JP7312824B2 - Compositions, membranes and optical sensors - Google Patents

Description

The present invention relates to compositions, films, and optical sensors containing high refractive index particles.

Titanium oxide is a particle with a high refractive index. Attempts to use such particles with a high refractive index for light scattering films and the like are being investigated.

Patent Document 1 describes an invention relating to a light diffusive transfer material having an organic film containing at least one type of light diffusing particles and at least one type of high refractive index inorganic filler on a support, wherein the content N [% by volume] of the light diffusing particles in the organic film is in the range of 25 to 50, and the thickness T [μm] of the organic film satisfies T≧150/N. Titanium oxide (TiO ₂ ) or the like is used as a high refractive index inorganic filler. Paragraph No. 0069 describes that the primary average particle size of the high refractive index inorganic filler is preferably 1 to 30 nm. The light diffusing transfer material of Patent Document 1 is said to be capable of providing a light diffusing transfer material that is excellent in transferability and capable of forming a light diffusing layer capable of improving the light extraction efficiency of an organic electroluminescence device.

Japanese Unexamined Patent Application Publication No. 2013-115008

In recent years, there is an increasing demand for films that moderately block visible light and have high light scattering properties. A method of using particles having a large particle size and a high refractive index is known to enhance the light scattering properties of a film. However, particles with a high refractive index (hereinafter also referred to as high refractive particles) generally tend to have a large specific gravity. When such particles having a large specific gravity are contained in a solvent-containing composition and used, the particles may settle during storage of the composition. For this reason, it has been difficult for conventionally known compositions to achieve both high levels of storage stability and light scattering properties of the resulting film.

The light diffusion transfer material of the invention described in Patent Document 1 is supposed to form a light diffusion layer capable of improving the light extraction efficiency of an organic electroluminescence device. Since Patent Document 1 aims to increase the light extraction efficiency of the organic electroluminescence device, the light diffusion layer obtained from the light diffusible transfer material of the invention described in Patent Document 1 is not a member that moderately blocks visible light, but rather has high visible light transmittance.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composition capable of forming a film having good storage stability and excellent light scattering properties. Another object is to provide a film and an optical sensor.

Under such circumstances, the present inventors conducted intensive studies, and as a result, found that the above-described objects can be achieved by the composition described later, and completed the present invention. The present invention provides the following.
<1> Particles A having a refractive index of less than 2.0 and an average primary particle size of 500 nm or more;
Particles B having a refractive index of 2.0 or more, an average primary particle diameter of 100 nm or less, and having a higher specific gravity than particles A;
a resin;
A composition comprising a solvent,
When a film having a thickness of 4 μm is formed by heating at 200° C. for 5 minutes using the composition, the maximum value of the transmittance of light in the wavelength range of 400 to 700 nm of the film is 70% or less.
Composition.
<2> The composition according to <1>, wherein the difference between the specific gravity of the particles B and the specific gravity of the particles A is 2.0 g/cm ³ or more.
<3> The composition according to <1> or <2>, wherein the particles A have a specific gravity of 2.2 g/cm ³ or less.
<4> The composition according to any one of <1> to <3>, wherein the particles A have an average primary particle size of 500 nm or more and less than 3000 nm.
<5> The composition according to any one of <1> to <4>, wherein the particles A are resin particles.
<6> The composition according to any one of <1> to <5>, wherein the particles A are hollow particles.
<7> The composition according to any one of <1> to <6>, containing two or more kinds of the particles A.
<8> The composition according to any one of <1> to <7>, wherein the particles B have an average primary particle size of 30 nm or more and 100 nm or less.
<9> The composition according to any one of <1> to <8>, wherein the particles B are inorganic particles.
<10> The composition according to any one of <1> to <9>, containing two or more kinds of the particles B.
<11> The composition according to any one of <1> to <10>, wherein the total content of the particles A and the particles B in the total solid content of the composition is 30% by mass or more.
<12> The composition according to any one of <1> to <11>, wherein the resin includes a resin having an ethylenically unsaturated bond-containing group.
<13> The composition according to any one of <1> to <12>, further comprising a photopolymerization initiator.
<14> A film obtained using the composition according to any one of <1> to <13>.
<15> Contains particles A having a refractive index of less than 2.0 and an average primary particle size of 500 nm or more, particles B having a refractive index of 2.0 or more and an average primary particle size of 100 nm or less, and a resin,
The specific gravity of the particles B is greater than the specific gravity of the particles A,
A film having a maximum transmittance of 70% or less for light in the wavelength range of 400 to 1000 nm.
<16> An optical sensor including the film according to <14> or <15>.

ADVANTAGE OF THE INVENTION According to this invention, the composition which can form the film|membrane which has favorable storage stability and was excellent in light-scattering property can be provided. Membranes and optical sensors can also be provided.

1 is a schematic diagram illustrating one embodiment of an optical sensor of the present invention; FIG. FIG. 4 is a schematic diagram showing another embodiment of the optical sensor of the present invention;

The contents of the present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not indicate substitution or unsubstituted includes a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, "(meth)acrylate" represents acrylate and methacrylate, "(meth)acryl" represents acrylic and methacryl, "(meth)allyl" represents allyl and methallyl, and "(meth)acryloyl" represents acryloyl and methacryloyl.
In the present specification, Me in the chemical formulas represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays and electron beams.
As used herein, the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured using, for example, HLC-8220GPC (manufactured by Tosoh Corporation), and a column formed by connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 as a column. It can be determined by using tetrahydrofuran as a solvent.
In this specification, the value of refractive index is the average value of the refractive index for light with a wavelength of 589 nm at 23° C., unless otherwise specified.

<Composition>
The compositions of the present invention are
Particles A having a refractive index of less than 2.0 and an average primary particle size of 500 nm or more;
Particles B having a refractive index of 2.0 or more, an average primary particle size of 100 nm or less, and having a higher specific gravity than particles A;
a resin;
A composition comprising a solvent,
When the composition is heated at 200° C. for 5 minutes to form a film having a thickness of 4 μm, the film has a maximum transmittance of 70% or less for light in the wavelength range of 400 to 700 nm.

The composition of the present invention has good storage stability and can form a film with excellent light scattering properties. That is, since the particles B, which are particles with a large specific gravity, have a small average primary particle size, sedimentation of the particles B in the composition in a solution state can be suppressed, and as a result, excellent storage stability can be obtained. In addition, the composition of the present invention has a characteristic that when a film having a thickness of 4 μm is formed by heating at 200° C. for 5 minutes, the maximum value of the transmittance of light in the wavelength range of 400 to 700 nm of the film is 70% or less, and contains the particles A and B described above. Scattering occurs with the particles B having a small value, and the light irradiated to the film can be efficiently scattered and transmitted. Therefore, by using the composition of the present invention, a film having excellent light scattering properties can be formed. Furthermore, the angular dependence of scattered light can also be reduced.

When a film having a thickness of 4 μm is formed by heating at 200° C. for 5 minutes using the composition of the present invention, the maximum value of the transmittance of light in the wavelength range of 400 to 700 nm of this film is preferably 65% or less, more preferably 60% or less, and even more preferably 50% or less from the viewpoint of reducing the wavelength dependence of light scattering. The lower limit of the maximum transmittance is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.
Further, the maximum transmittance of light of 400 to 1000 nm of the film is preferably 70% or less, more preferably 65% or less, further preferably 60% or less, and particularly preferably 50% or less. The lower limit of the maximum transmittance is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.
Moreover, the haze of the film based on JIS K 7136 is preferably 30 to 100%. The upper limit is preferably 99% or less, more preferably 95% or less, and even more preferably 90% or less. The lower limit is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.

Formation of a film having such spectral characteristics can be achieved by appropriately adjusting the types and contents of the particles A and B.

The solid content concentration of the composition of the present invention is preferably 5 to 80% by mass for storage stability reasons. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. Each component used in the composition of the present invention is described below.

<<Particle A>>
The composition of the present invention contains particles A having a refractive index of less than 2.0 and an average primary particle size of 500 nm or more.

The average primary particle diameter of the particles A is 500 nm or more, preferably 500 nm or more and 6000 nm or less, more preferably 500 nm or more and 5000 nm or less, even more preferably 500 nm or more and less than 3000 nm, even more preferably 500 nm or more and 2500 nm or less, even more preferably 500 nm or more and 2000 nm or less, and particularly preferably 500 nm or more and 1500 nm or less, Most preferably, it is 500 nm or more and 1000 nm or less.

In this specification, the average primary particle size of particles is a value measured by the following method. That is, the primary particle diameter of the particles can be obtained by observing the particles with a transmission electron microscope (TEM) and observing a portion where the particles are not aggregated (primary particles). The particle size distribution of the particles can be determined by taking a transmission electron micrograph of the primary particles using a transmission electron microscope and then using the photograph to measure the particle size distribution with an image processor. In the present specification, the average primary particle diameter of particles is defined as the number-based arithmetic mean diameter calculated from the particle size distribution. In this specification, an electron microscope (H-7000) manufactured by Hitachi Ltd. is used as a transmission electron microscope, and Luzex AP manufactured by Nireco Corporation is used as an image processing apparatus.

The refractive index of the particles A is less than 2.0, preferably 1.9 or less, more preferably 1.8 or less, particularly preferably 1.7 or less. Although the lower limit of the refractive index of the particles A is not particularly limited, it can be 1.0 or more, and can also be 1.1 or more.

In this specification, the refractive index of particles is a value measured by the following method. First, a dispersion liquid is prepared using particles, a resin (dispersant) having a known refractive index, and propylene glycol monomethyl ether acetate. Thereafter, the prepared dispersion is mixed with a resin having a known refractive index to prepare coating liquids having particle concentrations of 10% by mass, 20% by mass, 30% by mass, and 40% by mass in the total solid content of the coating liquid. These coating liquids are formed on a silicon wafer to a thickness of 300 nm, and the refractive index of the resulting film is measured using ellipsometry (Lambda Ace RE-3300, manufactured by SCREEN Holdings Co., Ltd.). The refractive index corresponding to the particle concentration is then plotted on a graph to derive the particle refractive index.

The specific gravity of the particles A is preferably 2.5 g/cm ³ or less, more preferably 2.4 g/cm ³ or less, even more preferably 2.2 g/cm ³ or less, and particularly preferably 2.0 g/cm ³ or less. Although the lower limit of the specific gravity of the particles A is not particularly limited, it can be 0.5 g/cm ³ or more, and can also be 0.9 g/cm ³ or more.

In this specification, the specific gravity of particles is a value measured by the following method. First, 50 g of particles are introduced into a 100 mL volumetric flask. 100 mL of water is then measured out using another 100 mL graduated cylinder. After that, first, the measured water was put into the volumetric flask to the extent that the particles were soaked, and then ultrasonic waves were applied to the volumetric flask so that the particles and the water were blended. After that, add water until it reaches the marked line of the volumetric flask, and calculate as 50 g/(volume of water remaining in the volumetric flask)=specific gravity.

The particles A are preferably transparent or white particles. According to this aspect, when the composition of the present invention is applied to an optical sensor, loss of light received by the sensor can be further reduced.

Examples of the particles A include inorganic particles and resin particles. Examples of the inorganic particles include silica particles, hollow titanium oxide, hollow zirconia, etc. Silica particles are preferred. Commercially available inorganic particles include Silysia series manufactured by Fuji Silysia Chemical Co., Ltd. (eg, Silysia 310P), and Seahoster series manufactured by Nippon Shokubai Co., Ltd. (eg, Seahoster KE-S250).

Examples of resin particles include particles made of synthetic resins such as (meth)acrylic resins, styrene resins, polyamide resins, polyimide resins, polyolefin resins, polyurethane resins, polyurea resins, polyester resins, melanin resins, and silicone resins, and particles made of natural polymers such as chitin, chitosan, cellulose, crosslinked starch, and crosslinked cellulose. Among them, synthetic resin particles are preferably used because they have advantages such as easy control of the particle size.

As a method for producing resin particles, in the case of a relatively hard resin such as polymethyl methacrylate (PMMA), it is possible to make fine particles by a crushing method, but a method for producing resin particles by an emulsion suspension polymerization method is preferable from the viewpoint of ease and accuracy in particle size control. The method for producing resin particles is described in detail in "Ultrafine Particles and Materials" edited by Japan Society of Material Science, published by Shokabo in 1993, and "Preparation and Application of Fine Particles and Powders" supervised by Haruma Kawaguchi, published by CMC Publishing in 2005.

Resin particles are also available as commercial products, for example, MX-40T, MX-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MR-2HG, MR-7HG, MR-10HG, MR-3GSN, MR-5GSN, MR-7G, MR -10G, MR-5C, MR-7GC (manufactured by Soken Chemical Co., Ltd., acrylic resin particles), SX-130H, SX-350H, SX-500H (manufactured by Soken Chemical Co., Ltd., styrene resin particles), MBX-5, MBX-8, MBX-12MBX-15, MBX-20, MB20X-5, MB30X-5 , MB30X-8, MB30X-20, SBX-6, SBX-8, SBX-12, SBX-17 (above, manufactured by Sekisui Plastics Co., Ltd., acrylic resin particles), Chemipearl W100, W200, W300, W308, W310, W400, W401, W405, W410, W500, WF640, W7 00, W800, W900, W950, WP100 (manufactured by Mitsui Chemicals, Inc., polyolefin resin particles), Tospearl 120 (manufactured by Momentive Performance Technologies, silicone resin particles), Optobeads 2000M (manufactured by Nissan Chemical Industries, Ltd., melanin resin particles).

Particles A are also preferably hollow particles. Hollow particles refer to particles having a void portion in which the material constituting the particles does not exist inside from the surface of the particles. The size, shape, and number of void portions are not particularly limited. It may have an outer shell structure with a void in the center, or may have a structure in which a plurality of fine voids are dispersed inside the particle.

The hollow particles preferably have a porosity of 1 to 90%. The lower limit of the porosity is preferably 5% or more, more preferably 10% or more. The upper limit of the porosity is preferably 85% or less, more preferably 80% or less. The porosity of the hollow particles refers to the ratio of the volume occupied by the voids to the total volume of the hollow particles. The porosity of the hollow particles can be measured by observing the hollow particles using a transmission electron microscope, measuring the outer diameter and the pore diameter, and calculating the "ratio of the volume occupied by the voids to the total volume" using the following formula.
Formula: {(void diameter) ³ /(outer diameter) ³ } x 100%

More specifically, 100 hollow particles observed with a transmission electron microscope are arbitrarily selected, the circle-equivalent diameters of the outside and voids of these hollow particles are measured to determine the outer diameter and the void diameter, and the porosity is calculated by the above formula, and the average value thereof is used as the porosity. It can also be known from the measurement of the particle refractive index if the shell material of the particle (its refractive index) and the hollow shape are known.

The shape of the hollow particles is preferably spherical, but may be irregular or other shapes other than spherical.

The hollow particles may be hollow particles composed of an inorganic material (hereinafter also referred to as hollow inorganic particles) or hollow particles composed of a resin material (hereinafter also referred to as hollow resin particles).

Materials constituting the hollow resin particles include (meth)acrylic resins, styrene resins, polyamide resins, polyimide resins, polyolefin resins, polyurethane resins, polyurea resins, polyester resins, silicone resins, melanin resins, etc. (meth)acrylic resins and styrene resins are preferred, and (meth)acrylic resins are more preferred. As a method of manufacturing hollow resin particles, for example, the resin particles contain a foaming agent, the foaming agents are later foamed, the volatile substances are enclosed in the resin particles, and then the volatile substances are gasted and expanded, and the resin particles are melted. There are a method of injecting, and a method of mixture of a polymerized monomer and non -polymerized solvent, obtaining a resin particles containing a solvent, and removing the solvent (hereinafter referred to as a solvent removal method).

The hollow inorganic particles are preferably hollow silica particles. That is, the hollow inorganic particles are preferably silica particles having a void in the center. Specific examples of hollow silica particles include hollow particles described in JP-A-2013-237593 and WO 2007/060884.

The content of particles A is preferably 1 to 90% by mass based on the total solid content of the composition. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The composition of the present invention may contain only one type of particles A, or may contain two or more types. When only one kind of particles A is contained, better storage stability is likely to be obtained. Moreover, when two or more types of particles A are included, the angle dependence of light scattering can be further reduced. When two or more types of particles A are included, the total amount thereof preferably falls within the above range.

<<Particle B>>
The composition of the present invention contains particles B having a refractive index of 2.0 or more, an average primary particle size of 100 nm or less, and a higher specific gravity than particles A.

The average primary particle diameter of the particles B is 100 nm or less, preferably 5 nm or more and 100 nm or less from the viewpoint of storage stability of the composition, more preferably 10 nm or more and 100 nm or less, even more preferably 20 nm or more and 100 nm or less, and still more preferably 30 nm or more and 100 nm or less from the viewpoint of storage stability and the light scattering properties of the resulting film, and even more preferably 40 nm or more and 100 nm or less, and 50 nm or more and 100 nm or less. The following are particularly preferred.

The refractive index of the particles B is 2.0 or more, preferably 2.2 or more, and more preferably 2.4 or more. Although the upper limit of the refractive index of the particles B is not particularly limited, it can be 5 or less, and can also be 4 or less.

The difference between the refractive index of particles B and that of particles A is preferably 0.5 or more, more preferably 0.7 or more, and even more preferably 0.9 or more, because a film with excellent light scattering properties can be easily obtained. When the composition of the present invention contains two or more types of particles A, the mass average value of the refractive indices of two or more types of particles A is used as the refractive index value of particles A in calculating the difference in refractive index. The same applies to the case where the composition of the present invention contains two or more types of particles B.

The specific gravity of the particles B is preferably 1-7 g/cm ³ . The upper limit is preferably 6 g/cm ³ or less, more preferably 5 g/cm ³ or less. Although the lower limit of the specific gravity is not particularly limited, it can be 1.5 g/cm ³ or more, and can also be 2 g/cm ³ or more. However, the specific gravity of the particles B is larger than that of the particles A.

Particles B are preferably transparent or white particles. According to this aspect, when the composition of the present invention is applied to an optical sensor, loss of light received by the sensor can be further reduced.

Particles B are preferably inorganic particles. Examples of inorganic particles include titanium oxide particles, strontium titanate particles, barium titanate particles, zinc oxide particles, magnesium oxide particles, zirconium oxide particles, aluminum oxide particles, barium sulfate particles, and zinc sulfide particles. The inorganic particles used as the particles B are preferably particles containing titanium atoms, more preferably titanium oxide particles.

The titanium oxide particles preferably have a titanium dioxide (TiO ₂ ) content (purity) of 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more. In the titanium oxide particles, the content of low-order titanium oxide, titanium oxynitride, etc. represented by Ti _n O _2n-1 (n represents a number of 2 to 4) is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

The titanium oxide may be rutile-type titanium oxide or anatase-type titanium oxide. Rutile-type titanium oxide is preferred from the viewpoint of colorability and stability over time of dispersions and compositions. In particular, rutile-type titanium oxide has good colorability with little change in color difference even when heated. Moreover, the rutile ratio of titanium oxide is preferably 95% or more, more preferably 99% or more.

A known rutile-type titanium oxide can be used. There are two methods for producing rutile-type titanium oxide, a sulfuric acid method and a chlorine method, and titanium oxide produced by any of these methods can be suitably used. Here, the sulfuric acid method refers to a production method in which ilmenite ore or titanium slag is used as a raw material, dissolved in concentrated sulfuric acid to separate the iron content as iron sulfate, and the separated solution is hydrolyzed to obtain a hydroxide precipitate, which is fired at a high temperature to obtain rutile-type titanium oxide. In addition, the chlorine method uses synthetic rutile or natural rutile as a raw material, reacts chlorine gas with carbon at a high temperature of about 1000 ° C to synthesize titanium tetrachloride, and oxidizes it to obtain rutile type titanium oxide. Rutile-type titanium oxide is preferably rutile-type titanium oxide obtained by a chlorine method.

The specific surface area of the titanium oxide particles is preferably 10 to 400 m ² /g, more preferably 10 to 200 m ² /g, still more preferably 10 to 150 m 2 /g, particularly preferably 10 to 40 m ² /g, most preferably 10 to 20 ^{m 2 /} g, as measured by the BET (Brunauer, Emmett, Teller) method. . The pH of titanium oxide is preferably 6-8. The oil absorption of titanium oxide is preferably 10 to 60 (g/100g), more preferably 10 to 40 (g/100g).

The total amount of Fe ₂ O ₃ , Al ₂ O ₃ , SiO ₂ , Nb ₂ O ₅ and Na ₂ O in the titanium oxide particles is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, further preferably 0.02% by mass or less, and particularly preferably substantially free of these.

The shape of the titanium oxide particles is not particularly limited. Examples thereof include isotropic shapes (eg, spherical, polyhedral, etc.), anisotropic shapes (eg, needle-like, rod-like, plate-like, etc.), irregular shapes, and the like. The hardness (Mohs hardness) of the titanium oxide particles is preferably 5 to 8, more preferably 7 to 7.5.

Inorganic particles such as titanium oxide particles may be surface-treated with a surface treatment agent such as an organic compound. Surface treatment agents used for surface treatment of titanium oxide include polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrated silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agents, titanate coupling agents, and the like. Among them, silane coupling agents are preferred. The surface treatment may be performed using one type of surface treatment agent, or two or more types of surface treatment agents may be used in combination.

Inorganic particles such as titanium oxide particles are also preferably coated with a basic metal oxide or basic metal hydroxide. Basic metal oxides or basic metal hydroxides include metal compounds containing magnesium, zirconium, cerium, strontium, antimony, barium, calcium, or the like.

As the titanium oxide particles, titanium oxide particles described in "Titanium Oxide, Physical Properties and Applied Techniques, Manabu Seino, pp. 13-45, June 25, 1991, published by Gihodo Publishing" can also be suitably used.

As the particles B, commercially available ones can be preferably used. A commercially available product may be used as it is, or a classified product may be used. For example, as a commercial product of titanium particles oxide, for example, the product name TiPake R -550, R -580, R -630, R -670, R -680, R -780, R -780-2, R -780-2, R -820, R -830, R -850, R -850, R -850, R -850, R -930 R -980, CR -50, CR -50-2, CR -57, CR -58-2, CR -58-2, CR -60-2, CR -63, CR -63, CR -67, CR -SUPER70, CR -80, CR -85, CR -90-2, CR -90-2 , CR -95, CR -953, CR -97, PF -736, PF -737, PF -742, PF -690, PF -690, PF -711, PF -711, PF -739, PF -739, PF -740, PC -3, S -305, CR -EL, CR -EL, PT -401m , PT -401L, PT -501A, PT -501R, UT771, TTO -51, TTO -51, TTO -80A, TTO -S -2, A -220, MPT -136, MPT -140, MPT -141;
Trade names R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44, R-45M, R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR-52, A-110, A-19 manufactured by Sakai Chemical Industry Co., Ltd. 0, SA-1, SA-1L, STR-100A-LP, STR-100C-LP, TCA-123E;
Trade names of JR, JRNC, JR-301, JR-403, JR-405, JR-600A, JR-600E, JR-603, JR-605, JR-701, JR-800, JR-805, JR-806, JR-1000, MT-01, MT-05, MT-10EX, manufactured by Teika Co., Ltd. MT-100S, MT-100TV, MT-100Z, MT-100AQ, MT-100WP, MT-100SA, MT-100HD, MT-150EX, MT-150W, MT-300HD, MT-500B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-70 0BS, MT-700HD, MT-700Z;
Trade names KR-310, KR-380, KR-380N, ST-485SA15 manufactured by Titan Kogyo Co., Ltd.;
Trade names TR-600, TR-700, TR-750, TR-840, TR-900 manufactured by Fuji Titanium Industry Co., Ltd.;
Brilliant 1500 (trade name) manufactured by Shiraishi Calcium Co., Ltd., and the like can be mentioned. Titanium oxide particles described in paragraphs 0025 to 0027 of JP-A-2015-067794 can also be used.

Commercially available strontium titanate particles include SW-100 (manufactured by Titan Kogyo Co., Ltd.). Commercially available barium sulfate particles include BF-1L (manufactured by Sakai Chemical Industry Co., Ltd.). Commercially available zinc oxide particles include Zincox Super F-1 (manufactured by Hakusui Tech Co., Ltd.). Commercially available zirconium oxide particles include Z-NX (manufactured by Taiyo Koko Co., Ltd.) and Zirconeo-Cp (manufactured by Itec Co., Ltd.).

The content of particles B is preferably 5 to 90% by mass based on the total solid content of the composition. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. The lower limit is preferably 6% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.

The total content of particles A and particles B in the total solid content of the composition is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

As for the ratio of the particles A and the particles B in the composition, it is preferable that the particles B are 20 to 500 parts by mass per 100 parts by mass of the particles A. The upper limit is preferably 450 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. The lower limit is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more.

The composition of the present invention may contain only one type of particles B, or may contain two or more types. When only one kind of particles B is contained, better storage stability is likely to be obtained. Moreover, when two or more types of particles B are included, the angle dependence of light scattering can be further reduced. When two or more types of particles B are included, the total amount thereof is preferably within the above range.

<<Resin>>
The composition of the invention contains a resin. The resin is blended, for example, for dispersing particles in the composition or as a binder. A resin mainly used for dispersing particles is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

Any known resin can be used as the resin. Examples thereof include (meth)acrylic resins, (meth)acrylamide resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyimide resins, polyamide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, silicone resins, and urethane resins.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.

In the composition of the present invention, a resin having an acid group can be used as the resin. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. A resin having an acid group can also be used as an alkali-soluble resin or a dispersant. The acid value of the resin having acid groups is preferably 30-500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less. Regarding the resin having an acid group, paragraph numbers 0558 to 0571 of JP-A-2012-208494 (corresponding paragraph numbers 0685 to 0700 of US Patent Application Publication No. 2012/0235099) can be referred to, and the description of paragraph numbers 0076 to 0099 of JP-A-2012-198408 can be considered, and the contents thereof are incorporated herein.

In the composition of the present invention, a resin containing a repeating unit derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as an "ether dimer") may be used.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168539 can be referred to.

Specific examples of the ether dimer can be referred to paragraph number 0317 of JP-A-2013-029760, the content of which is incorporated herein.

In the composition of the present invention, a resin containing a repeating unit derived from a compound represented by the following formula (X) can be used as the resin.
In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15;

In the composition of the present invention, a resin containing a repeating unit having a graft chain can also be used as the resin. When the resin contains a repeating unit having a graft chain, steric hindrance due to the graft chain can more effectively suppress aggregation of particles in the composition, and excellent storage stability can be obtained. A resin containing a repeating unit having a graft chain may be used as a dispersant or as a binder.

In the present invention, the graft chain means a polymer chain branching from the main chain of the repeating unit. The length of the graft chain is not particularly limited, but the longer the graft chain, the higher the steric repulsion effect, which can improve the dispersibility of the particles. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.

The graft chain preferably contains a repeating unit having at least one structure selected from a repeating unit having a polyester structure, a repeating unit having a polyether structure, a repeating unit having a poly(meth)acrylic structure, a repeating unit having a polyurethane structure, a repeating unit having a polyurea structure, and a repeating unit having a polyamide structure. Repeating units of the polyester structure include repeating units of structures represented by the following formula (G-1), formula (G-4), or formula (G-5). Further, repeating units having a polyether structure include repeating units having a structure represented by the following formula (G-2). Further, repeating units having a poly(meth)acrylic structure include repeating units having a structure represented by the following formula (G-3).
In the above formula, R ^G1 and R ^G2 each represent an alkylene group. The alkylene group represented by R ^G1 and R ^G2 is not particularly limited, but a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, a linear or branched alkylene group having 2 to 16 carbon atoms is more preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is even more preferable.
In the above formula, ^RG3 represents a hydrogen atom or a methyl group.
In the above formula, Q ^G1 represents -O- or -NH-, and L ^G1 represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, _{-SO 2} -, -CO-, -O-, -COO-, OCO-, -S- and two or more thereof. A group formed by combining
^RG4 represents a hydrogen atom or a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and the like.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable from the viewpoint of improving the dispersibility of particles. The alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.

The graft chain preferably has a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a).

In the above formula, R ^G1 and R ^G2 each represent an alkylene group, R ^G3 represents a hydrogen atom or a methyl group, Q ^G1 represents -O- or -NH-, L ^G1 represents a single bond or a divalent linking group, R ^G4 represents a hydrogen atom or a substituent, and W ¹⁰⁰ represents a hydrogen atom or a substituent. n1 to n5 each independently represent an integer of 2 or more. R ^G1 to R ^G4 , Q ^G1 and L ^G1 have the same meanings as R ^G1 to R ^G4 , Q ^G1 and L ^G1 described in formulas (G-1) to (G-5), and the preferred ranges are also the same.

In formulas (G-1a) to (G-5a), W ¹⁰⁰ is preferably a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable from the viewpoint of improving the dispersibility of pigments. The alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.

In formulas (G-1a) to (G-5a), each of n1 to n5 is preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and even more preferably an integer of 8 to 60.

In formula (G-1a), R ^{1 G1} in each repeating unit when n1 is 2 or more may be the same or different. In addition, when ^RG1 contains two or more different repeating units, the arrangement of each repeating unit is not particularly limited, and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-5a).

Repeating units having a graft chain include repeating units represented by the following formula (A-1-2).

In formula (A-1-2), ^X2 represents the main chain of the repeating unit, ^L2 represents a single bond or a divalent linking group, and ^W1 represents a graft chain.

Examples of the main chain of the repeating unit represented by X ² in formula (A-1-2) include the structures described for X ¹ in formula (A-1-1), and the preferred range is also the same. Examples of the divalent linking group represented by L ² in formula (A-1-2) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S- and a group formed by combining two or more of these. The graft chain represented by W ¹ in formula (A-1-2) includes the above-described graft chains.

Specific examples of the repeating unit represented by formula (A-1-2) include repeating units represented by the following formula (A-1-2a) and repeating units represented by the following formula (A-1-2b).

In formula (A-1-2a), R ^b1 to R ^b3 each independently represent a hydrogen atom or an alkyl group, Q ^b1 represents -CO-, -COO-, -OCO-, -CONH- or a phenylene group, ^L2 represents a single bond or a divalent linking group, and ^W1 represents a graft chain. The number of carbon atoms in the alkyl groups represented by R ^b1 to R ^b3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. Q ^b1 is preferably -COO- or -CONH-, more preferably -COO-.

In formula (A-1-2b), R ^b10 and R ^b11 each independently represent a hydrogen atom or an alkyl group, m2 represents an integer of 1 to 5, L ² represents a single bond or a divalent linking group, and W ¹ represents a graft chain. The number of carbon atoms in the alkyl group represented by R ^b10 and R ^b11 is preferably 1-10, more preferably 1-3.

The weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1,000 or more, more preferably 1,000 to 10,000, even more preferably 1,000 to 7,500. In addition, in the present invention, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for polymerization of the same repeating unit. For example, a repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, the macromonomer means a polymer compound in which a polymerizable group is introduced at the terminal of the polymer. When a repeating unit having a graft chain is formed using a macromonomer, the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.

In the composition of the present invention, it is also preferable to use a resin having a structure in which a polymer chain is bonded to a trivalent or higher linking group as the resin. Examples of such a resin include a resin having a structure represented by the following formula (SP-1) (hereinafter also referred to as resin (SP-1)). Resin (SP-1) can be preferably used as a dispersant, but may also be used as a binder.
In the formula, Z ¹ represents a (m+n)-valent linking group,
Y ¹ and Y ² each independently represent a single bond or a linking group;
A ¹ represents a group containing a substituent selected from a heterocyclic group, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxy group;
P ¹ represents the polymer chain,
n represents 1 to 20, m represents 1 to 20, m+n is 3 to 21,
n Y ¹ and A ¹ may be the same or different,
Each of m Y ² and P ¹ may be the same or different.

At least one of Z ¹ , A ¹ and P ¹ in formula (SP-1) may contain an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, vinyloxy groups, allyl groups, methallyl groups, (meth)acryloyl groups, styrene groups, cinnamoyl groups and maleimide groups, with (meth)acryloyl groups, styrene groups and maleimide groups being preferred, (meth)acryloyl groups being more preferred, and acryloyl groups being particularly preferred.

When the resin (SP-1) contains an ethylenically unsaturated bond-containing group, such a resin corresponds to the polymerizable resin described later. The ethylenically unsaturated bond-containing group may be contained in any one of Z ¹ , A ¹ and P ¹ in formula (SP-1), but is preferably contained in P ¹ . Moreover, when P ¹ contains an ethylenically unsaturated bond-containing group, P ¹ is preferably a polymer chain having a repeating unit containing an ethylenically unsaturated bond-containing group in its side chain.

In formula (SP-1), A ¹ represents a group containing the substituents described above. As the substituent, a heterocyclic group, an acid group, a group having a basic nitrogen atom, a hydrocarbon group having 4 or more carbon atoms and a hydroxy group are preferable, and an acid group is more preferable. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, with the carboxyl group being preferred.

One A ¹ may contain at least one of the substituents described above, and may contain two or more of them. A ¹ preferably contains 1 to 10, more preferably 1 to 6, substituents as described above. Examples of the group containing the above-described substituent represented by A ¹ include groups formed by combining the above-described substituent with a linking group consisting of 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 to 40 sulfur atoms. Examples thereof include a chain saturated hydrocarbon group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or a group formed by bonding one or more acid groups via an aromatic hydrocarbon group having 5 to 10 carbon atoms. The above chain saturated hydrocarbon group, cyclic saturated hydrocarbon group and aromatic hydrocarbon group may further have a substituent. Examples of substituents include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxy group, a carboxyl group, an amino group, a sulfonamide group, an N-sulfonylamide group, an acyloxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate group, and an ethylenically unsaturated bond-containing group. Also, the substituent itself may be ^A1 .

The chemical formula weight of A ¹ is preferably 30-2000. The upper limit is preferably 1000 or less, more preferably 800 or less. The lower limit is preferably 50 or more, more preferably 100 or more.

In formula (SP-1), Z ¹ represents a (m+n)-valent linking group. (m+n)-valent linking groups include groups consisting of 1-100 carbon atoms, 0-10 nitrogen atoms, 0-50 oxygen atoms, 1-200 hydrogen atoms, and 0-20 sulfur atoms. Examples of the (m+n)-valent linking group include the following structural units or groups (which may form a ring structure) formed by combining two or more of the following structural units.

The (m+n)-valent linking group may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxy group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acyloxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate group, an ethylenically unsaturated bond-containing group, and the like.

The (m+n)-valent linking group represented by Z ¹ is preferably a group represented by any one of the following formulae.
_L3 represents a trivalent group. _T3 represents a single bond or a divalent linking group, and three _T3s present may be the same or different.
_L4 represents a tetravalent group. _T4 represents a single bond or a divalent linking group, and the four _T4s present may be the same or different.
_L5 represents a pentavalent group. _T5 represents a single bond or a divalent linking group, and five _T5s may be the same or different.
_L6 represents a hexavalent group. _T6 represents a single bond or a divalent linking group, and the six _T6s present may be the same or different.

The divalent linking groups represented by T ₃ to T ₆ include -CH ₂ -, -O-, -CO-, -COO-, -OCO-, -NH-, aliphatic cyclic groups, aromatic hydrocarbon cyclic groups, heterocyclic groups, and groups consisting of combinations thereof. The aliphatic ring group, aromatic hydrocarbon ring group and heterocyclic group may be monocyclic or condensed. The divalent linking group may further have the substituents described above.

Examples of the trivalent group represented by _L3 include groups obtained by removing one hydrogen atom from the above divalent linking group. Examples of the tetravalent group represented by L ₄ include groups obtained by removing two hydrogen atoms from the above divalent linking group. Examples of the pentavalent group represented by _L5 include groups obtained by removing three hydrogen atoms from the above divalent linking group. Examples of the hexavalent group represented by _L6 include groups obtained by removing 4 hydrogen atoms from the above divalent linking group. The tri- to hexavalent groups represented by L ₃ to L ₆ may further have the substituents described above.

The chemical formula weight of Z ¹ is preferably 20-3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 50 or more, more preferably 100 or more. If the chemical formula weight of ^Z1 is within the above range, the dispersibility of the pigment in the composition can be improved. The chemical formula weight of ^Z1 is a value calculated from the structural formula.

Specific examples of the (m+n)-valent linking group can be referred to paragraphs 0043 to 0055 of JP-A-2014-177613, the contents of which are incorporated herein.

In Formula (SP-1), Y ¹ and Y ² each independently represent a single bond or a linking group. Linking groups include groups consisting of 1-100 carbon atoms, 0-10 nitrogen atoms, 0-50 oxygen atoms, 1-200 hydrogen atoms, and 0-20 sulfur atoms. The groups described above may further have the substituents described above. Examples of the linking group represented by Y ¹ and Y ² include the following structural units or groups formed by combining two or more of the following structural units.

In formula (SP-1), P ¹ represents a polymer chain. The polymer chain represented by ^P1 is preferably a polymer chain having, in the main chain, at least one type of repeating unit selected from repeating units having a poly(meth)acrylic structure, repeating units having a polyether structure, repeating units having a polyester structure, repeating units having a polyamide structure, repeating units having a polyimide structure, repeating units having a polyimine structure, and repeating units having a polyurethane structure. Further, the polymer chain represented by ^P1 is preferably a polymer chain containing repeating units represented by the following formulas (P1-1) to (P1-5).

In the above formula, R ^G1 and R ^G2 each represent an alkylene group. The alkylene group represented by R ^G1 and R ^G2 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and still more preferably a linear or branched alkylene group having 3 to 12 carbon atoms. The alkylene group may have a substituent. Examples of substituents include aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated bond-containing groups, and the like.
In the above formula, ^RG3 represents a hydrogen atom or a methyl group.
In the above formula, Q ^G1 represents -O- or -NH-, L ^G1 represents a single bond or an arylene group, and L ^G2 represents a single bond or a divalent linking group. Q ^G1 is preferably -O-. ^LG1 is preferably a single bond. The divalent linking group represented by L ^G2 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO _{2 -} , -CO-, -O-, -COO-, -OCO-, -S-, -NHCO-, -CONH-, and a group formed by combining two or more of these.
^RG4 represents a hydrogen atom or a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated bond-containing groups, acid groups, and the like.

The repeating number of the repeating unit in P ¹ is preferably 3-2000. The upper limit is preferably 1500 or less, more preferably 1000 or less. The lower limit is preferably 5 or more, more preferably 7 or more. Moreover, ^P1 is preferably a polymer chain having a repeating unit containing an ethylenically unsaturated bond-containing group in its side chain. In addition, the proportion of repeating units containing an ethylenically unsaturated bond-containing group in a side chain in all repeating units constituting ^P1 is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more. The upper limit can be 100 mol %. Further, when P ¹ is a polymer chain having a repeating unit containing an ethylenically unsaturated bond-containing group in its side chain, P ¹ preferably contains other repeating units in addition to the repeating unit containing an ethylenically unsaturated bond-containing group in its side chain. Other repeating units include repeating units containing acid groups in side chains. In addition to the repeating unit containing an ethylenically unsaturated bond-containing group in the side chain, P ¹ further contains a repeating unit containing an acid group in the side chain, so that when patterning is performed by photolithography, the generation of development residues can be more effectively suppressed. When P ¹ contains a repeating unit containing an acid group in its side chain, the proportion of repeating units containing an acid group in its side chain in all repeating units constituting P ¹ is preferably 50 mol% or less, more preferably 2 to 48 mol%, and even more preferably 4 to 46 mol%.

The weight average molecular weight of the polymer chain represented by P ¹ is preferably 1,000 or more, more preferably 1,000 to 10,000. The upper limit is preferably 9000 or less, more preferably 6000 or less, even more preferably 3000 or less. The lower limit is preferably 1200 or more, more preferably 1400 or more. The weight average molecular weight of ^P1 is a value calculated from the weight average molecular weight of the raw material used for introducing the polymer chain.

Specific examples of the resin (SP-1) include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A-2013-043962, polymer compounds (C-1) to (C-61) described in paragraph numbers 0256 to 0269 of JP-A-2014-177613, and paragraph number 0061 of WO 2018/163668. Resins of the structures described are included, the contents of which are incorporated herein.

In the composition of the present invention, a resin having an ethylenically unsaturated bond-containing group (hereinafter also referred to as a polymerizable resin) can be used as the resin. By using a polymerizable resin, it is possible to suppress excessive progress of phase separation in the cured film. The amount of ethylenically unsaturated bond-containing groups (hereinafter also referred to as C=C value) of the polymerizable resin is preferably 0.01 to 5.0 mmol/g. The upper limit is more preferably 4.0 mmol/g or less, still more preferably 3.0 mmol/g or less, even more preferably 2.0 mmol/g or less, and particularly preferably 1.5 mmol/g or less. The lower limit is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more. The C=C value of the polymerizable resin is a numerical value representing the molar amount of C=C groups per 1 g of the solid content of the polymerizable resin. As for the C=C value of the polymerizable resin, the value calculated from the charged raw materials is used when it can be calculated from the raw materials used for synthesizing the polymerizable resin. As for the C=C value of the polymerizable resin, if the value cannot be calculated from the raw materials used in the synthesis of the polymerizable resin, the value measured using the hydrolysis method is used. Specifically, the low-molecular-weight component (a) of the C═C group site is extracted from the polymerizable resin by alkali treatment, the content thereof is measured by high performance liquid chromatography (HPLC), and calculated from the following formula. In addition, when the C═C group site cannot be extracted from the polymerizable resin by alkali treatment, the value measured by the NMR method (nuclear magnetic resonance) is used.
C = C value of polymerizable resin [mmol/g] = (content of low-molecular-weight component (a) [ppm]/molecular weight of low-molecular-weight component (a) [g/mol])/(weighing value of polymerizable resin [g] x (solid concentration of polymerizable resin [mass%]/100) x 10)

Examples of the polymerizable resin include a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in a side chain, a resin represented by the above formula (SP-1), and having a structure in which at least one of Z ¹ , A ¹ and P ¹ contains an ethylenically unsaturated bond-containing group.

Examples of the repeating unit having an ethylenically unsaturated bond-containing group in its side chain include repeating units represented by the following formula (A-1-1). A resin containing a repeating unit represented by the following formula (A-1-1) may be used as a dispersant or as a binder. In the polymerizable resin, the content of repeating units having an ethylenically unsaturated bond-containing group is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70 mol% in all repeating units of the polymerizable resin.

In formula (A-1-1), X ¹ represents a main chain of repeating units, L ¹ represents a single bond or a divalent linking group, and Y ¹ represents an ethylenically unsaturated bond-containing group.

In formula (A-1-1), the main chain of the repeating unit represented by X ¹ is not particularly limited. There is no particular limitation as long as it is a linking group formed from a known polymerizable monomer. Examples include poly(meth)acrylic linking groups, polyalkyleneimine linking groups, polyester linking groups, polyurethane linking groups, polyurea linking groups, polyamide linking groups, polyether linking groups, polystyrene linking groups, and the like. Poly(meth)acrylic linking groups and polyalkyleneimine linking groups are preferred, and poly(meth)acrylic linking groups are more preferred, from the viewpoint of availability of raw materials and production suitability.

In formula (A-1-1), the divalent linking group represented by L ¹ includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -CO. O--, --OCO--, --S-- and groups formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and preferably linear or branched. An alkylene group, an alkylene group in an alkyleneoxy group, and an alkylene group in an oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group, and a hydroxy group is preferable from the viewpoint of production suitability.

In formula (A-1-1), the ethylenically unsaturated bond-containing group represented by Y ¹ includes a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth)acryloyl group, a styrene group, a cinnamoyl group and a maleimide group, preferably a (meth)acryloyl group, a styrene group and a maleimide group, more preferably a (meth)acryloyl group, and particularly preferably an acryloyl group.

The resin containing the repeating unit represented by formula (A-1-1) may further contain a repeating unit having a graft chain. Examples of the repeating unit having a graft chain include the repeating unit represented by formula (A-1-2) described above. In the polymerizable resin, the content of the repeating unit having a graft chain is preferably 1.0 to 60 mol%, more preferably 1.5 to 50 mol%, of the total repeating units of the polymerizable resin.

The resin containing repeating units represented by formula (A-1-1) may further contain repeating units having an acid group. The content of repeating units having an acid group is preferably 80 mol % or less, more preferably 10 to 80 mol %, of all repeating units in the polymerizable resin.

The composition of the invention may contain a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of the acid groups and the basic groups is 100 mol %, and more preferably a resin composed substantially only of acid groups. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably has an acid group. The resin used as the dispersant is also preferably a resin containing a repeating unit having a graft chain. It is also preferable that the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. As the polyimine-based dispersant, a resin having a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms and having a basic nitrogen atom in at least one of the main chain and the side chain is preferred. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein. The resin used as the dispersant preferably has a structure in which a polymer chain is bonded to a trivalent or higher linking group. Examples of such a resin include a resin having a structure represented by formula (SP-1) described above. Also, the resin used as the dispersant is preferably a resin containing an ethylenically unsaturated bond-containing group. The resin used as the dispersant is preferably a resin having a structure represented by the formula (SP-1) described above, because it is easy to obtain better storage stability.

Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 2001, etc.), the Solsperse series manufactured by Nippon Lubrizol Co., Ltd. (e.g., Solsperse 20000, 76500, etc.), and the Ajinomoto Fine-Techno Co., Ltd. Ajisper series. In addition, the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.

The resin content is preferably 0.1 to 60% by mass based on the total solid content of the composition. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less.

In addition, the resin used in the composition preferably contains 10% by mass or more of a resin containing an ethylenically unsaturated bond-containing group, more preferably 20% by mass or more, and more preferably 30% by mass or more.

Further, the resin used in the composition preferably contains 20% by mass or more of a resin as a dispersant, more preferably 40% by mass or more, and more preferably 60% by mass or more.

Moreover, the content of the dispersant in the composition is preferably 5 to 200 parts by mass with respect to the total of 100 parts by mass of the particles A and B described above. The upper limit is preferably 180 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more.

The composition of the present invention also preferably contains a resin having an ethylenically unsaturated bond-containing group and a resin having no ethylenically unsaturated bond-containing group. According to this aspect, the effect of optimizing the sensitivity can also be expected. The content of the resin having an ethylenically unsaturated bond-containing group is preferably 20 to 500 parts by mass with respect to 100 parts by mass of the resin having no ethylenically unsaturated bond-containing group. The upper limit is preferably 450 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. The lower limit is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more.

The composition of the present invention also preferably contains a resin having a structure in which a polymer chain is bonded to a trivalent or higher linking group, and a resin containing a repeating unit having a graft chain. According to this aspect, the angle dependence of light scattering can be further reduced. In this case, among the resin having a structure in which a polymer chain is bonded to a trivalent or higher linking group and the resin containing a repeating unit having a graft chain, one resin is preferably a dispersant and the other resin is a binder. In addition, the content of the resin having a structure in which a polymer chain is bonded to a trivalent or higher linking group is preferably 20 to 500 parts by mass with respect to 100 parts by mass of the resin containing a repeating unit having a graft chain. The upper limit is preferably 450 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. The lower limit is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more.

<<Solvent>>
The composition of the invention contains a solvent. An organic solvent is mentioned as a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, the description of paragraph number 0223 of International Publication No. 2015/166779 can be considered, and this content is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include acetone, methyl ethyl ketone, cyclohexane, cyclohexanone, cyclopentanone, ethyl acetate, butyl acetate, cyclohexyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate, butyl diglycol acetate, 3-methoxybutyl acetate, 3-methoxy-N,N-dimethylpropane amide, 3-butoxy-N,N-dimethylpropanamide, and the like. These organic solvents can be used singly or in combination.

In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a mass ppt (parts per trillion) level organic solvent may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.

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

The solvent content in the composition is preferably 10 to 95% by mass. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. Only one solvent may be used, or two or more solvents may be used in combination. When two or more solvents are used in combination, the total is preferably within the above range.

<<polymerizable monomer>>
The composition of the invention preferably contains a polymerizable monomer. As the polymerizable monomer, known compounds that can be crosslinked by radicals, acids, or heat can be used. Examples thereof include compounds having an ethylenically unsaturated bond-containing group and compounds having a cyclic ether group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Cyclic ether groups include epoxy groups and oxetanyl groups. The polymerizable monomer is preferably a radically polymerizable monomer or a cationically polymerizable monomer, more preferably a radically polymerizable monomer.

The content of the polymerizable monomer is preferably 0.1 to 40% by mass based on the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less. A polymerizable monomer may be used individually by 1 type, and may use 2 or more types together. When two or more polymerizable monomers are used in combination, the total amount is preferably within the above range. When two types of polymerizable monomers are used in combination, two or more types of radically polymerizable monomers may be used alone, or a combination of radically polymerizable monomers and cationic polymerizable monomers may be used.

(Radical polymerizable monomer)
The radically polymerizable monomer is not particularly limited as long as it is a compound that can be polymerized by the action of radicals. The radically polymerizable monomer is preferably a compound having an ethylenically unsaturated bond-containing group, more preferably a compound having two or more ethylenically unsaturated bond-containing groups, and more preferably a compound having three or more ethylenically unsaturated bond-containing groups. The upper limit of the number of ethylenically unsaturated bond-containing groups is, for example, preferably 15 or less, more preferably 6 or less. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styryl group, a (meth)allyl group, and a (meth)acryloyl group, with a (meth)acryloyl group being preferred. The radically polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. It is also preferred that the radically polymerizable monomer contains a ring structure.

The molecular weight of the radically polymerizable monomer is preferably 200-3000. The upper limit of the molecular weight is preferably 2500 or less, more preferably 2000 or less. The lower limit of the molecular weight is preferably 250 or more, more preferably 300 or more.

The radically polymerizable monomer is also preferably a compound having an ethylenically unsaturated bond-containing group having at least one addition-polymerizable ethylene group and having a boiling point of 100° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate). Acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate and mixtures thereof, preferably pentaerythritol tetra(meth)acrylate.

Compounds represented by formulas (MO-1) to (MO-5) can also be suitably used as radically polymerizable monomers. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side of T is bonded to R.

In the above formula, n is 0-14 and m is 1-8. Plural R and T in the same molecule may be the same or different. In each of the compounds represented by formulas (MO-1) to (MO-5), at least one of the multiple Rs represents a group represented by -OC(=O)CH=CH ₂ or -OC(=O)C(CH ₃ )=CH ₂ . Specific examples of the compounds represented by formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A-2007-269779, the contents of which are incorporated herein.

Examples of radically polymerizable monomers include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) ) Acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth)acryloyl groups are bonded via an ethylene glycol and/or propylene glycol residue (for example, SR454, SR499, commercially available from Sartomer), diglycerin EO (ethylene oxide)-modified (meth) acrylate (commercially available as M -460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemicals Co., Ltd.), light acrylate POB-A0, light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), and the like can also be used.

As the radically polymerizable monomer, it is also preferable to use a trifunctional (meth)acrylate compound such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, ethyleneoxy isocyanurate-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A- GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) and the like.

A radically polymerizable monomer may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Examples of radically polymerizable monomers having an acid group include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. Examples of commercially available products include Aronix series M-305, M-510 and M-520 manufactured by Toagosei Co., Ltd. The acid value of the radically polymerizable monomer having an acid group is preferably 0.1-40 mgKOH/g. The lower limit is preferably 5 mgKOH/g or more. The upper limit is preferably 30 mgKOH/g or less.

When the composition of the present invention contains a radically polymerizable monomer, the content of the radically polymerizable monomer is preferably 0.1 to 40% by mass based on the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less. The radically polymerizable monomers may be used singly or in combination of two or more. When two or more radically polymerizable monomers are used in combination, the total amount thereof is preferably within the above range.

(Cationically polymerizable monomer)
Examples of cationic polymerizable monomers include compounds having a cationic polymerizable group. Examples of cationic polymerizable groups include cyclic ether groups such as epoxy groups and oxetanyl groups. The cationically polymerizable monomer is preferably a compound having a cyclic ether group, more preferably a compound having an epoxy group (also referred to as an epoxy compound).

The molecular weight of the cationic polymerizable monomer is preferably 200-3000. The upper limit of the molecular weight is preferably 2500 or less, more preferably 2000 or less. The lower limit of the molecular weight is preferably 250 or more, more preferably 300 or more.

Epoxy compounds include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of epoxy groups is preferably two or more.

Examples of epoxy compounds include compounds represented by the following formula (EP1).

In formula (EP1), R ^EP1 to R ^EP3 each independently represent a hydrogen atom, a halogen atom or an alkyl group. The alkyl group may have a cyclic structure and may have a substituent. R ^EP1 and R ^EP2 , and R ^EP2 and R ^EP3 may combine with each other to form a ring structure. Q ^EP represents a single bond or an n ^EP -valent organic group. R ^EP1 to R ^EP3 may combine with Q ^EP to form a ring structure. ^nEP represents an integer of 2 or more, preferably 2-10, more preferably 2-6. However, n ^EP is 2 when Q ^EP is a single bond. Details of R ^EP1 to R ^EP3 and Q ^EP can be referred to paragraphs 0087 to 0088 of JP-A-2014-089408, and the contents thereof are incorporated herein. Specific examples of the compound represented by formula (EP1) include compounds described in paragraph 0090 of JP-A-2014-089408 and compounds described in paragraph No. 0151 of JP-A-2010-054632, the contents of which are incorporated herein.

A commercial item can also be used as a cationically polymerizable monomer. For example, ADEKA Co., Ltd. ADEKA GLYCIROL series (eg, ADEKA GLYCIROL ED-505, etc.), Daicel Corporation Epolead series (eg, Epolead GT401, etc.), and the like.

When the composition of the present invention contains a cationic polymerizable monomer, the content of the cationic polymerizable monomer is preferably 0.1 to 40% by mass based on the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less. One type of cationic polymerizable monomer may be used alone, or two or more types may be used in combination. When two or more cationic polymerizable monomers are used in combination, the total amount thereof is preferably within the above range.

<<Photoinitiator>>
The composition of the invention can contain a photoinitiator. Photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators. It is preferable to select and use according to the type of the polymerizable monomer. When a radically polymerizable monomer is used as the polymerizable monomer, it is preferable to use a radical photopolymerization initiator as the photopolymerization initiator. Moreover, when a cationic polymerizable monomer is used as the polymerizable monomer, it is preferable to use a photocationic polymerization initiator as the photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, based on the total solid content of the composition. The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are included, the total amount thereof preferably falls within the above range.

(Photoradical polymerization initiator)
Examples of photoradical polymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound, and an oxime compound. , α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and Japanese Patent No. 6301489, the contents of which are incorporated herein.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure. 127 (manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 3. 79EG (manufactured by BASF) and the like. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).

Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162) compound described in Journal of Photopolymer Science and Technology (1995, pp.202-232) compound described in JP-A-2000-066385, JP-A-2000-08006 8, the compound described in JP 2004-534797, the compound described in JP 2006-342166, the compound described in JP 2017-019766, the compound described in JP 6065596, the compound described in WO 2015/152153, the compound described in WO 2017/051680, 2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, compounds described in WO 2013/167515, and the like. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2 -ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., JP 2012-01 Photopolymerization initiator 2) described in JP-A-4052 can be mentioned. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831 and NCI-930 (manufactured by ADEKA Corporation).

An oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A-2014-137466.

As a photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505.

An oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, compounds (C-3) described in JP-A-2013-164471, and the like.

An oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249, paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466, compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-83. 1 (manufactured by ADEKA Corporation).

An oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.

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

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. In addition, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300000, even more preferably 2000 to 300000, and particularly preferably 5000 to 200000, from the viewpoint of sensitivity. The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using ethyl acetate as a solvent at a concentration of 0.01 g/L.

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is reduced, the solubility in solvents and the like is improved, the precipitation becomes difficult over time, and the stability over time of the colored composition can be improved. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include JP 2010-527339, JP 2011-524436, WO 2015/004565, JP 2016-532675, paragraph numbers 0407 to 0412, and WO 2017/033680, paragraphs 0039 to 0055. Dimers of oxime compounds described in JP-A-2013-522445, compound (E) and compound (G) described in JP-A-2013-522445, Cmpd1 to 7 described in WO 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP-A-2017-523465, paragraph number 0020 of JP-A-2017-167399. 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, and the like.

The content of the radical photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, based on the total solid content of the composition. The composition of the present invention may contain only one type of radical photopolymerization initiator, or may contain two or more types. When two or more photoradical polymerization initiators are included, the total amount thereof preferably falls within the above range.

(Photo cationic polymerization initiator)
A photoacid generator is mentioned as a photocationic polymerization initiator. Examples of the photoacid generator include onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts and iodonium salts, and sulfonate compounds such as imidesulfonates, oximesulfonates, diazodisulfones, disulfones and o-nitrobenzylsulfonate, which are decomposed by light irradiation to generate an acid.

Examples of photocationic polymerization initiators include compounds represented by the following formulas (b1), (b2), and (b3).

In the above formula, R ²⁰¹ to R ²⁰⁷ each independently represent an organic group. The number of carbon atoms in the organic group is preferably 1-30. An alkyl group, an aryl group, etc. are mentioned as an organic group. In formula (b1), two of R ²⁰¹ to R ²⁰³ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. In the above formula, X ^- represents a non-nucleophilic anion. Examples of non-nucleophilic anions include sulfonate anions, carboxylate anions, bis(alkylsulfonyl)amide anions, tris(alkylsulfonyl)methide anions, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ and the like. Details of the compounds represented by formulas (b1), (b2), and (b3) can be referred to paragraphs 0139 to 0214 of JP-A-2009-258603, the contents of which are incorporated herein.

Specific examples of photocationic polymerization initiators include compounds having the following structures.

A commercial item can also be used for a photocationic polymerization initiator. Commercially available photocationic polymerization initiators include ADEKA Corporation's ADEKA Arkles SP series (for example, ADEKA Arkles SP-606), BASF Corporation's IRGACURE250, IRGACURE270, and IRGACURE290.

The content of the photocationic polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, based on the total solid content of the composition. The composition of the present invention may contain only one type of photocationic polymerization initiator, or may contain two or more types. When two or more photocationic polymerization initiators are included, the total amount thereof preferably falls within the above range.

<<Pigment derivative>>
The composition of the present invention can further contain pigment derivatives. Pigment derivatives include compounds having a structure in which a portion of the chromophore is substituted with an acidic group, a basic group, or a phthalimidomethyl group. Acid groups include sulfo groups, carboxyl groups and their quaternary ammonium bases. An amino group etc. are mentioned as a basic group. Details of the pigment derivative can be referred to paragraphs 0162 to 0183 of JP-A-2011-252065, the contents of which are incorporated herein. The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination. When two or more pigment derivatives are used in combination, the total of them is preferably within the above range.

<< Anti-coloring agent >>
The composition of the present invention may contain an anti-staining agent. The color inhibitors described herein can also be used as polymerization inhibitors. Examples of anti-coloring agents include phenol compounds, phosphite compounds, thioether compounds, etc. Phenol compounds having a molecular weight of 500 or more, phosphite compounds having a molecular weight of 500 or more, or thioether compounds having a molecular weight of 500 or more are more preferable. Moreover, the anti-coloring agent is preferably a phenol compound, more preferably a phenol compound having a molecular weight of 500 or more.

As the phenolic compound, any phenolic compound known as a phenolic anti-staining agent can be used. Preferred phenolic compounds include hindered phenolic compounds. Particularly preferred are compounds having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Compounds having a phenol group and a phosphite ester group in the same molecule are also preferred.

As the phenolic hydroxyl group-containing compounds, polysubstituted phenolic compounds are particularly preferably used. There are three types of polysubstituted phenol-based compounds (the following formula (A) hindered type, formula (B) semi-hindered type, and formula (C) less hindered type) having different substitution positions and structures due to their reactivity to trapped peroxy radicals resulting from stable phenoxy radical generation.
In formulas (A) to (C), R is a hydrogen atom or a substituent. R is preferably a hydrogen atom, a halogen atom, an optionally substituted amino group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylamino group, an optionally substituted arylamino group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted amino group, an optionally substituted alkyl group, or an optionally substituted arylsulfonyl group. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, and an arylamino group which may have a substituent are more preferred.

A more preferred form is a composite anti-coloring agent in which a plurality of structures exhibiting the anti-coloring function represented by the above formulas (A) to (C) are present in the same molecule. Specifically, a compound in which 2 to 4 structures exhibiting the anti-coloring function represented by the above formulas (A) to (C) are present in the same molecule is preferred. Among these, the formula (B) semi-hindered type is more preferable from the viewpoint of colorability. Representative examples of commercially available products include Sumilizer BHT (manufactured by Sumitomo Chemical), Irganox 1010, 1222 (manufactured by BASF), ADEKA STAB AO-20, AO-50, and AO-60 (manufactured by ADEKA Corporation) as (A). (B) includes Sumilizer BBM-S (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 245 (manufactured by BASF), and ADEKA STAB AO-80 (manufactured by ADEKA Corporation). Examples of (C) include ADEKA STAB AO-30 and AO-40 (manufactured by ADEKA Corporation).

The phosphite compounds include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethylbisphosphite. (2,4-di-tert-butyl-6-methylphenyl) and the like. Representative examples of commercially available phosphite ester compounds include ADEKA STAB PEP-36A (manufactured by ADEKA Corporation).

Thioether compounds include dilauryl thiodipropionate, dimyristyl thiodipropionate, dialkylthiodipropionates such as distearyl thiodipropionate, and pentaerythritol tetra(β-alkylthiopropionate) esters; pentaerythrityl tetrakis(3-laurylthiopropionate), etc.; (C12/C14)thiopropionyloxy]5-t-butylphenyl)sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl/stearylthiodipropionate, 4,4'-thiobis(6-t-butyl-methacrylate sol), 2,2'-thiobis(6-t-butyl-paracresol), distearyl-disulfide and the like. Representative examples of commercially available thioether compounds include ADEKA STAB AO-412S (CAS: 29598-76-3, manufactured by ADEKA Corporation), ADEKA STAB AO-503 (CAS: 10595-72-9, manufactured by ADEKA Corporation), KEMINOX PLS (CAS: 29598-76-3, manufactured by Chemipro Kasei Co., Ltd.), and the like. mentioned.

Commercially available anti-coloring agents include, in addition to the representative examples described above, Adekastab AO-50F, Adekastab AO-60G, Adekastab AO-330 (ADEKA Corporation), and the like.

In addition, as an anti-coloring agent,
N-oxide compounds such as 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide;
Piperidine-1-oxyl free radical, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-maleimide-2,2,6 piperidine-1-oxyl free radical compounds such as ,6-tetramethylpiperidine-1-oxyl free radical and 4-phosphonooxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical;
pyrrolidine 1-oxyl free radical compounds such as 3-carboxyproxyl free radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical;
N-nitrosophenylhydroxyamines such as N-nitrosophenylhydroxyamine cerium salt and N-nitrosophenylhydroxyamine aluminum salt;
diazonium compounds such as 4-diazophenyldimethylamine hydrogen sulfate, 4-diazodiphenylamine tetrafluoroborate, and 3-methoxy-4-diazodiphenylamine hexafluorophosphate;
cationic dyes;
nitro group-containing compounds;
Transition metal compounds such as FeCl ₃ and CuCl ₂ can also be used. Details thereof include compounds described in paragraphs 0211 to 0223 of JP-A-2015-034961, the contents of which are incorporated herein.

The content of the anti-coloring agent is preferably 0.01 to 20% by mass of the total solid content of the composition from the viewpoint of colorability and solvent resistance, more preferably 0.1 to 15% by mass, and particularly preferably 0.3 to 5% by mass. Only one anti-coloring agent may be used, or two or more anti-coloring agents may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.

<<Ultraviolet absorber>>
The composition of the invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminobutadiene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, and hydroxyphenyltriazine compounds. For details of the ultraviolet absorber, paragraph numbers 0052 to 0072 of JP-A-2012-208374 and paragraph numbers 0317-0334 of JP-A-2013-068814 can be referred to, and the contents thereof are incorporated herein. Examples of commercially available conjugated diene compounds include UV-503 (manufactured by Daito Kagaku Co., Ltd.). As the benzotriazole compound, the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016) may also be used.

The content of the ultraviolet absorber is preferably 0.1 to 10% by mass in the total solid content of the composition from the viewpoint of pattern shape and solvent resistance, more preferably 0.1 to 7% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.

<<adherence agent>>
The composition of the present invention may contain an adhesion agent. The adhesion agent is not particularly limited, and known adhesion agents can be used. Examples of adhesion agents include silane coupling agents.

As used herein, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate group, phenyl group and the like, with amino group, (meth)acryloyl group and epoxy group being preferred. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) ), etc. Further, specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604, the contents of which are incorporated herein.

The content of the adhesion agent is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, particularly preferably 1 to 5% by mass, based on the total solid content of the composition. Only one type of the adhesion agent may be used, or two or more types may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.

<<polymerization inhibitor>>
The composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, 1,4-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the composition.

<<chain transfer agent>>
The composition of the invention may contain a chain transfer agent. Chain transfer agents include N,N-dialkylaminobenzoic acid alkyl esters and thiol compounds, with thiol compounds being preferred. The thiol compound is preferably a compound having two or more (preferably 2 to 8, more preferably 3 to 6) mercapto groups in the molecule. Specific examples of thiol compounds include thiol compounds having a heterocyclic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptobutyl rate), 1,4-bis(3-mercaptobutyryloxy)butane and other aliphatic thiol compounds. Commercially available chain transfer agents include PEMP (manufactured by SC Organic Chemical Co., Ltd., thiol compound), Suncellar M (manufactured by Sanshin Chemical Industry Co., Ltd., thiol compound), and Karenz MT BD1 (manufactured by Showa Denko K.K., thiol compound). It is also preferable to use a compound having the following structure.

The content of the chain transfer agent is preferably 0.2 to 5.0% by mass, more preferably 0.4 to 3.0% by mass, based on the total solid content of the composition. The content of the chain transfer agent is preferably 1-40 parts by mass, more preferably 2-20 parts by mass, per 100 parts by mass of the polymerizable monomer. Only one type of chain transfer agent may be used, or two or more types may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.

<<Sensitizer>>
The composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator and lengthening the photosensitive wavelength. The sensitizer is preferably one that sensitizes the photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism. Sensitizers include compounds having absorption in the range of 300 to 450 nm. For details of the sensitizer, paragraph numbers 0231 to 0253 of JP-A-2010-106268 (corresponding paragraph numbers 0256 to 0273 of US Patent Application Publication No. 2011/0124824) can be referred to, and the contents thereof are incorporated herein.

The content of the sensitizer is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, based on the total solid content of the composition. Only one type of sensitizer may be used, or two or more types may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.

<<Co-sensitizer>>
It is also preferred that the composition of the present invention further contains a co-sensitizer. The co-sensitizer has actions such as further improving the sensitivity of the photopolymerization initiator and the sensitizer to actinic radiation, or suppressing inhibition of polymerization of the polymerizable monomer by oxygen. Regarding the co-sensitizer, the description of paragraph numbers 0254 to 0257 of JP-A-2010-106268 (corresponding paragraph numbers 0277 to 0279 of US Patent Application Publication No. 2011/0124824) can be considered, and the contents thereof are incorporated herein.

The content of the co-sensitizer is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, even more preferably 1.5 to 20% by mass, based on the total solid content of the composition. Only one co-sensitizer may be used, or two or more co-sensitizers may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.

<<Surfactant>>
The composition of the present invention may contain various types of surfactants from the viewpoint of further improving coatability. As the surfactant, various kinds of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used.

By including a fluorine-based surfactant in the composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving can be further improved. That is, when a film is formed using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the suitability for coating to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.

Examples of fluorine-based surfactants include surfactants described in paragraph numbers 0060 to 0064 of JP 2014-041318 (corresponding paragraph numbers 0060 to 0064 of WO 2014/017669), and surfactants described in paragraph numbers 0117 to 0132 of JP 2011-132503, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (manufactured by DIC Corporation), and Florard FC. 430, FC431, FC171 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, P F6320, PF6520, PF7002 (manufactured by OMNOVA), Futergent FTX218 (manufactured by Neos) and the like.

In addition, the fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved when heat is applied and the fluorine atom volatilizes can also be suitably used. Such fluorosurfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as Megafac DS-21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. Such fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.

A block polymer can also be used as the fluorosurfactant. As the fluorine-based surfactant, a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a (meth)acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). A fluorine-containing polymer compound containing repeating units derived from the compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.

A fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorosurfactant. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, Megafac RS-101, RS-102, RS-718K, RS-72-K manufactured by DIC Corporation, and the like. Further, as the fluorosurfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

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

The surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition. Only one type of surfactant may be used, or two or more types may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.

<<Other Additives>>
Furthermore, known additives such as plasticizers and oil sensitizers may be added to the composition to improve the physical properties of the film. Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. The content of the plasticizer is preferably 10% by mass or less with respect to the total amount of the compound (1), the polymerizable monomer, and the resin.

<Container>
The storage container for the composition of the present invention is not particularly limited, and known storage containers can be used. In addition, it is also preferable to use a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin or a bottle in which 6 types of resin are used in 7 layers for the purpose of suppressing the contamination of the raw materials and the composition with impurities. Examples of such a container include the container described in JP-A-2015-123351. Further, the inner wall of the container is preferably made of glass, stainless steel, or the like for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the composition, and suppressing deterioration of components.

<Method for preparing composition>
The compositions of the present invention can be prepared by mixing the aforementioned ingredients. In preparing the composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then blended successively. In addition, there are no particular restrictions on the order of charging or working conditions when blending.
Moreover, it is preferable that the preparation of the composition includes a process of dispersing the particles. In the process of dispersing particles, mechanical forces used for dispersing particles include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to treat under conditions in which pulverization efficiency is enhanced by using small-diameter beads, increasing the filling rate of beads, or the like. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing particles can be suitably used as described in "Dispersion Technology Encyclopedia, Information Organization Co., Ltd., July 15, 2005" and "Dispersion Technology Centered on Suspension (Solid/Liquid Dispersion System) and Industrial Application Practice Comprehensive Materials Collection, Management Development Center Publishing Department, October 10, 1978", JP 2015-157893, paragraph number 0022. Further, in the process of dispersing the particles, the particles may be refined in the salt milling step. Materials, equipment, processing conditions, and the like used in the salt milling step can be referred to, for example, JP-A-2015-194521 and JP-A-2012-046629.

In preparing the composition, it is preferable to filter it with a filter for the purpose of removing foreign matter and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g. nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultrahigh-molecular-weight polyolefin resins), and filters using such materials. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01 to 10.0 μm, more preferably 0.05 to 3.0 μm, even more preferably about 0.5 to 2.0 μm. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like can be used as filters.

It is also preferable to use a fibrous filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.

<Membrane>
A first aspect of the membrane of the invention is a membrane obtained using the composition of the invention as described above. In the film of the first aspect, the maximum transmittance of light in the wavelength range of 400 to 700 nm is preferably 70% or less, more preferably 65% or less, even more preferably 60% or less, and particularly preferably 50% or less. The lower limit of the maximum transmittance is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.

A second aspect of the film of the present invention is a film containing particles A having a refractive index of less than 2.0 and an average primary particle diameter of 500 nm or more, particles B having a refractive index of 2.0 or more and an average primary particle diameter of 100 nm or less, and a resin, wherein the specific gravity of the particles B is greater than the specific gravity of the particles A, and the maximum value of the transmittance of light in the wavelength range of 400 to 700 nm is 70% or less. The particles A, particles B, and resin contained in the film of the second aspect include the materials described in the section of the composition of the present invention, and the preferred ranges are also the same. The film of the second aspect preferably has a maximum transmittance of light in the wavelength range of 400 to 700 nm of 70% or less, more preferably 65% or less, even more preferably 60% or less, and particularly preferably 50% or less. The lower limit of the maximum transmittance is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.

The maximum transmittance of light of 400 to 1000 nm of the films of the first aspect and the second aspect of the present invention (hereinafter also simply referred to as the film of the present invention) is preferably 70% or less, more preferably 65% or less, further preferably 60% or less, and particularly preferably 50% or less. The lower limit of the maximum transmittance is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.

The haze based on JIS K 7136 of the film of the present invention is preferably 30 to 100%. The upper limit is preferably 99% or less, more preferably 95% or less, and even more preferably 90% or less. The lower limit is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more. The haze of the film is a value measured by the method described in Examples below.

The value of L* in the CIE 1976 L*a*b* color system of the film of the present invention is preferably 35-100. The value of L* is preferably 40 or more, more preferably 50 or more, and even more preferably 60 or more. According to this aspect, a film having excellent whiteness can be obtained. Also, the value of L* is preferably 95 or less, more preferably 90 or less, and even more preferably 85 or less. According to this aspect, the film can have appropriate visible transparency.

The value of a* is preferably -15 or more, more preferably -10 or more, and still more preferably -5 or more. The value of a* is preferably 10 or less, more preferably 5 or less, and even more preferably 0 or less. According to this aspect, a film having excellent whiteness can be obtained.

Also, the value of b* is preferably -35 or more, more preferably -30 or more, and still more preferably -25 or more. Also, the value of b* is preferably 20 or less, more preferably 10 or less, and even more preferably 0 or less. According to this aspect, a film having excellent whiteness can be obtained.

The thickness of the membrane of the present invention is preferably 2-40 μm. The upper limit of the film thickness is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. The lower limit of the film thickness is preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more. If the film thickness is within the above range, effects such as reduction in the thickness of the sensor and improvement in device optical sensitivity due to suppression of crosstalk can be expected.
The film of the present invention can be suitably used as a scattering layer for light-emitting devices and a scattering layer for display devices.

<Method for producing membrane>
The membrane of the invention can be produced through the process of applying the composition of the invention onto a support. Examples of the support include substrates made of materials such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. An organic film, an inorganic film, or the like may be formed on these substrates. Examples of materials for the organic film include resins. A substrate made of resin can also be used as the support. Moreover, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. In some cases, the support also has a black matrix that isolates each pixel. If necessary, the support may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate. Moreover, when a glass substrate is used as the support, it is preferable to form an inorganic film on the glass substrate or dealkalize the glass substrate before use.

A known method can be used as a method for applying the composition to the support. For example, dripping method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); cast coating method; method; nanoimprint method and the like. The method of application in inkjet is not particularly limited, and for example, the method described in the patent publication shown in "Spreading and Usable Inkjet-Infinite Possibilities Seen in Patents-, Published in February 2005, Sumibe Techno Research" (especially pages 115 to 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, and JP-A-2012-126830. JP-A-2006-169325 and the like. From the viewpoint of coating aptitude, spin coating is preferably performed at a speed of 300 to 6000 rpm, and more preferably at a speed of 400 to 3000 rpm. The temperature of the support during spin coating is preferably 10 to 100.degree. C., more preferably 20 to 70.degree. If it is said range, it will be easy to manufacture the film|membrane excellent in coating uniformity. In the case of the dropping method (drop casting), it is preferable to form a dropping region of the composition on the support using a photoresist as a partition so that a uniform film having a predetermined film thickness can be obtained. A desired film thickness can be obtained by controlling the amount of the composition to be dropped, the solid content concentration, and the area of the drop region.

The composition layer formed on the support may be dried (pre-baked). Pre-baking conditions are preferably, for example, a temperature of 60 to 150° C. for 30 seconds to 15 minutes.

The film manufacturing method may further include a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method. In addition, when the film of the present invention is used as a flat film, the step of forming a pattern may not be performed. The process of forming the pattern will be described in detail below.

(When patterning by photolithography)
The pattern forming method by photolithography preferably includes a step of patternwise exposing a composition layer formed by applying the composition of the present invention (exposure step), and a step of developing by removing an unexposed portion of the composition layer to form a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Each step will be described below.

<<Exposure process>>
In the exposure step, the composition layer is exposed patternwise. For example, the composition layer can be pattern-exposed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. Thereby, the exposed portion can be cured. Radiation (light) that can be used for exposure includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable.

Further, the exposure may be performed by continuously irradiating the light, or by pulsing the light (pulse exposure). Note that the pulse exposure is an exposure method in which light irradiation and pause are repeated in a cycle of short time (for example, less than millisecond level). In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more. The frequency is preferably 1 kHz or higher, more preferably 2 kHz or higher, and even more preferably 4 kHz or higher. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less. The maximum instantaneous illuminance is preferably 50000000 W/ ^m2 or more, more preferably 100000000 W/ ^m2 or more, and even more preferably 200000000 W/ ^m2 or more. The upper limit of the maximum instantaneous illuminance is preferably 1000000000 W/m ² or less, more preferably 800000000 W/m ² or less, and even more preferably 500000000 W/m ² or less. It should be noted that the pulse width is the time during which the light is applied in the pulse period. Also, the frequency is the number of pulse cycles per second. Further, the maximum instantaneous illuminance is the average illuminance within the time during which the light is irradiated in the pulse period. Further, the pulse cycle is a cycle in which light irradiation and rest in pulse exposure are set as one cycle.

The dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² and most preferably 0.08 to 0.5 J/cm ² . The oxygen concentration during exposure can be appropriately selected. For example, it may be exposed in the air, it may be exposed in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, substantially oxygen-free), or it may be exposed in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, 50% by volume). Also, the exposure illuminance can be set as appropriate, and is preferably selected from the range of 1000 to 100000 W/m ² . The oxygen concentration and exposure illuminance may be appropriately combined. For example, the illuminance may be 10000 W/m ² at an oxygen concentration of 10% by volume and 20000 W/m ² at an oxygen concentration of 35% by volume.

<<development process>>
Next, an unexposed portion of the composition layer after exposure is removed by development to form a pattern. The development and removal of the composition layer in the unexposed area can be carried out using a developer. As a result, the unexposed portion of the composition layer in the exposure step is eluted into the developer, leaving only the photocured portion on the support. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Moreover, in order to improve the residue removability, the process of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

Examples of the developer include organic solvents and alkaline developers, and the alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene. and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. Examples of surfactants include the surfactants described above, and nonionic surfactants are preferred. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. When an alkaline aqueous solution is used as the developer, it is preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the composition layer after development while rotating the support on which the composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotational speed of the support while moving the nozzle from the center of the support to the periphery.

After development, it is preferable to carry out additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is preferably 100 to 260° C., for example. The lower limit of the heating temperature is preferably 120°C or higher, more preferably 160°C or higher. The upper limit of the heating temperature is preferably 240°C or lower, more preferably 220°C or lower. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), a high-frequency heater, etc. so that the film after development meets the above conditions. When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

(When patterning by dry etching method)
Pattern formation by a dry etching method can be performed by a method such as curing a composition layer formed by applying the composition of the present invention on a support to form a cured product layer, then forming a patterned resist layer on the cured product layer, and then dry-etching the cured product layer using an etching gas using the patterned resist layer as a mask. Regarding pattern formation by a dry etching method, descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated into this specification.

<Optical sensor>
The optical sensor of the invention comprises the membrane of the invention. Types of optical sensors include ambient light sensors, illuminance sensors, and the like, which are preferably used as ambient light sensors. An ambient light sensor is a sensor that detects the color of ambient light (environmental light).

In addition to the film of the present invention, the optical sensor of the present invention also preferably has an optical filter having at least one type of pixels selected from colored pixels and infrared transmission filter pixels. Examples of colored pixels include red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. Moreover, the film of the present invention is preferably provided on the light incident side of the optical filter. By providing the film of the present invention on the light incident side of the optical filter, it is possible to further reduce the angular dependence of each pixel. The optical sensor of the present invention may have the pixel configuration described in WO2019/102887.

An embodiment of the optical sensor is shown using the drawings. The optical sensor 1 shown in FIG. 1 is provided with an optical filter 110 having pixels 111 to 114 on a photoelectric conversion element 101 . A film 121 of the present invention is formed on the optical filter 110 . An example of the pixels 111 to 114 forming the optical filter 110 is a combination of the pixel 111 being a red pixel, the pixel 112 being a blue pixel, the pixel 113 being a green pixel, and the pixel 114 being an infrared transmission filter pixel. In the optical sensor 1 shown in FIG. 1, the optical filter 110 has four types of pixels (pixels 111 to 114), but the number of types of pixels may be one to three, or five or more. It can be appropriately selected depending on the application. A flattening layer may be interposed between the photoelectric conversion element 101 and the optical filter 110 or between the optical filter 110 and the film 121 of the present invention.

Another embodiment of the optical sensor is shown in FIG. In the photosensor 2 shown in FIG. 2, an optical filter 110 having pixels 111 to 114 is provided on a photoelectric conversion element 101. In FIG. The optical filter 110 has a configuration similar to that of the embodiment described above. A member having the film 122 of the present invention formed on the surface of a transparent support 130 is arranged on the optical filter 110 . Examples of the transparent support 130 include a glass substrate and a resin substrate. In the optical sensor 2 shown in FIG. 2, the member having the film 122 of the present invention formed on the surface of the transparent support 130 is arranged above the optical filter 110 at a predetermined interval. 2, the film 122 of the present invention is formed only on one side of the transparent support 130, but the film 122 of the present invention may be formed on both sides of the transparent support 130. FIG. In the optical sensor 2 shown in FIG. 2, the film 122 of the present invention is formed on the surface of the transparent support 130 facing the optical filter 110, but the film 122 of the present invention may be formed on the surface of the transparent support 130 opposite to the optical filter 110. A planarizing layer may be interposed between the photoelectric conversion element 101 and the optical filter 110 or between the film 122 of the present invention and the transparent support 130 .

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. "Parts" and "%" are based on mass unless otherwise specified.

<Measurement of average primary particle size of particles>
The primary particle size of the particles was obtained by observing the particles with a transmission electron microscope (TEM) and observing the portion where the particles were not aggregated (primary particles). Specifically, after taking a transmission electron micrograph of the primary particles using a transmission electron microscope, the particle size distribution was determined by measuring the particle size distribution with an image processor using the photograph. The average primary particle diameter of the particles was defined as the number-based arithmetic mean diameter calculated from the particle size distribution. An electron microscope (H-7000) manufactured by Hitachi, Ltd. was used as a transmission electron microscope, and Luzex AP manufactured by Nireco Corporation was used as an image processing apparatus.

<Measurement of refractive index of particles>
A dispersion was prepared using particles, a resin (dispersant) having a known refractive index, and propylene glycol monomethyl ether acetate. Thereafter, the prepared dispersion liquid and a resin having a known refractive index were mixed to prepare coating liquids having particle concentrations of 10% by mass, 20% by mass, 30% by mass, and 40% by mass in the total solid content of the coating liquid. These coating liquids were formed on a silicon wafer to a thickness of 300 nm, and the refractive index of the resulting film was measured using ellipsometry (Lambda Ace RE-3300, manufactured by SCREEN Holdings Co., Ltd.). The particle concentration and refractive index were then plotted on a graph to derive the particle refractive index.

<Measurement of specific gravity of particles>
50 g of particles were placed in a 100 mL volumetric flask. Subsequently, 100 mL of water was measured using another 100 mL graduated cylinder. After that, the measured amount of water was added to the volumetric flask to the extent that the particles were soaked, and then ultrasonic waves were applied to the volumetric flask to blend the particles with the water. After that, additional water was added until reaching the marked line of the volumetric flask, and the specific gravity was calculated as 50 g/(volume of water remaining in the volumetric flask) = specific gravity.

<Measurement of weight average molecular weight>
The weight average molecular weights of dispersants and resins were measured by gel permeation chromatography (GPC) according to the following conditions.
Column type: Column connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 Developing solvent: Tetrahydrofuran Column temperature: 40°C
Flow rate (sample injection volume): 1.0 μL (sample concentration 0.1% by mass)
Apparatus name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve Base resin: Polystyrene resin

<C = C value>
The C=C value of the resin was calculated from the raw materials used to synthesize the resin.

<Method for measuring acid value>
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. A measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1, and a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) was used to neutralize and titrate the resulting solution at 25°C with a 0.1 mol/L sodium hydroxide aqueous solution. Using the inflection point of the titration pH curve as the titration end point, the acid value was calculated by the following formula.
A = 56.11 x Vs x 0.5 x f/w
A: Acid value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L aqueous sodium hydroxide solution required for titration
f: titer of 0.1 mol / L sodium hydroxide aqueous solution w: mass of measurement sample (g) (converted to solid content)

<Production of dispersion liquid>
Using an Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd. as a circulating dispersing device (bead mill), the mixed liquid having the composition shown in the table below was subjected to the following dispersion treatment to produce a dispersion liquid. Bead diameter: 0.2 mm in diameter
Bead filling rate: 65% by volume
Peripheral speed: 6 m/sec Pump supply volume: 10.8 kg/h Cooling water: Tap water Bead mill circular passage internal volume: 0.15 L
Amount of mixed liquid to be dispersed: 0.65 kg

The raw materials listed in the above table are as follows.
(particle)

The refractive index values in the above table are the refractive index values for light with a wavelength of 589 nm.

(resin)
B-1: Resin having the following structure (resin having a structure in which a polymer chain containing a substituent and a repeating unit of a poly(meth)acrylic structure is bonded to a hexavalent linking group (group Z). Weight average molecular weight: 10000, acid value: 80.4 mgKOH/g, C=C value: 0 mmol/g)
B-2: Resin having the following structure (a resin containing a repeating unit having a graft chain containing a repeating unit of a polyester structure. The numerical value attached to the main chain represents the molar ratio of the repeating unit, and the numerical value attached to the side chain represents the number of repeating units. Weight average molecular weight: 34000, acid value: 57.2 mgKOH/g, C=C value: 0 mmol/g)
B-3: Resin having the following structure (resin having a structure in which a polymer chain containing a substituent and a repeating unit of a poly(meth)acrylic structure is bonded to a hexavalent linking group (group Z). Weight average molecular weight: 6000, acid value: 31 mgKOH/g, C=C value: 1 mmol/g)

(solvent)
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: Propylene glycol monomethyl ether (PGME)
S-3: Cyclohexanone

<Preparation of composition>
A composition was produced by mixing raw materials shown in the table below.

The raw materials listed in the above table are as follows.
(dispersion liquid)
Dispersions 001-017, 101-119: Dispersions 001-017, 101-119 as described above

(Polymerizable monomer)
M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
M-2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)
M-3: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-4: Light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd., dimethylol-tricyclodecane diacrylate)

(resin)
B-1, B-2: Resins B-1, B-2 described above
B-4: Resin having the following structure (the numerical values attached to the main chain represent the molar ratio of repeating units. Weight average molecular weight: 11000, acid value: 69 mgKOH/g, C=C value: 1.4 mmol/g)
B-5: Resin having the following structure (the numerical values attached to the main chain represent the molar ratio of repeating units. Weight average molecular weight: 12000, acid value: 76.8 mgKOH/g, C=C value: 0 mmol/g)

(Photoinitiator)
I-1: Irgacure OXE01 (manufactured by BASF)
I-2: Omnirad 369 (manufactured by IGM Resins B.V.)
I-3: Omnirad TPO (manufactured by IGM Resins B.V.)

(Additive)
A-1: Adekastab AO-80 (manufactured by ADEKA Co., anti-coloring agent)
A-2: Irganox 1010 (manufactured by BASF, coloring inhibitor)
A-3: KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)

(Surfactant)
Su-1: the following compound (% indicating the proportion of repeating units is mol%. Weight average molecular weight: 14000)
Su-2: Futergent FTX218 (manufactured by Neos)

(polymerization inhibitor)
In-1: p-methoxyphenol In-2: 1,4-benzoquinone

(solvent)
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: Propylene glycol monomethyl ether (PGME)
S-3: Cyclohexanone

<Maximum Transmittance>
Each composition was applied to an 8-inch (=203.2 mm) glass wafer with an undercoat layer (CT-4000L, thickness 0.1 μm, manufactured by Fuji Film Electronic Materials Co., Ltd.) using a spin coater so that the thickness after post-baking was 4 μm, and heat treatment (pre-baking) was performed using a hot plate at 110 ° C. for 30 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm was irradiated with an exposure amount of 1000 mJ/cm ² for exposure, and then a heat treatment (post-baking) was performed using a hot plate at 200 ° C. for 5 minutes to form a film with a thickness of 4 μm.
The transmittance of light in the wavelength range of 400 to 700 nm of the resulting film was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), and the maximum value of transmittance in the above range was measured. The maximum value of transmittance was evaluated according to the following criteria.
5: The maximum transmittance is 50% or less.
4: The maximum transmittance is greater than 50% and 60% or less.
3: The maximum transmittance is greater than 60% and 70% or less.
2: The maximum transmittance is greater than 70% and 80% or less.
1: The maximum transmittance is greater than 80%.

<Light scattering>
Each composition was applied to an 8-inch (=203.2 mm) glass wafer with an undercoat layer (CT-4000L, thickness 0.1 μm, manufactured by Fuji Film Electronic Materials Co., Ltd.) using a spin coater so that the thickness after post-baking was 4 μm, and heat treatment (pre-baking) was performed using a hot plate at 110 ° C. for 30 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed by irradiating light with a wavelength of 365 nm at an exposure amount of 1000 mJ/cm ² , and then heat treatment (post-baking) was performed using a hot plate at 200 ° C. for 5 minutes to form a film. The haze value Hz of the obtained film was measured using a haze meter (NDH7000, manufactured by Nippon Denshoku Industries Co., Ltd.). It means that the higher the haze value Hz, the better the light scattering properties. Scattering performance was evaluated according to the following criteria.
5: Haze value Hz is 60% or more.
4: The haze value Hz is 40% or more and less than 60%.
3: The haze value Hz is 30% or more and less than 60%.
2: The haze value Hz is 10% or more and less than 30%.
1: Haze value Hz is less than 10%.

<Storage stability>
Each composition obtained above was placed in a container having a liquid height of 20 cm and allowed to stand in a refrigerator (4±1° C.) for 12 months. After standing, the liquid of 1 cm from the top and the liquid of 1 cm from the bottom were sampled, and each of them was post-baked onto an 8-inch (= 203.2 mm) glass wafer with an undercoat layer (CT-4000L manufactured by Fuji Film Electronic Materials Co., Ltd.; thickness 0.1 μm).
Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed by irradiating light with a wavelength of 365 nm at an exposure amount of 1000 mJ/cm ² , and then heat treatment (post-baking) was performed using a hot plate at 200 ° C. for 5 minutes to form a film.
The transmittance of the obtained film at a wavelength of 400 to 700 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
The maximum value (T1) of transmittance at a wavelength of 400 to 700 nm for a film formed using a liquid 1 cm from the top and the maximum value (T2) of transmittance at a wavelength of 400 to 700 nm for a film formed using a liquid 1 cm from the bottom, and ΔT, which is the difference (T1−T2), were determined, and the storage stability was evaluated according to the following criteria. A smaller ΔT means better storage stability.
5: ΔT is 3% or less.
4: ΔT is greater than 3% and less than or equal to 5%.
3: ΔT is greater than 5% and less than or equal to 10%.
2: ΔT is greater than 10% and less than or equal to 20%.
1: ΔT is greater than 20% and less than or equal to 100%.

<Adhesion>
Each composition was coated on an 8-inch (= 203.2 mm) glass wafer with an undercoat layer (CT-4000L manufactured by Fuji Film Electronic Materials Co., Ltd.; thickness 0.1 μm) using a spin coater so that the thickness after pre-baking was 4 μm, and heat treatment (pre-baking) was performed using a hot plate at 110 ° C. for 120 seconds.
Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm was exposed through a pattern mask forming 25 lines of width 100 μm×length 1000 μm (exposure amount 50 to 1700 mJ/cm ² ).
Then, the exposed composition layer was developed using a developing device (Act8 manufactured by Tokyo Electron). A 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used as a developer, and shower development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower using pure water, then spin-dried, and then subjected to heat treatment (post-baking) using a hot plate at 200° C. for 5 minutes to obtain a pattern.
The difference ΔE between the minimum exposure dose E1 required to form a pattern of 100 μm width×1000 μm length and the minimum exposure dose E2 required for all the above-described patterns to adhere was determined, and adhesion was evaluated according to the following criteria. Smaller ΔE means better adhesion. The adherence of the patterns and the size of the patterns were observed using an optical microscope (1000x magnification).
5: ΔE exceeds 100 mJ/cm ² .
4: ΔE exceeds 0 mJ/cm ² and is 100 mJ/cm ² or less.
3: ΔE is 0 mJ/cm ² .
At an exposure amount of 2:50 to 1700 mJ/cm ² , at least one line pattern of width 100 μm×length 1000 μm could be formed, but all 25 lines could not be formed.
A pattern of width 100 μm×length 1000 μm could not be formed with an exposure amount of 1:50 to 1700 mJ/cm ² .

As shown in the above table, Examples were excellent in evaluation of storage stability and light scattering property.

1, 2: Optical sensor 101: Photoelectric conversion elements 111 to 114: Pixel 110: Optical filters 121, 122: Film 130: Transparent support

Claims (17)

Particles A, which are transparent or white particles having a refractive index of less than 2.0, a specific gravity of 2.2 g/cm ³ or less, and an average primary particle diameter of 500 nm or more and 6000 nm or less;
Particles B, which are transparent or white particles having a refractive index of 2.0 or more, an average primary particle diameter of 5 nm or more and 100 nm or less, and a specific gravity greater than that of particles A;
a resin;
A composition comprising a solvent,
The difference between the refractive index of the particles B and the refractive index of the particles A is 0.5 or more,
The total content of the particles A and the particles B in the total solid content of the composition is 30 to 90% by mass,
The ratio of the particles A and the particles B is 20 to 500 parts by mass of the particles B with respect to 100 parts by mass of the particles A,
The resin includes a resin containing a repeating unit having a graft chain,
When a film having a thickness of 4 μm is formed by heating at 200° C. for 5 minutes using the composition, the maximum value of the transmittance of light in the wavelength range of 400 to 700 nm of the film is 60% or less.
Composition. Particles A, which are transparent or white particles having a refractive index of less than 2.0, a specific gravity of 2.2 g/cm ³ or less, and an average primary particle diameter of 500 nm or more and 6000 nm or less;
Particles B, which are transparent or white particles having a refractive index of 2.0 or more, an average primary particle diameter of 5 nm or more and 100 nm or less, and a specific gravity greater than that of particles A;
a resin;
A composition comprising a solvent,
The particles A are hollow particles,
The difference between the refractive index of the particles B and the refractive index of the particles A is 0.5 or more,
The total content of the particles A and the particles B in the total solid content of the composition is 30 to 90% by mass,
The ratio of the particles A and the particles B is 20 to 500 parts by mass of the particles B with respect to 100 parts by mass of the particles A,
When the composition is heated at 200° C. for 5 minutes to form a film having a thickness of 4 μm, the maximum transmittance of light in the wavelength range of 400 to 700 nm of the film is 70% or less.
Composition. 3. The composition of claim 2, wherein said particles A are hollow silica particles. The composition according to any one of claims 1 to 3, wherein the difference between the specific gravity of the particles B and the specific gravity of the particles A is 2.0 g/cm ³ or more. The composition according to claim 1, wherein said particles A are resin particles. 2. The composition of claim 1, wherein said particles A are hollow particles. The composition according to any one of claims 1 to 6 , comprising two or more kinds of said particles A. The composition according to any one of claims 1 to 7 , wherein the particles B have an average primary particle size of 30 nm or more and 100 nm or less. The composition according to any one of claims 1 to 8 , wherein said particles B are inorganic particles. The composition according to any one of claims 1 to 9 , comprising two or more kinds of said particles B. The composition according to any one of claims 1 to 10 , wherein the resin comprises a resin having an ethylenically unsaturated bond-containing group. A composition according to any preceding claim, further comprising a photoinitiator . A membrane obtainable using the composition according to any one of claims 1-12 . Particles A, which are transparent or white particles having a refractive index of less than 2.0, a specific gravity of 2.2 g/cm ³ or less, and an average primary particle diameter of 500 nm or more and 6000 nm or less;
Particles B, which are transparent or white particles having a refractive index of 2.0 or more, an average primary particle diameter of 5 nm or more and 100 nm or less, and a specific gravity greater than that of particles A;
A film containing a resin,
The difference between the refractive index of the particles B and the refractive index of the particles A is 0.5 or more,
The total content of the particles A and the particles B in the film is 30 to 90% by mass,
The ratio of the particles A and the particles B is 20 to 500 parts by mass of the particles B with respect to 100 parts by mass of the particles A,
The resin includes a resin containing a repeating unit having a graft chain,
A film having a maximum transmittance of 60% or less for light in the wavelength range of 400 to 1000 nm. Particles A, which are transparent or white particles having a refractive index of less than 2.0, a specific gravity of 2.2 g/cm ³ or less, and an average primary particle diameter of 500 nm or more and 6000 nm or less;
Particles B, which are transparent or white particles having a refractive index of 2.0 or more, an average primary particle diameter of 5 nm or more and 100 nm or less, and a specific gravity greater than that of particles A;
A film containing a resin,
The particles A are hollow particles,
The difference between the refractive index of the particles B and the refractive index of the particles A is 0.5 or more,
The total content of the particles A and the particles B in the film is 30 to 90% by mass,
The ratio of the particles A and the particles B is 20 to 500 parts by mass of the particles B with respect to 100 parts by mass of the particles A,
A film having a maximum transmittance of 70% or less for light in the wavelength range of 400 to 1000 nm. 16. The membrane of claim 15 , wherein said particles A are hollow silica particles. A photosensor comprising a film according to any one of claims 13-16 .