryloyl group and a compound containing two (meth) acryloyl groups. Specific examples of the compound containing one (meth) acryloyl group and the compound containing two (meth) acryloyl groups include specific examples described as components in the ink of the present disclosure, respectively.

The light-shielding film according to the second embodiment may appropriately contain components that can be contained in the ink of the present disclosure, in addition to the black dye, titanium dioxide particles, and acrylic resin.
The preferable contents of the black dye, the titanium dioxide particles, and the acrylic resin (and other components contained as necessary) in the light-shielding film according to the second embodiment are the preferable contents of each component in the ink of the present disclosure. Is similar to.
However, in the description of the preferable content in the ink of the present disclosure, "relative to the total amount of ink" shall be read as "relative to the total solid content of the light-shielding film".
Further, in the description of the preferable content in the ink of the present disclosure, "content of photopolymerizable monomer" shall be read as "content of acrylic resin".

The preferred properties (refractive index, film thickness) and preferred use of the light-shielding film according to the second embodiment are the same as the preferable properties (refractive index, film thickness) and preferred use of the light-shielding film according to the first embodiment, respectively. ..

The method for producing the light-shielding film according to the second embodiment is not particularly limited, but the above-mentioned method for producing the light-shielding film according to the present disclosure is preferable.
That is, the light-shielding film according to the first embodiment and the light-shielding film according to the second embodiment may have a conceptually overlapping portion.
However, the light-shielding film according to the second embodiment can also be formed by using a non-curable composition containing a black dye, titanium dioxide particles, and an acrylic resin as a binder.

[Optical member]
The optical member of the present disclosure includes a base material and a light-shielding film according to the first embodiment described above or a light-shielding film according to the second embodiment described above.
As described above, as the base material in the optical member, a glass base material or a resin base material is preferable.
Examples of glass substrates or resin substrates include lenses (ie, resin lenses or glass lenses), prisms (ie, resin lenses or resin prisms), optical substrates (ie, optical glass substrates or optical resin substrates). , Etc. can be mentioned.
The light-shielding film is preferably provided on at least a part of the outer peripheral surface of the base material when the thickness direction of the base material (for example, the lens) (that is, the incident direction of light) is the axis.
In this case, the light obliquely incident on the base material (for example, a lens) hits the outer peripheral surface of the base material (that is, the interface with the light-shielding film) before passing through the base material and is absorbed by the light-shielding film. In this way, internal reflection at the interface between the light-shielding film and the base material is suppressed. As a result, the occurrence of flare or ghost is suppressed.

The method for manufacturing the optical member of the present disclosure is not particularly limited.
The optical member of the present disclosure can be manufactured, for example, by the method for manufacturing a light-shielding film of the present disclosure described above.
In this case, when the optical member of the above-described embodiment (that is, the mode in which the light-shielding film is provided on at least a part of the outer peripheral surface of the base material) is manufactured, the patterning property is improved by the ink of the present disclosure. The effect is more effectively exhibited. That is, it is possible to form a light-shielding film having a desired pattern shape while suppressing the formation (protrusion) of the light-shielding film in a region where the light-shielding film should not be formed.
For example, in a device including an optical member (for example, a digital camera including a lens), the outer peripheral surface of the optical member (base material) may be provided with a concave-convex structure for attachment to the device body. When a light-shielding film having a desired pattern is formed on a part of the uneven structure of the outer peripheral surface, the effect of improving the patterning property by the ink of the present disclosure is more effectively exhibited.

The ink, the light-shielding film, and the optical member described above can be used in various applications in which a light-shielding property is required and a high refractive index is required.
Specific applications include optical members used in optical equipment such as cameras, binoculars, microscopes, and semiconductor exposure equipment (eg, lenses, prisms, optical substrates); decorative films with a blackish hue having surface gloss; And so on.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, "parts" and "%" are based on mass.

[Examples 1 to 16, Comparative Examples 1 to 4]
<Ink preparation>
Each component shown in Tables 1 and 2 is mixed, and using a bead mill NPM (manufactured by Simmal Enterprises) and a circulation type piping and charging tank, dispersion treatment is performed under the following conditions, and Tables 1 and 2 show. 5000 g of each ink having the composition shown was obtained.

− Dispersion condition −
Bead diameter: φ0.05 mm
Bead filling rate: 60% by volume
Mill peripheral speed: 10 m / sec Amount of mixed liquid to be dispersed: 5000 g
Circulation flow rate (pump supply amount): 30 kg / hour
Treatment liquid temperature: 25 ° C to 30 ° C
Cooling water: Tap water Treatment time: 30 passes

<Formation of light-shielding film>
Using each ink prepared as described above, a light-shielding film was formed as follows.
A coating film is obtained as an ink film by applying the above ink on a glass substrate (Corning 1737 (manufactured by Corning Inc.), thickness 0.7 mm) by a spin coating method (2000 rpm (revolutions per minute), 60 seconds). It was.
The obtained coating film is irradiated with ultraviolet light (wavelength 365 nm) using an ultraviolet light emitting diode NC4U134 (manufactured by Nichia Corporation) with ^{an exposure energy amount of 1200 mJ / cm 2} (that is, an integrated amount of ultraviolet light). By doing so, the coating film was cured. As a result, a light-shielding film having a thickness of 1.0 μm after curing was obtained.
However, in Examples 15 and 16 using the ink containing an organic solvent, an operation of drying the coating film in a heating furnace at 70 ° C. for 30 minutes was added before irradiating the coating film with ultraviolet light.

<Evaluation>
The following evaluations were carried out on the ink and the light-shielding film.
The results are shown in Tables 1 and 2.

(Refractive index of light-shielding film)
The refractive index of the light-shielding film was measured at a wavelength of 590 nm using a high-speed spectroscopic ellipsometer M-2000 (JA Woolam Japan Co., Ltd.). Based on the obtained measured values, the refractive index of the light-shielding film was evaluated according to the following evaluation criteria.

-Evaluation criteria for refractive index-
AA: The refractive index is 1.85 or more.
A: The refractive index is 1.80 or more and less than 1.85.
B: The refractive index is 1.75 or more and less than 1.80.
C: The refractive index is less than 1.75.

(Light-shielding property of light-shielding film)
With respect to the glass substrate on which the light-shielding film was formed, the optical density at transmission (transmission OD; “OD” is an abbreviation for Optical Density) was measured using a desktop transmission densitometer 361T (manufactured by X-Rite). Based on the obtained permeation OD, the light-shielding property of the light-shielding film was evaluated according to the following evaluation criteria.
The larger the transmitted OD, the better the light-shielding property.

-Evaluation criteria for light blocking effect-
AA: The transmission OD is 0.4 or more.
A: The transmission OD is 0.3 or more and less than 0.4.
B: The transmission OD is 0.1 or more and less than 0.3.
C: The transmission OD is less than 0.1.

(Ink patterning property)
The operation of forming the coating film as the ink film was changed to the operation of drawing 10 line patterns as the ink film, and the same operation as the above "formation of the light-shielding film" was performed, and the target line width was 1 mm. 10 light-shielding patterns (that is, line patterns cured by ultraviolet light irradiation) were formed.
Here, the line pattern was formed by applying the above ink on a glass substrate by an inkjet method using an inkjet printer DMP-3000 manufactured by FUJIFILM Corporation. At this time, the dot density was 1200 dpi × 1200 dpi, and the ink ejection amount per drop ejected from the inkjet head was 10 pL (picolitre).

For 10 light-shielding patterns, the line width of 10 points (that is, 100 points in total) was measured for each light-shielding pattern, and the average line width was calculated as the arithmetic mean value of the obtained measured value group, and the obtained average was obtained. Based on the line width, the average fluctuation width of the line width was calculated by the following formula.
Average fluctuation width of line width (%) = (Average line width-1) x 100

Based on the obtained average fluctuation range, the patterning property of the ink was evaluated according to the following evaluation criteria.
In the following evaluation criteria, the rank with the best patterning property of the ink is "AA".

-Evaluation criteria for patterning property-
AA: The average fluctuation range is less than 10%.
A: The average fluctuation range is 10% or more and less than 15%.
B: The average fluctuation range is 15% or more and less than 20%.
C: The average fluctuation range is 20% or more and less than 25%.
D: The average fluctuation range is 25% or more and less than 30%.
E: The line width cannot be measured due to poor ejection or poor line pattern drawing.

Details of each component shown in Tables 1 and 2 are as follows.
-Black dye-
BONJET BLACK AS-0850: Orient Chemical Industry Co., Ltd.-Titanium dioxide particles-
TTO-55A: manufactured by Ishihara Sangyo Co., Ltd. (rutile type; average primary particle size: 50 nm, surface treatment: Al (OH) ₃ )
MPT-142: manufactured by Ishihara Sangyo Co., Ltd. (rutile type; average primary particle size: 80 nm, surface treatment: Al (OH) _3, stearic acid)
A-220; manufactured by Ishihara Sangyo Co., Ltd. (anatase type; average primary particle size: 160 nm, surface treatment: Al (OH) ₃ )
R-550: manufactured by Ishihara Sangyo Co., Ltd. (rutile type; average primary particle size: 240 nm, surface treatment: Al, Si)

-Basic dispersant-
EFKA PX4731: BASF (basic dispersant, amine value: 25 mgKOH / g; compound having a polyethyleneimine skeleton)

-Photopolymerizable monomer-
EOEOEA (Specific Monomer A): 2- (2-ethoxyethoxy) Ethyl Acrylate IOCA (Specific Monomer A): Isooctyl Acrylate IDA (Specific Monomer A): Isodecyl Acrylate VEEA (Specific Monomer A): 2- (2-Bini) Loxyethoxy) Ethyl Acrylate NPGDA: Neopentyl Glycol Diacrylate IBOA: Isobornyl Acrylate PEA: 2-Phenoxyethyl Acrylate-Photopolymerization Initiator-
IRG819: IRGACURE® 819 (BASF; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide))
IRG2959: IRGACURE® 2959 (BASF; 2-hydroxy-4'-(2-hydroxyethoxy) -2-methylpropiophenone)
-Polymerization inhibitor-
MEHQ: p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

-Organic solvent-
-DEGdEE: Diethylene glycol diethyl ether (boiling point 180 ° C)

As shown in Tables 1 and 2, it contains a black dye, titanium dioxide particles, and a photopolymerizable monomer, and the content of the titanium dioxide particles is 15% by mass or more and 45% by mass or less, and the content mass ratio [titanium dioxide]. In Examples 1 to 16 using an ink having [particle / black dye] of 2.0 or more and 15.0 or less, a light-shielding film having excellent light-shielding properties and a high refractive index (preferably 1.75 or more) was used. It could be formed and had excellent ink patterning properties.

On the other hand, in Comparative Example 1 in which the content mass ratio [titanium dioxide particles / black dye] was less than 2.0, the refractive index of the light-shielding film decreased.
In Comparative Example 2 in which the content mass ratio [titanium dioxide particles / black dye] was more than 15.0, the light-shielding property of the light-shielding film was lowered.
In Comparative Example 3 in which the content of the titanium dioxide particles was less than 15% by mass, the refractive index of the light-shielding film was lowered.
In Comparative Example 4 in which the content of the titanium dioxide particles was more than 45% by mass, the patterning property of the ink was lowered. Specifically, due to the high viscosity of the ink, poor ink ejection occurred, making it impossible to measure the line width.

From the results of Examples 1 to 16, it can be seen that the content of the photopolymerizable monomer is preferably 30% by mass or more, more preferably 35% by mass or more (Examples 1 to 14) from the viewpoint of patterning property.

From the results of Examples 1 and 7 to 9, it can be seen that the average primary particle size of the titanium dioxide particles is preferably 100 nm or less (Examples 1 and 7) from the viewpoint of the light-shielding property of the light-shielding film.

From the results of Examples 1 to 16, the content of the organic solvent in the ink is preferably 20% by mass or less (Examples 1 to 15), and 15% by mass or less (Examples 1 to 14) from the viewpoint of patterning property. ) Is more preferable.

From the results of Examples 13 and 14, it can be seen that the photopolymerizable monomer preferably contains the specific monomer A (Example 13) from the viewpoint of patterning property.

The disclosure of Japanese Patent Application No. 2018-175589 filed on September 20, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (14)

Contains black dye, titanium dioxide particles and photopolymerizable monomer,
The content of the titanium dioxide particles is 15% by mass or more and 45% by mass or less with respect to the total amount of the black ink composition.
A black ink composition in which the mass ratio of the content of the titanium dioxide particles to the content of the black dye is 2.0 or more and 15.0 or less. The black ink composition according to claim 1, wherein the content of the photopolymerizable monomer is 30% by mass or more with respect to the total amount of the black ink composition. The black ink composition according to claim 1 or 2, wherein the average primary particle size of the titanium dioxide particles is 10 nm or more and 100 nm or less. The photopolymerizable monomer contains at least one of a compound having one photopolymerizable group and a compound having two photopolymerizable groups.
Claims 1 to claim that the total content of the compound having one photopolymerizable group and the compound having two photopolymerizable groups is 30% by mass or more with respect to the total amount of the black ink composition. The black ink composition according to any one of 3. The black ink composition according to any one of claims 1 to 4, wherein the content of the organic solvent is 20% by mass or less with respect to the total amount of the black ink composition. The photopolymerizable monomer comprises 2- (2-ethoxyethoxy) ethyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. The black-based ink composition according to any one of claims 1 to 5, which comprises at least one selected from the group. The 2- (2-ethoxyethoxy) ethyl (meth) acrylate, the isooctyl (meth) acrylate, the isodecyl (meth) acrylate, and the 2- (2-vinyloxyethoxy) in the entire photopolymerizable monomer. The black ink composition according to claim 6, wherein the total proportion of ethyl (meth) acrylate is 15% by mass or more. The black ink composition according to any one of claims 1 to 7, which is used as an inkjet ink. A light-shielding film that is a cured product of the black ink composition according to any one of claims 1 to 8. Contains black dye, titanium dioxide particles and acrylic resin,
A light-shielding film in which the mass ratio of the content of the titanium dioxide particles to the content of the black dye is 2.0 or more and 15.0 or less. The light-shielding film according to claim 9 or 10, which is a light-shielding film for an optical member. With the base material
The light-shielding film according to any one of claims 9 to 11.
An optical member comprising. The base material is a glass base material or a resin base material, and the base material is a glass base material or a resin base material.
The optical member according to claim 12, wherein the light-shielding film is provided on at least a part of the outer peripheral surface of the base material when the thickness direction of the base material is the axis. A step of applying the black ink composition according to any one of claims 1 to 8 to form an ink film on a base material.
A step of irradiating the ink film with active energy rays to obtain a light-shielding film,
A method for producing a light-shielding film having a light-shielding film.