JP2024045033A - Photosensitive composition, film, optical lens, and optical waveguide for use in an infrared sensor or an infrared communication device, or an optical lens for use in an infrared sensor or an infrared communication device - Google Patents

Abstract

[Problem] The present invention aims to provide a photosensitive composition that has a high refractive index and is excellent in transparency, heat resistance, light resistance, and photolithography properties for use as a high refractive index material in optical lenses or optical waveguides for infrared sensors or infrared communication devices. [Solution] A photosensitive composition for use in optical lenses used in infrared sensors or infrared communication devices, or optical waveguides used in infrared sensors or infrared communication devices, comprising an isoindoline pigment, an acidic resin, a dispersant, a photopolymerizable monomer, and a photopolymerization initiator, wherein the acidic resin has an acid value of 30 to 140 mg KOH/g, the content of the acidic resin is 2 mass% or more based on the total mass of the solids in the photosensitive composition, the dispersant contains a basic resin-type dispersant, and the refractive index at 23°C and a wavelength of 850 nm is 1.65 or more. [Selected Figures] None

Description

The present invention relates to a photosensitive composition for use in an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device, as well as a film, an optical lens, and an optical waveguide that include the photosensitive composition.

Conventionally, a surface protective layer made of an inorganic or organic material is provided on the surface of glass, film, and sheet used in sensor elements such as CCD and CMOS, and display elements such as displays. In recent years, coating layers in which high and low refractive index layers are alternately laminated have been used for the surface protective layer in order to impart functions such as anti-reflection and optical waveguide. For the high refractive index layer, a high refractive index inorganic film formed by deposition of ceramics such as titania, zirconia, and alumina, or a high refractive index organic film made of aromatic resin is used according to the purpose. However, when a high refractive index inorganic film is used, there are problems such as insufficient adhesion to the substrate and fragility of the film. Therefore, in recent years, a high refractive index organic film has been widely used.

In addition, organic electroluminescence (hereinafter referred to as organic EL) panels, which are attracting attention as next-generation displays, have a laminated structure of inorganic layers made of silicon oxide, silicon nitride, alumina, etc., and organic layers made of organic sealing materials whose main components are acrylic resin and epoxy resin, in order to prevent deterioration of the organic EL elements due to the penetration of moisture and gas from the outside. These inorganic and organic layers are laminated alternately. Here, the smaller the difference in refractive index between the inorganic layer and the organic layer, the higher the refractive index of the organic layer, as this improves the light extraction efficiency. Therefore, there is a demand for organic sealing materials with a high refractive index.

Furthermore, in recent years, molded bodies using three-dimensional printing apparatuses have been widely used in the medical field, optical field, and the like. As a modeling resin used for three-dimensional modeling, a photocurable resin is used (Patent Documents 1 and 2). In particular, in lens moldings used for medical equipment, microscopes, various cameras, etc., resins for stereolithography with a high refractive index are required in order to make lenses thinner.

High refractive index organic materials for surface protective layers, organic encapsulants for organic EL panels, and stereolithography resins include resins containing sulfur and fluorene, which has a structure in which aromatic rings are conjugated. There are known resins (Patent Documents 2, 3, and 4).

Recently, sensing and communication using near-infrared rays have become popular, such as solid-state image sensors for photographing objects at night, infrared sensors such as Lidar used for distance measurement, and infrared communication devices that propagate light through optical waveguides. It is becoming widespread. It is important to use an optical material with a high refractive index in the near-infrared region for lenses and the like for condensing these light rays.

Patent Document 5 discloses a composition used for manufacturing an infrared transmission filter, etc. that blocks visible light and transmits near infrared rays, and a film obtained using the same, and the film has a composition that blocks visible light and transmits near infrared rays. It is stated that the refractive index is high in the range of . However, the material described in Patent Document 5 has absorption in a wavelength region longer than 800 nm, and is not preferable for use in sensing or communication using near-infrared rays in the range of 800 to 1600 nm. Further, since the dispersibility of the dye used is not sufficient, problems remain in terms of transparency of the film obtained from the composition.

Patent Document 6 discloses a film-like material for optical members containing an organic dye that exhibits a high refractive index and high transmittance in the near-infrared region, but the amount of the dye added is very small and is sufficiently high. Refractive index is not available.

Patent Document 7 discloses a resin composition containing a thermoplastic resin and a coloring material that exhibits a high refractive index and high transmittance in the near-infrared region, but it does not have sufficient light resistance or heat resistance, There was a problem in terms of practicality.

JP 2011-157543 A JP 2019-019245 A Japanese Patent Application Publication No. 2000-281787 JP2011-168721A International Publication No. 2019/065475 International Publication No. 2020/085499 WO 2020/138050

Among sensing and communications using near-infrared rays, sensing and communications using 800 to 1600 nm light rays, which have become particularly widespread in recent years, require optical lenses to condense these rays and propagate these rays. It is important to use an optical material with a high refractive index, high transparency, and high durability for the optical waveguide.
However, at present, no progress has been made in developing high refractive index materials with sufficient durability.

Furthermore, for use in optical lenses for infrared sensors or infrared communication devices, or optical waveguides for infrared sensors or infrared communication devices, it is very useful for the material to have photolithographic properties. Today's infrared sensors are finely processed, and the optical lenses used for these sensors are required to be very small lenses such as microlenses. In addition, optical waveguides for infrared communication devices also require fine processing. For this reason, it is very useful for the material to have photolithographic properties and the ability to be processed into fine patterns by exposure.

In view of the above problems, the present invention aims to provide a photosensitive composition that has a high refractive index and is excellent in transparency, heat resistance, light resistance, and photolithography properties for use as a high refractive index material in optical lenses or optical waveguides for infrared sensors or infrared communication devices that use light rays of 800 to 1600 nm.

That is, the present invention is
A photosensitive composition for use in an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device, comprising:
The ink contains an isoindoline pigment, an acidic resin, a dispersant, a photopolymerizable monomer, and a photopolymerization initiator,
the acidic resin has an acid value of 30 to 140 mgKOH/g, and the content of the acidic resin is 2 mass% or more based on the total mass of the solid content in the photosensitive composition;
The dispersant contains a basic resin-type dispersant,
The photosensitive composition has a refractive index of 1.65 or more at 23° C. and a wavelength of 850 nm.

The present invention also relates to the above photosensitive composition, wherein the isoindoline pigment has a structure represented by the following general formula (1):
General formula (1)


(X ₁ and X ₂ each independently represent the following general formula (2), (3) or (4). Y ₁ to Y ₄ each independently represent a hydrogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, a sulfo group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, an alkylcarboxy group having 2 to 4 carbon atoms, a halogen atom, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, -SO ₂ -O-R ₁₁₁ or -SO ₂ -NH-R ₁₁₂ , two of which may form a ring by removing a hydrogen atom, or a divalent organic group may be inserted between them when forming a ring. R ₁₁₁ and R ₁₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

General formula (2)


( _Y5 and _Y6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and * represents a bond.)

General formula (3)


(Each _Y7 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and * represents a bond.)

General formula (4)

The present invention also relates to the photosensitive composition, wherein the pigment content is 30% by mass or more based on the total mass of solids in the photosensitive composition.

The present invention also relates to the photosensitive composition, in which the photopolymerization initiator is an oxime ester compound.

The present invention also relates to the photosensitive composition used as a high refractive index material at 800 nm to 1600 nm.

The present invention also relates to a film containing the photosensitive composition.

The present invention also relates to an optical material containing the photosensitive composition.

The present invention also relates to an optical lens containing the photosensitive composition.

The present invention also relates to an optical waveguide containing the photosensitive composition.

The present invention also relates to an infrared sensor comprising the above film, the above optical material, the above optical lens, or the above optical waveguide.
The present invention also relates to an infrared communication device comprising the above film, the above optical material, the above optical lens, or the above optical waveguide.

According to the present invention, it is possible to provide a photosensitive composition that has a high refractive index in the wavelength range of 800 to 1600 nm and is excellent in transparency, heat resistance, light resistance, and photolithography properties when used as a high refractive index material for optical lenses or optical waveguides for infrared sensors or infrared communication devices.

The organic photosensitive composition of the present invention can be used as an optical material for infrared sensors or infrared communication devices that require a high refractive index in the wavelength range of 800 to 1600 nm, and can be used as an optical material for optical lenses, optical waveguides, etc. It can be used particularly suitably.

<Photosensitive Composition of the Present Invention>
The photosensitive composition of the present invention contains an isoindoline pigment, an acidic resin, and a dispersant, and when formed into a film having a thickness of 1.0 μm, the refractive index at 23° C. and a wavelength of 850 nm is 1.65 or more.

<Optical Properties of Photosensitive Composition>
The photosensitive composition of the present invention has a high refractive index in the wavelength region of 800 to 1600 nm, and therefore can provide a film with a high refractive index even without containing sulfur atoms or iodine atoms, which are known to contribute to a high refractive index.

The photosensitive composition of the present invention has a refractive index at 23° C. and a wavelength of 850 nm of 1.65 or more, preferably 1.7 or more, more preferably 1.75 or more, and even more preferably 1.8. That's all. The upper limit of the refractive index is not particularly limited, but is preferably 2.5 or less, more preferably 2.4 or less.
Note that this is the refractive index when the photosensitive composition of the present invention forms a film with a thickness of 1.0 μm, and if the organic photosensitive composition of the present invention contains a solvent, this is the refractive index after coating. This corresponds to the refractive index of the film after it has been volatilized.

<Pigments>
The photosensitive composition of the present invention contains an isoindoline pigment in order to have the above optical properties. Pigments have higher heat resistance, light resistance, and chemical resistance than dyes. Light resistance is essential for optical materials used in optical lenses that collect near-infrared rays and optical waveguides that propagate near-infrared rays. In addition, since the composition is incorporated into various devices and used, it is important that the composition can withstand high-temperature processes and solvent immersion processes in the manufacturing process, and heat resistance and chemical resistance are required. Since the pigment has excellent heat resistance and light resistance, the photosensitive composition of the present invention can be used as a high refractive index material in infrared sensors or infrared communication devices.

In the photosensitive composition of the present invention, the content of the isoindoline pigment is preferably 30% by mass or more based on the total mass of solids in the photosensitive composition. The content is more preferably 40% by mass or more, further preferably 50% by mass or more, particularly preferably 60% or more.
As a result, a film having a high refractive index in the wavelength range of 800 to 1600 nm can be obtained. The upper limit of the pigment content is not particularly limited, but if it is less than 95% by mass, the pigment has excellent dispersibility, a highly transparent film can be obtained, and the photosensitive composition has excellent stability. preferable.
In addition, in this specification, the solid content means all components excluding volatile components such as organic solvents from the photosensitive composition.

<Isoindoline pigment>
Examples of isoindoline pigments include Pigment Yellow 185, 139, Pigment Red 260, and Pigment Orange 61, 66, and 69.

The isoindoline pigment preferably has a structure represented by general formula (1). General formula (1)


(X ₁ and X ₂ each independently represent the following general formula (2), (3), or (4). Y ₁ to Y ₄ each independently represent a hydrogen atom, a hydroxy group, a carboxy group , cyano group, nitro group, sulfo group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 4 carbon atoms, alkylcarboxy group having 2 to 4 carbon atoms, halogen atom , an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, -SO ₂ -O-R ₁₁₁ , or -SO ₂ -NH-R represents ₁₁₂ , and two of these may form a ring by removing hydrogen atoms, or a divalent organic group may be inserted between them when forming the ring.R ₁₁₁ and R ₁₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
General formula (2)


(Y ₅ and Y ₆ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cyclo Represents an alkyl group or an aryl group having 6 to 12 carbon atoms, and * represents a bond.)
General formula (3)


(Y ₇ is each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or represents an aryl group having 6 to 12 carbon atoms, and * represents a bond.)
General formula (4)

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and tertiary butyl group, and examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group. , ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, t-butyloxy group and the like. Examples of the alkenyl group having 2 to 4 carbon atoms include ethylenyl group, propenyl group, butylenyl group, and the like. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopentyl substrate and cyclohexyl group, and examples of the aryl group having 6 to 12 carbon atoms include phenyl group, benzyl group, naphthyl group, and the like.
In Y ₁ to Y ₄ , two of the above groups may each remove a hydrogen atom to form a ring, or, for example, Y ₁ and Y ₂ may be combined to form a phenyl group.

The isoindoline pigment represented by the general formula (1) may be used alone or in combination of two or more kinds. It may also be a mixture containing isomers.

Examples of the isoindoline pigment having the structure represented by general formula (1) include the following compounds.

The photosensitive composition of the present invention may further contain a pigment other than an isoindoline pigment.
Examples of yellow pigments include Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12,
13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 12 6, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, and 221.

Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81
:4, 97, 122, 123, 146, 149, 150, 168, 169, 170, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215, 216 , 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282 , 283, 284, 285, 286, 287.
Examples of orange pigments include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 71, and 73.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15: 3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, 64.

Examples of green pigments include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, and 63.
It is also preferable to use aluminum phthalocyanine pigments, and for example, aluminum phthalocyanine pigments described in JP-A No. 2004-333817, Japanese Patent No. 4893859, etc. can also be used.

Examples of purple pigments include C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50.

(Inorganic pigment)
In addition, inorganic pigments can also be used together. Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, deep blue, chromium oxide green, cobalt green, amber, and synthetic pigments. Examples include iron black. Inorganic pigments are used in combination with organic pigments in order to balance saturation and brightness while ensuring good coating properties, sensitivity, developability, etc.

Moreover, a dye can also be used in combination. Examples of the dye include oil-soluble dyes, acidic dyes, and basic dyes, all of which can be used in combination. Further examples include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, triphenylmethane dyes, cyanine dyes, squarylium dyes, Both can be used together.

Hereinafter, the above pigments and dyes will be collectively referred to as colorants.

Furthermore, a UV absorber can also be used in combination. Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzoate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers, all of which can be used in combination.

Furthermore, a UV absorber can also be used in combination. Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzoate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers, all of which can be used in combination.

When it is desired to control not only the performance as a high refractive index material but also the transmission and absorption in a specific wavelength region, the above-mentioned dyes and ultraviolet absorbers are preferably used.
For example, when sensing near-infrared rays, if you want to cut out a region with a shorter wavelength than the rays, add a yellow pigment or an ultraviolet absorber to a blue, red, or violet pigment to have a function as an IR pass material. can be set.

(Refining of pigment)
In the photosensitive composition of the present invention, from the viewpoint of obtaining high transmittance, the organic pigment is preferably micronized by salt milling or the like. The primary particle size of the pigment is preferably 10 nm or more because it is well dispersed in the colorant carrier. Furthermore, since a coating film with less scattering can be formed, the thickness is preferably 400 nm or less, more preferably 200 nm or less. A particularly preferred range is from 20 to 60 nm.

(Salt milling process)
The salt milling process is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heating using a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or other kneading machine, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during the salt milling process by utilizing the high hardness of the inorganic salt. By optimizing the conditions for the salt milling process of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

Sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used as the water-soluble inorganic salt, but sodium chloride (table salt) is preferred from the viewpoint of cost. From the viewpoints of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total weight of the pigment (100% by mass).

The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, dissolves (is miscible with) water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high-boiling point solvent with a boiling point of 120°C or higher is preferred from the standpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, and more preferably 50 to 500% by mass, based on the total weight of the pigment (100% by mass).

When the pigment is subjected to salt milling, a resin may be added as necessary. There are no particular limitations on the type of resin used, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of resin used is preferably in the range of 5 to 200% by mass, based on the total weight of the pigment (100% by mass).

<Binder resin>
The photosensitive composition of the present invention may contain a binder resin. The binder resin is preferably one capable of binding substances such as pigments together, and examples of the binder resin include thermoplastic resins and thermosetting resins.

Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region.

It is preferable that the binder resin contains an acidic resin having an acid value of 30 to 140 mgKOH/g. By containing an acidic resin having an acid value of 30 to 140 mgKOH/g, the photosensitive composition of the present invention has excellent photolithography properties even if it contains a basic dispersant with poor alkali solubility. Therefore, it can be suitably used as an alkali-developable resist material. More preferably, the acid value of the acidic resin is 50 to 120 mgKOH/g.
In particular, in the photosensitive composition of the present invention, it is preferable to increase the concentration of the isoindoline pigment in the solid content in order to obtain a high refractive index, but since these pigments have low alkali solubility, the binder resin and/or dispersant Its contribution to photolithographic performance is very important.

The content of the acidic resin is 2% by mass or more, preferably 3% by mass or more, and preferably 40% by mass or less, based on the total mass of the solids in the photosensitive composition. If the amount of the acidic resin is too small, the effect of imparting alkali solubility is poor, and if the amount is too large, the pigment concentration in the solids tends to be low and the refractive index tends to be low. Also, if the acid value is too low, the effect of imparting alkali solubility is poor, and if the acid value is too high, it may interact strongly with the basic resin-type dispersant, which may cause the generation of foreign matter.

The acidic resin is preferably an alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer.
The acidic resin may be contained in the photosensitive composition as a dispersant, which will be described later.

Examples of alkali-soluble resins copolymerized with acidic group-containing ethylenically unsaturated monomers include resins having acidic groups such as carboxy groups and sulfone groups. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or Examples include isobutylene/(anhydrous) maleic acid copolymer. Among them, at least one resin selected from the group consisting of acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, particularly acrylic resins having acidic groups, is preferably used because of its high heat resistance and transparency. used.

In order to improve the photosensitivity of an alkali-soluble resin copolymerized with an acidic group-containing ethylenic nonmonomer, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used. In addition, the use of an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is preferable from the viewpoint of various resistances.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenically double bonds are introduced by methods (a) and (b) shown below.

[Method (a)]
Method (a) includes a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a carboxy group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction with the side-chain epoxy group of the copolymer, and further, a polybasic acid anhydride is reacted with the resulting hydroxy group to introduce an unsaturated ethylenic double bond and a carboxy group.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and these may be used alone or in combination of two or more. good. To increase the number of carboxyl groups, if necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Moreover, when etrahydrophthalic anhydride or maleic anhydride, which has unsaturated ethylenic double bonds, is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

A method similar to method (a) is, for example, a method in which an unsaturated ethylenic monomer having an epoxy group is added to some of the side chain carboxy groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxy group with one or more other monomers, thereby introducing an unsaturated ethylenic double bond and a carboxy group.

[Method (b)]
As method (b), by using an unsaturated ethylenic monomer having a hydroxy group and copolymerizing it with another unsaturated monobasic acid monomer having a carboxy group or other monomers. There is a method in which the side chain hydroxy groups of the obtained copolymer are reacted with an isocyanate group of an unsaturated ethylenically monomer having an isocyanate group.

Examples of the unsaturated ethylenically monomer having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Examples include hydroxyalkyl (meth)acrylates such as glycerol (meth)acrylate and cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone, etc. , and/or (poly)ester mono(meth)acrylate to which (poly)12-hydroxystearic acid or the like is added can also be used. From the viewpoint of suppressing coating film foreign matter, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

Examples of unsaturated ethylenic monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited to these and two or more types can be used in combination.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to preferably disperse the colorant. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

(Dispersant)
The dispersant functions to disperse and stabilize the pigment in the photosensitive composition and to prevent re-aggregation after dispersion, thereby obtaining a film with high spectral transmittance. Examples of the dispersant include resin-type dispersants, dye derivatives, resin-type dispersants, surfactants, etc.

The photosensitive composition of the present invention contains a basic resin-type dispersant as a resin-type dispersant. The basic resin type dispersant means a resin type dispersant having a basic site in its structure. Isoindoline pigments have an affinity for basic resin type dispersants and can be dispersed very effectively.

Resin-type dispersant
The resin-type dispersant has a pigment-affinity portion that has the property of being adsorbed to the pigment, and a portion that is compatible with the colorant carrier, and functions to adsorb to the added pigment and stabilize the dispersion in the colorant carrier.
Specifically, as the resin type dispersant, polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylate esters, and modified products thereof, poly (lower alkylene imine) and free carboxyl group-containing polyesters formed by reaction with amides and their salts, oil-based dispersants such as amides and their salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble resins such as polyvinylpyrrolidone and water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used, which can be used alone or in a mixture of two or more, but are not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 21 50, 2155, Anti-Terra-U, 203, 204, BYK-P104, P104S, 220S, 6919, Lactimon, Lactimon-WS, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 2400 manufactured by Lubrizol Japan Co., Ltd.
EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 452, 40 ...
401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.
Examples of commercially available basic resin-type dispersants include BYK-6919 manufactured by BYK Japan, SOLSPERSE-76500 manufactured by Lubrizol Japan, EFKA-4300 manufactured by BASF Japan, and AJISPER PB821 manufactured by Ajinomoto Fine-Techno Co., Ltd.

《Block acrylic basic dispersant》
In the photosensitive composition of the present invention, it is preferable to use a block acrylic type basic dispersant as the basic resin type dispersant. The block acrylic basic dispersant is a block type acrylic polymer having a basic group. Among these, it is more preferable that one block is a polymer of an ethylenically unsaturated monomer having a basic group and the other block is a polymer of an ethylenically unsaturated monomer having no basic group. .

When the block acrylic type basic dispersant is an AB type block, a more preferable embodiment is as described above, but in the case of a BAB type block, the A block is a polymer of ethylenically unsaturated monomers having a basic group. It is more preferable that the B block is a polymer of ethylenically unsaturated monomers having no basic group.

By using a block acrylic basic dispersant as a resin type dispersant, the block with a basic group adsorbs to the surface of the pigment, while the other block without a basic group maintains its affinity with the solvent. It is thought that good dispersibility is achieved by acting as a steric hindrance.

In general, resin-type dispersants tend to achieve good dispersibility when used in combination with dye derivatives, but when block acrylic-type basic dispersants are used, they can be used without dye derivatives due to the above mechanism. Good dispersibility is often obtained. Since the dye derivative often has a different spectrum from the pigment used in the present invention, the photosensitive composition can exhibit a higher refractive index by not using the dye derivative.

As the ethylenically unsaturated monomer having a basic group, an ethylenically unsaturated monomer having a tertiary amino group and an ethylenically unsaturated monomer having a quaternary ammonium salt are preferable, and these may be used in combination. is particularly preferred.

Examples of ethylenically unsaturated monomers having a tertiary amino group include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and dipropylaminoethyl methacrylate, and examples of ethylenically unsaturated monomers having a quaternary ammonium group include: Methacrylic acid dimethylaminoethyl methyl chloride salt, methacrylic acid dimethylaminoethylbenzyl chloride salt, methacrylic acid dimethylaminoethylpropyl chloride salt, methacrylic acid dimethylaminoethylbutyl chloride salt, methacrylic acid diethylaminoethylmethyl chloride salt, methacrylic acid diethylaminoethylbenzyl chloride salt salt, methacrylic acid diethylaminoethylpropyl chloride salt, methacrylic acid diethylaminoethylbutyl chloride salt, acrylic acid dimethylaminoethylmethyl chloride salt, acrylic acid dimethylaminoethylbenzyl chloride salt, acrylic acid dimethylaminoethylpropyl chloride salt, dimethyl acrylate Examples include aminoethyl butyl chloride salt.

When an ethylenically unsaturated monomer having a tertiary amino group and an ethylenically unsaturated monomer having a quaternary ammonium salt are used together as the ethylenically unsaturated monomer having a basic group, a block acrylic base is used. There are two typical methods for synthesizing dispersants.

The first method is to synthesize these ethylenically unsaturated monomers separately and then mix them together when polymerizing the block having a basic group.

The second method is to polymerize a block having a basic group using an ethylenically unsaturated monomer having a tertiary amino group, polymerize the other block having no basic group, and after completing the block polymerization, react with a quaternizing agent such as benzyl chloride to convert a part of the tertiary amino group into a quaternary ammonium salt. Examples of the quaternizing agent include alkyl halides such as benzyl chloride, iodobutane, iodopropane, iodoethane, bromobutane, bromopropane, bromoethane, and chlorobutane.
The ethylenically unsaturated monomer having a tertiary amino group and the ethylenically unsaturated monomer having a quaternary ammonium salt are preferably those having an amide bond in the molecule, since they are easily adsorbed to the surface of the organic pigment and can provide higher dispersibility.

When synthesizing a block polymer, for example, an A-B block polymer can be produced by first synthesizing the A block and then the B block. Alternatively, a B-A-B block polymer can be produced by first synthesizing the B block, then the A block, and then the B block. The order in which the A block and the B block are synthesized is arbitrary.

The radical polymerization initiator used in living radical polymerization is preferably an azo compound or a peroxide.

Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(methyl isobutyrate), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

Examples of peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide. The polymerization initiators may be used alone or in combination of two or more kinds.

The polymerization reaction temperature is preferably 40 to 150°C, more preferably 50 to 110°C. The reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

Living radical polymerization can be performed by any known polymerization method, but RAFT polymerization (reversible addition-fragmentation chain transfer polymerization) is preferred. RAFT polymerization is a method of radically polymerizing monomers in the presence of a RAFT agent, and it is easy to control the molecular weight and molecular weight distribution of the polymer.

The RAFT agent is a compound having a chain transfer effect and a polymerization initiation effect, and includes, for example, a dithiobenzoate type, a trithiocarbonate type, a dithiocarbamate type, a xanthet type, and a disulfide type which is a precursor thereof.

Examples of the dithiobenzoate type include 2-cyano-2-propyl dithiobenzoate, 4-cyano-4-(thiobenzoylthio)pentanoic acid, and 2-phenyl-2-propyl benzodithioate.

Examples of the trithiocarbonate type include 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanopentanoic acid, 2-{[(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl}propanoic acid, -Cyano-4-[(
dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-cyano-2-[
(dodecylsulfanylthiocarbonyl)sulfanyl]propane, 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, 2-methyl-2-[ (dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, S,S-dibenzyltrithiocarbonate, trithiocarbonate = bis[4-(allyloxycarbonyl)benzyl], trithiocarbonate = bis[4-(2,3-dihydroxypropoxy) carbonyl)benzyl], trithiocarbonic acid = bis{4-[ethyl-(2-acetyloxyethyl)carbamoyl]benzyl}, trithiocarbonic acid bis{4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl}, trithiocarbonic acid = Bis[4-(2-hydroxyethoxycarbonyl)benzyl] is mentioned.

As the dithiocarbamate type, for example, 4-chloro-3,5-dimethylpyrazole-1
Examples of such compounds include 2'-cyanobutan-2'-yl 3,5-dimethylpyrazole-1-carbodithioate, 2'-cyanobutan-2'-yl 3,5-dimethylpyrazole-1-carbodithioate, cyanomethyl 3,5-dimethylpyrazole-1-carbodithioate, and cyanomethyl N-methyl-N-phenyldithiocarbamate.

Examples of the disulfide type include bis(dodecylsulfanylthiocarbonyl) disulfide and bis(thiobenzoyl) disulfide. These are preferred for the production of AB block polymers.

Among these, trithiocarbonate type compounds are preferred because they are easy to control the reaction during synthesis; ) sulfanyl]propane, methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, bis{4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl} trithiocarbonate}, bis(dodecylsulfanylthiocarbonyl) ) Disulfide is more preferred.

The amount of RAFT agent used is preferably 0.1 to 10 parts by mass per 100 parts by mass of monomer.

In the synthesis of the block acrylic basic dispersant, it is preferable to use an organic solvent. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Examples include ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate. The organic solvents may be used alone or in combination of two or more.

(Acidic resin type dispersant)
The acidic resin-type dispersant is a resin-type dispersant having an acidic group in its structure. The photosensitive composition may contain an acidic resin having an acid value of 30 to 140 mgKOH/g as a dispersant. The content of the acidic resin is preferably 5% by mass or more and 40% by mass or less based on the total mass of the solid content in the photosensitive composition. If the amount of the acidic resin-type dispersant is too small, the effect of imparting alkali solubility is poor, and if the amount is too large, the pigment concentration in the solid content tends to be low and the refractive index tends to be low. In addition, if the acid value is too low, the effect of alkali solubility is poor, and if the acid value is too high, it may cause foreign matter generation due to strong interaction with the basic resin-type dispersant.

For example, it is also preferable to contain the following (S1) or (S2) as an acidic resin type dispersant.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride.
(S2) A polymer obtained by polymerizing ethylenically unsaturated monomers in the presence of a reaction product between the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and/or tetracarboxylic dianhydride. A resin-type dispersant that is a combination.

[Resin type dispersant (S1)]
The resin type dispersant (S1) can be produced by a known method such as WO2008/007776, JP2008-029901, JP2009-155406, and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, an ethylenically unsaturated monomer (r) is polymerized in the presence of a compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that there be a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferred example of a polymer having two hydroxyl groups at one end can be obtained as a polymer (p1) by polymerizing an ethylenically unsaturated monomer (r) including a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. The hydroxyl groups of the polymer (p) having hydroxyl groups react with the acid anhydride groups of the tricarboxylic acid anhydride and/or tetracarboxylic acid dianhydride to form ester bonds, while the anhydride ring opens to produce a carboxylic acid.

[Resin type dispersant (S2)]
The resin type dispersant (S2) can be produced by a known method such as JP-A No. 2009-155406, JP-A No. 2010-185934, and JP-A No. 2011-157416. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic anhydride and/or tetracarboxylic dianhydride. can get. Among them, in the presence of a reaction product between the hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic anhydride and/or tetracarboxylic dianhydride. In addition, it is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing monomer (r1).

The difference between (S1) and (S2) is whether the polymer site in which the ethylenically unsaturated monomer (r) is polymerized is introduced first or later. The molecular weight etc. may differ slightly depending on various conditions, but if the raw materials and reaction conditions are the same, theoretically the same product can be produced.

The resin type dispersant may be used alone or in combination of two or more types.

《Pigment derivative》
Examples of pigment derivatives include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone, or triazine. Those described in Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used. They can be used alone or in combination of two or more.

From the viewpoint of improving pigment dispersibility, the blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight based on the total amount of pigment (100% by weight). % or more. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount of added pigment (100% by weight).

《Surfactant》
As surfactants, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkyl betaines such as alkyldimethylaminoacetic acid betaines, and alkylimidazolines; these may be used alone or in combination of two or more. They can be used in combination.

When a resin-type dispersant or surfactant is added, the amount is preferably 0.1 to 200% by weight, and more preferably 0.1 to 150% by weight, based on the total amount of pigment (100% by weight). By keeping the amount of the resin-type dispersant or surfactant within the above range, favorable dispersibility can be achieved.

<Organic solvent>
The colored composition of the present invention may contain an organic solvent in order to sufficiently disperse and permeate the coloring agent into the colorant carrier and to facilitate molding of the high refractive index material.

Examples of organic solvents include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, and 1,4-dioxane. , 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-
Methyl butyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol , n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ- Butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol Monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl Ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Examples include isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among them, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and benzyl are used because they have good pigment dispersibility and solubility. It is preferable to use aromatic alcohols such as alcohols and ketones such as cyclohexanone. In particular, propylene glycol monomethyl ether acetate is more preferred from the viewpoints of safety and hygiene and low viscosity.

These organic solvents can be used alone or in combination of two or more. When using a mixed solvent of two or more, it is preferable that the above preferred organic solvents are contained in an amount of 65 to 95% by weight.

In addition, the organic solvent should be used in an amount of 800 to 4000% by weight based on the total weight of the colorant (100% by weight) in order to adjust the viscosity of the photosensitive composition to an appropriate level and improve the formability of a high refractive index material. Preferably, it is used in amounts.

<Dispersion>
The photosensitive composition of the present invention can be prepared in a coloring agent carrier consisting of a pigment and, if necessary, a resin and a solvent, preferably together with a dispersant, using a three-roll mill, a two-roll mill, a sand mill, or the like.
It is preferable to obtain the pigment composition by adding a photopolymerizable monomer and/or a photopolymerization initiator to a pigment composition produced by finely dispersing it using various dispersion means such as a kneader or an attritor. The photosensitive composition of the present invention can also be produced by mixing pigments, dyes, other colorants, etc., separately dispersed in a colorant carrier.

<Photopolymerizable Monomer>
The photopolymerizable monomer includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin, and these can be used alone or in combination of two or more kinds.

Examples of monomers and oligomers that can be cured by ultraviolet rays or heat to produce transparent resins include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. , cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate Acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6 -Hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate ) various acrylic esters and methacrylic esters such as acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic ester of methylolated melamine, epoxy (meth)acrylate, urethane acrylate,
Examples include, but are not necessarily limited to, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. It's not something you can do.

These commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, and GPO- manufactured by Nippon Kayaku Co., Ltd. 303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Aronix M-303, M manufactured by Toagosei Co., Ltd. -305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403 , M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295 manufactured by Osaka Organic Co., Ltd. , #330, #360, #GPT, #400, #405, NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., etc. can be suitably used.

(Polymerizable compound having an acid group)
The photopolymerizable monomer in the present invention may contain a polymerizable compound having an acid group.
Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.
Since a polymerizable compound having an acid group has high alkali solubility, it is preferable to contain a polymerizable compound having an acid group, particularly for forming a fine pattern.

Examples of polymerizable compounds having an acid group include esters of dicarboxylic acids and free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid; esters of polycarboxylic acids and monohydroxyalkyl(meth)acrylates. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid); Examples include free carboxyl group-containing oligoesters of tricarboxylic acids such as butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, but the effects of the present invention are not limited to these.

As these commercially available products, Viscoat #2500P manufactured by Osaka Organic Co., Ltd. and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd., etc. can be suitably used. .

(Polymerizable compound having a urethane bond)
The photopolymerizable monomer in the present invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. For example, there may be mentioned a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate Examples include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc.

Commercially available products of these include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., and UV-41 manufactured by Osaka Organic Chemical Industry Co., Ltd.
08F, UV-4117F, etc. can be suitably used.
In addition, since a polymerizable compound having a hydroxyl group has a high affinity with an alkaline developer, it is preferable to contain a compound having a hydroxyl group in order to form a fine pattern.

The above photopolymerizable monomers can be used alone or in a mixture of two or more types in any ratio as required.

The blending amount of the photopolymerizable monomer is preferably 1 to 70 parts by mass based on the total nonvolatile content of the photosensitive coloring composition (100 parts by mass), and from the viewpoint of photocurability and developability, it is preferably 2 to 70 parts by mass. More preferably, the amount is 50 parts by mass. Furthermore, based on the total weight of the colorant (100% by weight), the amount is preferably 5 to 300% by weight, and more preferably 10 to 150% by weight from the viewpoint of photocurability and developability.

<Photopolymerization initiator>
The photosensitive composition of the present invention can be cured by exposure to ultraviolet light.

Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ether, and the like. Benzoin compounds such as benzoyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazanthone; 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl) )-6-triazine; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.
In particular, oxime ester compounds have high sensitivity and exhibit photocurability even in small amounts, so that it is preferable to use oxime ester compounds in forming fine patterns.

These photopolymerization initiators can be used alone or in a mixture of two or more in any ratio as necessary. The amount of these photopolymerization initiators is preferably 0.1 to 30 parts by weight based on the total nonvolatile content of the photosensitive coloring composition (100 parts by weight), and more preferably 0.2 to 15 parts by weight from the viewpoint of photocurability and developability. Furthermore, based on the total amount of colorants in the photosensitive composition (100% by weight), the amount is preferably 0.5 to 50% by weight, and more preferably 1 to 30% by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the photosensitive composition of the present invention can contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, Polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrin derivatives Radin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-alpha Siloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4 '－
Examples include tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-diethylaminobenzophenone.

More specifically, examples of sensitizers include those described in "Dye Handbook" edited by Okawara Makoto et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Okawara Makoto et al. (CMC, 1981), "Tokushu No Futon Zairyo" edited by Ikemori Chuzaburo et al., and "Tokushu No Futon Zairyo" (CMC, 1986), but are not limited to these. In addition, sensitizers that absorb light from the ultraviolet to near infrared regions can also be included.

Two or more sensitizers may be used in any ratio as necessary. The amount of the sensitizer used is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the photosensitive composition (100% by weight), and , more preferably from 5 to 50% by weight from the viewpoint of developability.

<Amine compounds>
Further, the photosensitive composition of the present invention can contain an amine compound that has a function of reducing dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethylparatoluidine.

<Leveling Agent>
In order to improve the leveling property of the composition, it is preferable to add a leveling agent to the photosensitive composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight based on the total weight of the photosensitive composition (100% by weight).

Particularly preferred as a leveling agent is a type of so-called surfactant that has a hydrophobic group and a hydrophilic group in the molecule, and although it has a hydrophilic group, it has low solubility in water, and when added to the photosensitive composition, It is useful to have a low ability to reduce surface tension, and to have good wettability to glass plates despite the low ability to reduce surface tension. Those that can sufficiently suppress charging properties can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having polyalkylene oxide units can be preferably used. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

The bonding form of the polyalkylene oxide unit with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modified type in which the polyalkylene oxide unit is bonded to the terminal of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide unit is bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., and examples thereof include, but are not limited to, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

The leveling agent may be supplemented with an anionic, cationic, nonionic, or amphoteric surfactant. Two or more types of surfactants may be mixed together.

Examples of anionic surfactants that can be added to the leveling agent as an auxiliary include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

Examples of cationic surfactants that can be added to the leveling agent as supplementary agents include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants that can be added to the leveling agent as supplementary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, alkyl betaines such as alkyl dimethylamino acetate betaines, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

<Other additive components>
The photosensitive composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Furthermore, an adhesion improver such as a silane coupling agent may be included in order to improve adhesion to the base material.

Examples of storage stabilizers include quaternary ammonium chloride such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples include organic phosphines and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of colorant (100% by weight).

Examples of adhesion enhancers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of the silane coupling agents include epoxy silanes such as silane, amino silanes such as N-β (aminoethyl) γ-aminopropyl trimethoxy silane, N-β (aminoethyl) γ-aminopropyl triethoxy silane, N-β (aminoethyl) γ-aminopropyl methyl diethoxy silane, γ-aminopropyl triethoxy silane, γ-aminopropyl trimethoxy silane, N-phenyl-γ-aminopropyl trimethoxy silane, and N-phenyl-γ-aminopropyl triethoxy silane, and thio silanes such as γ-mercaptopropyl trimethoxy silane and γ-mercaptopropyl triethoxy silane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the photosensitive composition (100% by weight).

<Removal of coarse particles>
The photosensitive composition of the present invention can be mixed with coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, sintered filters, membrane filters, etc. It is preferable to remove the dust. As described above, it is preferable that the photosensitive composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Film containing photosensitive composition and its use>
The photosensitive composition of the present invention is cured, for example, by volatilizing the solvent, exposing to light (photocuring) or heating (thermal curing), to obtain a film containing the photosensitive composition of the present invention. The method for forming the film is not limited to the above.
Examples of light rays to be exposed in photocuring include ultraviolet rays, electron beams, and X-rays. Examples of light sources that can be used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. After exposure, post-baking may be performed to stabilize the physical properties of the cured product. There are no particular limitations on the method of post-baking, but it is usually performed at 50 to 260° C. for 1 to 120 minutes using a hot plate, oven, or the like.
The heating conditions for thermal curing are not particularly limited, but are usually appropriately selected from the ranges of 50 to 300° C. and 1 to 120 minutes. The heating means is not particularly limited, but examples thereof include a hot plate and an oven.

The film containing the photosensitive composition of the present invention has a high refractive index in the wavelength range of 800 to 1600 nm, and forms an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device. Suitable as a material.

The photosensitive composition of the present invention can be molded into any shape, such as a dome or sheet, to produce a film.

For example, it can be molded as follows. The photosensitive composition of the present invention is potted on a transparent substrate such as glass, and a desired molding mold is pressed against it to fill the mold with the photosensitive composition, which can then be cured by irradiating light thereto. Then, the molding mold is removed to obtain a cured product of the photosensitive composition integrated on the transparent substrate. Alternatively, the photosensitive composition can be filled in a transparent mold that transmits light and photocured. By such a manufacturing method, for example, a hybrid lens can be produced. The photosensitive composition of the present invention can also be cured by itself in a molding mold to form an optical component such as an optical lens.
It can also be molded into a microlens. An etch-back method is known as one of the methods for manufacturing a microlens. A resist pattern is formed on the coating film of the photosensitive composition of the present invention, and the resist pattern is reflowed by heat treatment to form a lens pattern. The coating film of the photosensitive composition of the present invention as the lower layer is etched back using the lens pattern formed by reflowing the resist pattern as an etching mask, and the lens pattern shape is transferred to the film of the photosensitive composition of the present invention to manufacture a microlens. In addition, as another method for manufacturing a microlens, there is a method in which a resist pattern is formed by exposing and developing the photosensitive composition of the present invention, and the microlens is manufactured by reflowing the resist pattern by heat treatment.
When molding into an optical waveguide, for example, the photosensitive composition of the present invention is exposed and developed to form a resist pattern, and then another resin composition or photosensitive composition containing a photopolymerization initiator and an alkali-soluble resin and having a different refractive index is exposed and developed to form an adjacent resist pattern, thereby forming a core and a clad, and an optical waveguide can be produced.

Note that in this specification, an infrared sensor or an optical lens for an infrared communication device refers to a lens for condensing infrared rays, and includes, for example, a spectacle lens, an optical device lens, an optoelectronics lens, a laser lens, Examples include pickup lenses, in-vehicle camera lenses, mobile camera lenses, digital camera lenses, OHP lenses, and microlenses.

In this specification, an optical waveguide for an infrared sensor or infrared communication device refers to a waveguide for propagating infrared rays, and its shape is not limited to a sheet or plate. Examples of applications include cables used for optical communication in computers and sensor devices, optical interconnections used for optical communication inside devices, and materials used on the optical path when an infrared sensor or the like senses infrared rays.

The present invention will be described in more detail below, but is not limited to these examples as long as they do not deviate from the technical concept of the present invention. In the following, "parts by mass" will simply be written as "parts" and "% by mass" will simply be written as "%".

<Production of isoindoline pigment>

(Synthesis Example 1-1)
In a 3 L 4-neck flask equipped with a reflux condenser, a dropping funnel, and a stirrer, add 700 parts water, 1
344.5 mmol of 1,3-diiminoisoindoline and 100 parts of 28% aqueous ammonia were added in this order and stirred. A solution of 361.7 mmol of 2-cyano-N-methylacetamide dissolved in 100 parts of water was added dropwise thereto using a dropping funnel over 30 minutes. The mixture was heated and stirred at 30°C until the raw material 1,3-diiminoisoindoline disappeared. The disappearance of the raw material was confirmed by UPLC (ultra performance high resolution liquid chromatography). This reaction slurry was filtered using a Buchner funnel to obtain a solid content. The entire amount of this solid content was used in the following reaction.
In a 3 L 4-neck flask equipped with a reflux condenser, a dropping funnel, and a stirrer, the entire amount of the solids obtained in the previous preparation as raw materials, 1200 parts of water, and 400 parts of 80% acetic acid were added and stirred. 396.1 mmol of barbituric acid was added thereto and stirred at 85°C. Heating and stirring were continued until the solids used as raw materials disappeared. The disappearance of the raw materials was confirmed by UPLC.
After that, the reaction slurry was cooled to room temperature, filtered using a Buchner funnel, and washed three times with 2000 parts of water to obtain a solid content, which was then dried in a hot air dryer at 80° C. to obtain 105.7 parts (yield 91%) of an isoindoline pigment (a-1).

(Synthesis example 1-2)
800 parts of water and 800 parts of 80% acetic acid were added to a 3L 4-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the mixture was stirred. 688.9 mmol of barbituric acid was added thereto, and the mixture was stirred at 85°C to dissolve the barbituric acid. 344.5 mmol of 1,3-diiminoisoindoline was added thereto, and the mixture was stirred at 85°C. Stirring was continued until the raw material 1,3-diiminoisoindoline disappeared. Disappearance of the raw material was confirmed by UPLC. Thereafter, this reaction slurry was cooled to room temperature, filtered using a Buchner funnel, and washed three times with 2000 parts of water to obtain a solid content. This solid content was dried in a hot air dryer at 80°C to obtain 121.5 parts of isoindoline compound (a-2) (yield 96%).

(Synthesis Example 1-3)
The reaction was carried out in the same manner as in Synthesis Example 1-1, except that 2-cyano-N-methylacetamide in Synthesis Example 1-1 was changed to 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile, to obtain 130.7 g of isoindoline pigment (a-3) (yield 89%).

(Synthesis example 1-4)
1200 parts of water, 344.5 mmol of 1,3-diiminoisoindoline, and 200 parts of 28% aqueous ammonia were added in this order to a 3 L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the mixture was stirred. A solution prepared by dissolving 792.3 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide in 200 parts of water was added dropwise thereto using a dropping funnel over 30 minutes. The mixture was heated and stirred at 30° C. until the raw material 1,3-diiminoisoindoline disappeared. Disappearance of the raw material was confirmed by UPLC (ultra high performance high separation liquid chromatography). This reaction slurry was filtered using a Buchner funnel to obtain solid content.
Thereafter, this reaction slurry was filtered using a Buchner funnel and washed three times with 2000 parts of water to obtain a solid content. This solid content was dried in a hot air dryer at 80° C. to obtain 127.5 parts of isoindoline pigment (a-4) (yield: 65%).

(Synthesis Example 1-5)
Except for changing 2-cyano-N-methylacetamide to N-(4-chlorophenyl)-2-cyanoacetamide and barbituric acid to 1-(4-methylphenyl)barbituric acid in Synthesis Example 1-1, the reaction was carried out in the same manner as in Synthesis Example 1-1, to obtain 158.8 parts of an isoindoline pigment (a-5) (yield 88%).

(Synthesis Example 1-6)
The reaction was carried out in the same manner as in Synthesis Example 1-1, except that the barbituric acid in Synthesis Example 1-1 was changed to 1,3-dimethylbarbituric acid, and 115.8 parts (
The yield was 92%).

(Synthesis Example 1-7)
The reaction was carried out in the same manner as in Synthesis Example 1-2, except that the barbituric acid in Synthesis Example 1-2 was changed to 1,3-dimethylbarbituric acid, to obtain 138.6 parts (yield 95%) of an isoindoline pigment (a-7).

(Synthesis Example 1-8)
Except for changing the amounts of 1,3-diiminoisoindoline (344.5 mmol) to 1,3-diiminobenzo[f]isoindoline (256.1 mmol), 2-cyano-N-methylacetamide (361.7 mmol) to 268.9 mmol, and barbituric acid (396.1 mmol) to 294.5 mmol in Synthesis Example 1-1, the reaction was carried out in the same manner as in Synthesis Example 1-1, to obtain 88.3 parts (yield 89%) of an isoindoline pigment (a-8).

(Synthesis example 1-9)
Synthesis except that 344.5 mmol of 1,3-diiminoisoindoline in Synthesis Example 1-2 was changed to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline, and 688.9 mmol of barbituric acid was changed to 537.9 mmol. The reaction operation was carried out in the same manner as in Example 1-2, and 96.2 parts (yield 90%) of isoindoline pigment (a-9) was obtained.

(Synthesis example 1-10)
The reaction procedure was carried out in the same manner as in Synthesis Example 1-4, except that 2-cyano-N-(3,4-dichlorophenyl)acetamide in Synthesis Example 1-4 was changed to 2-cyano-N-methylacetamide, and the isoindoline 54.0 parts (yield 51%) of pigment (a-10) were obtained.

(Synthesis example 1-11)
700 parts of water, 344.5 mmol of 1,3-diiminoisoindoline, and 100 parts of 28% aqueous ammonia were added in this order to a 3L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and stirred. A solution prepared by dissolving 396.1 mmol of 2-cyano-N-methylacetamide in 100 parts of water was added dropwise thereto using a dropping funnel over 30 minutes. The mixture was heated and stirred at 30° C. until the raw material 1,3-diiminoisoindoline disappeared. Disappearance of the raw material was confirmed by UPLC (ultra high performance high separation liquid chromatography). This reaction slurry was filtered using a Buchner funnel to obtain solid content. The entire amount of this solid content was used in the following reaction.
Into a 3L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, the entire solid content obtained in the previous preparation as raw materials, 1200 parts of water, and 150 parts of 28% aqueous ammonia were added in this order and stirred. A solution of 396.1 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide dissolved in 100 parts of water was added dropwise thereto using a dropping funnel over 30 minutes. The heating was continued at 30° C. until the solid content used as the raw material disappeared. Disappearance of the raw material was confirmed by UPLC.
Thereafter, this reaction slurry was filtered using a Buchner funnel and washed three times with 2000 parts of water to obtain a solid content. This solid content was dried in a hot air dryer at 80° C. to obtain 69.4 parts of isoindoline pigment (a-11) (yield: 46%).

(Synthesis Example 1-12)
Except for changing 2-cyano-N-(3,4-dichlorophenyl)acetamide in Synthesis Example 1-4 to 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile, the reaction was carried out in the same manner as in Synthesis Example 1-4 to obtain 73.6 parts of an isoindoline pigment (a-12) (yield 44%).

(Synthesis example 1-13)
The reaction procedure was carried out in the same manner as in Synthesis Example 1-2, except that the barbituric acid in Synthesis Example 1-2 was changed to 1-(4-methylphenyl)barbituric acid, and the isoindoline pigment (a-13) was 160.3 parts (yield 85%) were obtained.

(Synthesis example 1-14)
The reaction procedure was carried out in the same manner as in Synthesis Example 1-1, except that the barbituric acid in Synthesis Example 1-1 was changed to 1-(4-methylphenyl)barbituric acid, and the isoindoline pigment (a-14) was 123.7 parts (yield 84%) were obtained.

(Synthesis example 1-15)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-1 was changed to 285.4 mmol of 4-methoxy-1,3-diiminoisoindoline, and 361.7 mmol of 2-cyano-N-methylacetamide was changed to 299.7 mmol. The reaction procedure was carried out in the same manner as in Synthesis Example 1-1, except that 396.1 mmol of barbituric acid was changed to 328.2 mmol, and 81.8 parts of isoindoline pigment (a-15) (yield 78%) was prepared. )Obtained.

(Synthesis example 1-16)
The reaction operation was carried out in the same manner as in Synthesis Example 1-15, except that the barbituric acid in Synthesis Example 1-15 was changed to 1,3-dimethylbarbituric acid, and the isoindoline pigment (a-16) was (yield 77%).

(Synthesis example 1-17)
Except that 344.5 mmol of 1,3-diiminoisoindoline in Synthesis Example 1-2 was changed to 285.4 mmol of 4-methoxy-1,3-diiminoisoindoline, and 688.9 mmol of barbituric acid was changed to 570.8 mmol. The reaction operation was carried out in the same manner as in Synthesis Example 1-2 to obtain 93.0 parts (yield: 82%) of isoindoline pigment (a-17).

(Synthesis Example 1-18)
The same reaction procedure as in Synthesis Example 1-17 was carried out except that the barbituric acid in Synthesis Example 1-17 was changed to 1,3-dimethylbarbituric acid, to obtain 103.5 parts (yield 80%) of an isoindoline pigment (a-18).

(Synthesis Example 1-19)
Except for changing 2-cyano-N-methylacetamide in Synthesis Example 1-15 to 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile, the reaction was carried out in the same manner as in Synthesis Example 1-15 to obtain 96.4 parts of an isoindoline pigment (a-19) (yield 74%).

(Synthesis Example 1-20)
The same reaction procedure as in Synthesis Example 1-17 was carried out except that the barbituric acid in Synthesis Example 1-17 was changed to 1-(4-methylphenyl)barbituric acid, to obtain 118.6 parts (yield 75%) of an isoindoline pigment (a-20).

(Synthesis example 1-21)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-4 was changed to 285.4 mmol of 4-methoxy-1,3-diiminoisoindoline, and 792 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide was added. The reaction operation was carried out in the same manner as in Synthesis Example 1-4, except that .3 mmol was changed to 656.4 mmol, and 71.8 parts (yield: 42%) of isoindoline pigment (a-21) was obtained.

(Synthesis example 1-22)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-4 was changed to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline, and 792.3 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide was added. The reaction operation was carried out in the same manner as in Synthesis Example 1-4, except that 589.1 mmol of 2-cyano-N-methylacetamide was used, and 36.6 parts of isoindoline pigment (a-22) (yield 40%) )Obtained.

(Synthesis example 1-23)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-11 was changed to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline, 396.1 mmol of 2-cyano-N-methylacetamide was changed to 294.5 mmol, The reaction operation was carried out in the same manner as in Synthesis Example 1-11, except that 396.1 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide was changed to 294.5 mmol, and the isoindoline pigment (a-23) was 48.8 parts (yield 39%) were obtained.

(Synthesis Example 1-24)
Except for changing 2-cyano-N-methylacetamide in Synthesis Example 1-22 to 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile, the reaction was carried out in the same manner as in Synthesis Example 1-22 to obtain 53.5 parts of an isoindoline pigment (a-24) (yield 39%).

(Synthesis example 1-25)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-11 was changed to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline, 396.1 mmol of 2-cyano-N-methylacetamide was changed to 294.5 mmol, Synthesis Example 1- except that 396.1 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide was changed to 294.5 mmol of 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile. The reaction operation was carried out in the same manner as in 11 to obtain 46.9 parts (yield 41%) of isoindoline pigment (a-25).

(Synthesis Example 1-26)
The same reaction procedure as in Synthesis Example 1-9 was carried out except that the barbituric acid in Synthesis Example 1-9 was changed to 1-(4-methylphenyl)barbituric acid, to obtain 105.6 parts (yield 69%) of an isoindoline pigment (a-26).

(Synthesis Example 1-27)
The same reaction procedure as in Synthesis Example 1-8 was carried out except that the barbituric acid in Synthesis Example 1-8 was changed to 1-(4-methylphenyl)barbituric acid, to obtain 83.2 parts (yield 68%) of an isoindoline pigment (a-27).

The structures of the isoindoline pigments obtained in Synthesis Examples 1-1 to 1-27 are shown in Table 1. For example, as seen in the compound of Synthesis Example 1-15, when the relationship between _Y1 and _Y2 and the relationship between _Y3 and _Y4 are asymmetric, the compound is obtained as a mixture of isomers.

The isoindoline compound was identified by comparing the molecular ion peak of the mass spectrum with the mass number (theoretical value) obtained by calculation. The molecular ion peak of the mass spectrum was measured using Waters' ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm x 50 mm)/Ms TAP XEVO TQD. Table 1 shows the theoretical molecular weights and mass spectrometry measurements of the isoindoline compounds (Synthesis Examples 1-1 to 1-27). Due to the nature of the measurement, H (protons) from the compound are eliminated, so if the measured value is the mass number of the theoretical molecular weight - (minus) 1, the compounds will match.

In Table 1, Ph represents a phenyl group, for example, Ph-Me represents a structure in which one hydrogen atom in a phenyl group is replaced with a methyl group, and Np represents a structure in which Y ₁ and Y ₂ in general formula (1) are as follows:

<Production of finely divided pigment>
(Micronization of isoindoline pigment (a-1))
10 parts of the isoindoline pigment (a-1), 100 parts of sodium chloride, and 12.5 parts of ethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 60° C. Next, the kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 80° C. to form a slurry, which was then filtered and washed with water to remove the salt and diethylene glycol, and then dried overnight at 80° C. and pulverized to obtain 9.4 parts of an isoindoline fine pigment (a-1K).

(Refining of isoindoline pigments (a-2) to (a-12))
The isoindoline pigments (a-2) to (a-12) were also subjected to the same refinement treatment as the isoindoline pigment (a-1), resulting in finely divided isoindoline pigments (a-2K) to (a- 12K) was obtained.

(Production of Yellow Micronized Pigment (PY-1))
200 parts of yellow pigment C.I. Pigment Yellow 74 ("LIONOGEN YELLOW 0390" manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 8 liters of warm water, and stirred for 2 hours while heating to 80°C to form a slurry. This slurry was filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night to obtain a yellow fine pigment (PY-1).

(Production of yellow finely divided pigment (PY-2))
Yellow pigment C. I. Pigment Yellow 74, yellow pigment C. I. Pigment Yellow 12 ("FINESS YELLOW G-20S-12" manufactured by Toyo Color Co., Ltd.) was manufactured in the same manner as in the production of yellow finely divided pigment (PY-1), and 97 parts of yellow finely divided pigment (PY-1) was used. 2) was obtained.

(Manufacture of red finely divided pigment (PR-1))
Commercially available C. I. 100 parts of Pigment Red 242 (PR242) ("Sandorin Scarlet 4RF" manufactured by Clariant), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 6 hours. , salt milled. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. , 98 parts of red finely divided pigment (PR-1) were obtained.

(Production of Red Micronized Pigment (PR-2))
C.I. Pigment Red 242 (PR242) (Clariant's "Sandorin Scarlet 4RF") was replaced with C.I. Pigment Red 269 (PR269) (Sanyo Pigment Co., Ltd.'s "Permanent Carmine 3810"), and the same procedure as for the production of the red fine pigment (PR-1) was carried out to obtain 97 parts of a red fine pigment (PR-2).

(Manufacture of red finely divided pigment (PR-3))
C. I. Pigment Red 242 (PR242) (“Sandorin Scarlet 4RF” manufactured by Clariant) was mixed with C.I. I. Pigment Red 57:1 (LIONOL RED TT-5701G manufactured by Toyo Color Co., Ltd.) was manufactured in the same manner as the production of red finely divided pigment (PR-1), and 96 parts of red finely divided pigment (PR-1) was used. 3) was obtained.

(Manufacture of red finely divided pigment (PR-4))
C. I. Pigment Red 242 (PR242) (“Sandorin Scarlet 4RF” manufactured by Clariant) was mixed with C.I. I. Pigment Red 48:3 (LIONOL RED TT-4803 manufactured by Toyo Color Co., Ltd.) was manufactured in the same manner as the production of red finely divided pigment (PR-1), and 99 parts of red finely divided pigment (PR-1) was used. 4) was obtained.

(Production of Red Micronized Pigment (PR-5))
C.I. Pigment Red 242 (PR242) (Clariant's "Sandorin Scarlet 4RF") was replaced with C.I. Pigment Red 146 (Toyo Color's "LIONOL RED 5620"), and the same procedure as for the production of the red fine pigment (PR-1) was carried out to obtain 97 parts of a red fine pigment (PR-5).

(Manufacture of blue finely divided pigment (PB-1))
Phthalocyanine blue pigment C. I. 100 parts of Pigment Blue 15:6 ("Lionor Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of crushed common salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. did. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove the salt and solvent, the mixture was heated to about 70°C for 24 hours. It was dried to obtain 98 parts of blue finely divided pigment (PB-1).

(Production of Purple Micronized Pigment (PV-1))
120 parts of dioxazine-based purple pigment C.I. Pigment Violet 23 (Clariant's "FastViolet RL"), 1600 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 18 hours at 90 ° C. This mixture was added to 5000 parts of hot water, heated to about 70 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 118 parts of purple fine pigment (PV-1).

<Measurement of average primary particle size of pigment>
The average primary particle diameter of the pigment was measured by directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment were measured, and the average was taken as the particle diameter of the pigment particle. Next, for 100 or more pigment particles, the volume (weight) of each particle was determined by approximating it to a cube of the determined particle size, and the volume average particle size was taken as the average primary particle size.
Note that a transmission type (TEM) electron microscope was used.
As a result of measurement using this method, the average primary particle diameter of the isoindoline pigment (a-1) was 460 nm.
Table 2 shows the average primary particle diameters of the pigments and finely divided pigments measured by the above method. Note that (a-1) and (a-2) are crude pigments before being subjected to the above-mentioned refining treatment.

<Manufacture of dye>
(Manufacture of red dye (DR-1))
Red acid dye C. I. 39.2 parts of Basic Red 12, 392 parts of water, and 39.2 parts of methanol were mixed, and a solution of 36.2 parts of didecyldimethylammonium chloride dissolved in 362 parts of water was added little by little. Powder gradually precipitated, so it was filtered on a Nutsche filter and washed by sprinkling 200 parts of water twice. Thereafter, the powder was taken out and dried at 80°C for 8 hours. I. 70.1 parts of a red dye (DR-1), which is a salt formed from Basic Red 12 and didecyldimethylammonium chloride, was obtained.

(Production of Red Dye (DR-2))
58.0 parts of red acid dye C.I. Acid Red 52, 580 parts of water, and 58.0 parts of methanol were mixed, and a solution of 36.2 parts of didecyldimethylammonium chloride dissolved in 362 parts of water was added little by little. Powder gradually precipitated, so this was filtered on a Nutsche and washed by sprinkling 200 parts of water twice. Thereafter, the powder was taken out and dried at 80°C for 8 hours to obtain 90.6 parts of red dye (DR-2), which is a salt product of C.I. Acid Red 52 and didecyldimethylammonium chloride.

(Production of yellow dye (DY-1))
Yellow acid dye C. I. 42.6 parts of Acid Yellow 49, 426 parts of water, and 42.6 parts of methanol were mixed, and a solution of 36.2 parts of didecyldimethylammonium chloride dissolved in 362 parts of water was added little by little. Powder gradually precipitated, so it was filtered on a Nutsche filter and washed by sprinkling 200 parts of water twice. Thereafter, the powder was taken out and dried at 80°C for 8 hours. I. 90.6 parts of a yellow dye (DY-1), which is a salt formed from Acid Red 52 and didecyldimethylammonium chloride, was obtained.

<Method of preparing binder resin solution>
(Binder resin solution 1)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. A reaction vessel was charged with 70.0 parts of cyclohexanone, and the temperature was raised to 80° C. The atmosphere inside the reaction vessel was replaced with nitrogen. Then, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), 2,2'-
A mixture of 0.4 parts of azobisisobutyronitrile was dropped over 2 hours. After the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin with a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 20 wt% to prepare binder resin solution 1. Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The acid value was measured and found to be 94.

(Binder resin solution 2)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80°C. After the atmosphere in the flask was replaced with nitrogen, a mixture of 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After the dropping, the mixture was reacted for another 3 hours at 100°C, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued for another 1 hour at 100°C. Next, the atmosphere in the vessel was replaced with air,
9.3 parts of acrylic acid (100% of glycidyl groups) to 0.
Into the vessel, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120°C for 3.5 hours to obtain a copolymer solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content became 20% by weight to prepare binder resin solution 2. The weight average molecular weight (Mw) was 19,000 and the acid value was 72.

(Comparative Binder Resin Solution 1)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. A reaction vessel was charged with 70.0 parts of cyclohexanone, and the temperature was raised to 80° C. The atmosphere in the reaction vessel was replaced with nitrogen. Then, 16.7 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 0.9 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd.'s "Aronix M110"), 2,2'-
A mixture of 0.4 parts of azobisisobutyronitrile was dropped over 2 hours. After the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin with a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 20 wt% to prepare binder resin solution 1. Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The acid value was measured and found to be 20.

(Comparative binder resin solution 2)
70.0 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and the temperature was raised to 80°C. After purging the inside of the reaction vessel with nitrogen, 10.2 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 7.4 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), 2,2'-
A mixture of 0.4 part of azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain a solution of acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Binder resin solution 1 was prepared by adding the following. Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The acid value was measured and found to be 160.

<Preparation method of resin type dispersant solution>
(Basic resin type dispersant solution 1): Block acrylic type basic dispersant [Synthesis of monomer (b-1)]
A reaction vessel equipped with a stirrer and a thermometer was charged with 60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3-(dimethylamino)propylamine, and 120 parts of THF, and stirred at room temperature for 5 hours. After confirming the completion of the reaction by FT-IR, the solvent was distilled off using a rotary evaporator to obtain 73 parts of the following monomer (b-1) as a pale yellow transparent liquid (yield: 82%). ). The obtained compound was identified by ¹ H-NMR.

Monomer (b-1)

[Synthesis of monomer (b-2)]
A reaction vessel equipped with a stirrer and a thermometer was charged with 6.6 parts of monomer (b-1) obtained in the synthesis of monomer (b-1) and 5 parts of ion-exchanged water, and stirred at room temperature. % aqueous hydrochloric acid solution was added dropwise. Completion of the reaction was confirmed by amine value measurement, and 20 parts of a monomer (b-2) aqueous solution was obtained as a pale yellow transparent liquid. The obtained compound was identified by ¹ H-NMR.

Monomer (b-2)

In a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 20 parts of PGMAc, 21.2 parts of monomer (b-1) as a second block monomer, and 27 parts of an aqueous solution of monomer (b-2) (non-volatile content 38%) were added to this reaction tank, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. After 2 hours, a sample of the polymerization solution was taken to measure the non-volatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the non-volatile content, and the reaction solution was cooled to room temperature to terminate the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by weight. In this way, a basic resin-type dispersant solution 1 was obtained, which had an amine value per non-volatile content of 50 mgKOH/g, a quaternary ammonium salt value of 20 mgKOH/g, and a weight average molecular weight (Mw) of 9,800.

(Basic resin type dispersant solution 2): Block acrylic type basic dispersant In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of methylethylenediamine was charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and the inside of the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were charged into this reactor, and the reaction was continued by stirring while maintaining the temperature at 110° C. and a nitrogen atmosphere. Two hours after adding dimethylaminoethyl methacrylate, the polymerization solution was sampled to measure the nonvolatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of nonvolatile content, and the reaction solution was cooled to room temperature. Polymerization was stopped by cooling.
PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by weight. In this way, a basic resin type dispersant solution 2 having a poly(meth)acrylate skeleton and a tertiary amino group with an amine value per non-volatile content of 71.4 mgKOH/g and a weight average molecular weight of 9900 (Mw) was obtained. Ta.

(Basic resin type dispersant solution 3): Block acrylic type basic dispersant A reaction apparatus equipped with a gas inlet tube, a condenser, an agitator blade, and a thermometer was charged with 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and stirred at 50 ° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were added to the reactor, and the reaction was continued by stirring while maintaining 110° C. and a nitrogen atmosphere. Two hours after the addition of methacryloyloxyethyl trimethyl ammonium chloride, the polymerization solution was sampled and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to stop the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by weight. In this way, a basic resin-type dispersant solution 3 having a poly(meth)acrylate skeleton and a quaternary ammonium salt group, an amine value per non-volatile content of 29.4 mgKOH/g and a weight average molecular weight of 9800 (Mw), was obtained.

(Basic resin type dispersant solution 4): Block acrylic type basic dispersant
In a reaction vessel equipped with a stirrer and a thermometer, 55 parts of 4-dimethylamino-1,2-epoxybutane and 120 parts of tetrahydrofuran (THF) were charged, and the mixture was heated and stirred at 70° C., and 35 parts of methacrylic acid was added dropwise over 60 minutes. After completion of the dropwise addition, the mixture was heated and stirred at 70° C. for another 2 hours, and the reaction was confirmed to be complete by ¹ H-NMR, and then the mixture was allowed to cool to room temperature. The reaction solution was washed successively with 300 parts of ion-exchanged water, 200 parts of saturated sodium bicarbonate, and 200 parts of saturated saline, and then 20 g of magnesium sulfate was added to the organic layer, and the mixture was stirred and filtered. The solvent of the obtained solution was distilled off with a rotary evaporator, and 31 parts of the following monomer (b-3) was obtained as a pale yellow transparent liquid (yield 42%). The obtained compound was identified by ¹ H-NMR.

Monomer (b-3)

In a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 17.6 parts of methyl methacrylate, 52.8 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 25 parts of PGMAc and 25.1 parts of ethylenically unsaturated monomer (b-3) as a second block monomer were added to this reaction tank, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of the ethylenically unsaturated monomer (b-3), a sample was taken from the polymerization solution and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more based on the nonvolatile content.
Further, 4.5 parts of benzyl chloride was added to the reaction vessel, and the mixture was stirred for 3 hours while maintaining the temperature at 110° C. under a nitrogen atmosphere, and then cooled.
PGMAc was added to the block copolymer solution synthesized above so that the nonvolatile content was 40% by weight. In this way, a basic resin-type dispersant solution 4 was obtained, which had an amine value per nonvolatile content of 50 mgKOH/g, a quaternary ammonium salt value of 20 mgKOH/g, a weight average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by weight.

(Basic resin type dispersant solution 5)
A resin-type dispersant having the following structure was obtained by a known method (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Mw = 21000). PGMAc was added so that the nonvolatile content was 40% by weight to obtain basic resin type dispersant solution 5. The numerical value appended to the repeating unit is the molar ratio, and the numerical value appended to the side chain is the number of repeating units.

(Acidic resin type dispersant solution 1)
A resin-type dispersant having the following structure was obtained by a known method (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Mw = 26,000). PGMAc was added so that the non-volatile content became 40% by weight, and an acidic resin-type dispersant solution 1 with an acid value of 53 was obtained. The number attached to the repeating unit is the molar ratio, and the number attached to the side chain is the number of repeating units.

(Acidic resin type dispersant solution 2)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 45 parts of methyl methacrylate, 5 parts of methacrylic acid, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol were added, and further 0.12 part of AIBN (azobisisobutyronitrile) was added, and the mixture was reacted for 12 hours. It was confirmed by non-volatile content measurement that 95% had reacted. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the mixture was heated to 120°C. The mixture was allowed to react for 7 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. PGMAc was added to adjust the nonvolatile content to 40%. In this way, an acidic resin type dispersant solution 2 having an acid value of 75, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton, and an aromatic carboxy group was obtained.

<Production of Comparative High Refractive Index Resin>
(Comparative high refractive index resin solution 1)
As the high refractive index resin, a comparative high refractive index resin 1, which is a fluorene-based polyester, was synthesized.
In a 1L separable flask, 45 g of 9-fluorenone (0.25 mol, manufactured by Osaka Gas Chemicals Co., Ltd.), 188 g (1 mol) of ethylene glycol mono(2-naphthyl)ether, and 1 g of 3-mercaptopropionic acid were added, and then heated to 60°C to completely dissolve. Thereafter, 54 g of sulfuric acid was gradually added, and the mixture was stirred for 5 hours while maintaining the temperature at 60°C. It was confirmed by HPLC (high performance liquid chromatography) that the conversion rate of 9-fluorenone was 99% or more. After neutralizing the reaction liquid obtained by adding a 48% by mass aqueous solution of sodium hydroxide, 400 g of xylene was added, and the mixture was washed several times with distilled water and cooled to precipitate crystals. Furthermore, after filtering and drying, 87 g (yield 67%) of the target 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) was obtained as crystals. The HPLC purity of the obtained crystals was measured to be 98.3%. The obtained sample was confirmed to be 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) by 1H-NMR and mass spectrometry.

In a reactor, the above BNEF (0.80 mol), ethylene glycol (hereinafter referred to as EG) (0.20 mol), and dimethyl 2,6-naphthalene dicarboxylate (hereinafter referred to as DMN) (0.30 mol) were added. , 9,9-di(2-methoxycarbonylethyl)fluorene (9,9-di(carboxyethyl)fluorene or dimethyl ester of fluorene-9,9-dipropionic acid, hereinafter referred to as FDPM) 0.70 mol, ester As an exchange catalyst, 2 x 10-4 mol of manganese acetate tetrahydrate and 8 x 10-4 mol of calcium acetate monohydrate were added and gradually heated and melted while stirring, and the temperature was raised to 250°C. The pressure was reduced stepwise to 10,000 Pa. Ethylene glycol was removed while gradually increasing the temperature and reducing the pressure until the temperature reached 270° C. and 0.13 kPa or less. After reaching the predetermined stirring torque, the contents are removed from the reactor and
Pellets of polyester resin were obtained.

Note that FDPM was synthesized in Example 1 of JP-A No. 2005-89422 using methyl acrylate instead of t-butyl acrylate.

When the obtained pellets were analyzed by NMR, 80 mol% of the diol component introduced into the polyester resin was derived from BNEF, 20 mol% was derived from EG, and 30 mol% of the dicarboxylic acid component introduced into the polyester resin was derived from EG. was derived from DMN, and 70 mol% was derived from FDPM.

Moreover, the weight average molecular weight Mw of the obtained polyester resin was 31,300, and the refractive index at 589 nm was 1.66.

The obtained polyester resin was dissolved in cyclohexanone so that the nonvolatile content was 20%, and a comparative high refractive index resin solution 1 was prepared.

<Production of Pigment Composition>
(Production of Pigment Composition (D-1))
The mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a pigment composition (D-1).
Isoindoline-based fine pigment (a-1K): 8.0 parts Resin-type dispersant 1 solution: 8.0 parts Binder resin solution 1: 44.0 parts PGMAc (methoxypropyl acetate): 40.0 parts

(Pigment compositions (D-2) to (D-38), (DD-1) to (DD-12), (DC-1) to (DC-2))
Except for changing the composition as shown in Table 3, pigment compositions (D-2) to (D-38), (DD-1) to (DD-12), (DC-1) to (DC-2) were prepared in the same manner as pigment composition (D-1).

(Manufacture of dye composition (DDD-1))
After uniformly stirring and mixing a mixture having the composition shown below, it was dispersed in an Eiger mill for 3 hours using zirconia beads with a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to obtain the dye composition (DDD-1). Created.
Red dye (DR-1): 10.0 parts Resin type dispersant solution 1: 10.0 parts Binder resin solution 1: 30.0 parts PGMAc (methoxypropyl acetate): 50.0 parts

(Dye Compositions (DDD-2) to (DDD-3))
Dye compositions (DDD-2) to (DDD-3) were prepared in the same manner as dye composition (DDD-1), except that the composition was changed as shown in Table 3.

(Pigment composition (E-1))
A pigment composition (E-1) was prepared by uniformly stirring and mixing a mixture having the composition shown below.
Pigment composition (DC-1): 20.0 parts Pigment composition (DC-2): 20.0 parts Pigment composition (D-2): 60.0 parts This is a dispersion liquid containing the isoindoline-based finely divided pigment (a-2K) at a pigment concentration of 70% in the solid content, and the solid content of the pigment composition (E-1) contains the isoindoline-based finely divided pigment (a-2K). -2K) is included in 42%. This is shown in Table 4.

<Manufacture of photosensitive composition>
[Example 1]
(Manufacture of photosensitive composition (XR-1))
A photosensitive composition (XR-1) was prepared by stirring and mixing a mixture having the composition shown below to make it uniform.
Photosensitive composition (D-1): 100.0 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.87 parts Photopolymerization initiator ("Irgacure OXE02" manufactured by BASF Corporation) ): 0.47 parts PGMAc: 52.2 parts

[Examples 2 to 44, Comparative Examples 1 to 15]
(Production of photosensitive compositions (XR-2) to (XR-44), (XXR-1) to (XR-15))
Photosensitive compositions (XR-2) to (XR-44), (XXR-1) to (XR -15) was produced.
In Table 5, M-402 indicates "Aronix M-402", M-5300 indicates "Aronix M-5300", OXE02 indicates "Irgacure OXE02", and 907 indicates "Irgacure 907".

<Preparation of film for evaluation of photosensitive composition>

Photosensitive compositions (XR-1) to (XR-45) and (XXR-1) to (XR-15) were applied onto a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater. After that, it was dried at 70°C for 20 minutes. Next, after cooling this substrate to room temperature, it was exposed to ultraviolet light using an ultra-high pressure mercury lamp.
Thereafter, this substrate was spray developed with a 0.2% by mass aqueous sodium carbonate solution at 23° C. for 30 seconds, washed with ion-exchanged water, and dried. Furthermore, heat treatment was performed at 230° C. for 30 minutes in a clean oven.
In the above procedure, the rotational speed of the spin coating was adjusted to obtain a substrate on which a film with a thickness of 1.0 μm was formed.

<Evaluation of Photosensitive Composition>
The following evaluations were carried out using the above evaluation membrane. The results are shown in Table 6.
[Refractive index]
The substrate on which the above-mentioned film was formed was subjected to spectroscopic ellipsometry measurement at 23° C. to determine the refractive indexes at 850 nm, 940 nm, and 1550 nm.

[Light resistance]
A light resistance test was performed on the substrate on which the above film was formed by exposing it to an illumination intensity of 60 W/m ² at 300 to 400 nm for 20 hours using a xenon weather meter.
The change in absorbance at the maximum absorption wavelength between 400 and 700 nm was evaluated based on the following criteria.
〇: The rate of decrease in absorbance at the maximum absorption wavelength is less than 5% △: The rate of decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30% ×: The rate of decrease in absorbance at the maximum absorption wavelength is 30% or more

[Heat-resistant]
The substrate on which the film was formed was heated at 250° C. for 1 hour to conduct a heat resistance test.
The change in absorbance at the maximum absorption wavelength between 400 and 700 nm was evaluated based on the following criteria.
〇: The rate of decrease in absorbance at the maximum absorption wavelength is less than 5% △: The rate of decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30% ×: The rate of decrease in absorbance at the maximum absorption wavelength is 30% or more

[transparency]
The haze of the substrate on which the film was formed was measured using a haze meter, and the transparency was determined based on the following criteria.
〇: Haze is less than 0.5 △: Haze is 0.5 or more and less than 1.0 ×: Haze is 1.0 or more

<Formation of filter segments>
A black matrix was patterned on a 100 mm x 100 mm, 0.7 mm thick glass substrate, and the obtained photosensitive coloring composition was applied onto the substrate using a spin coater, and the solvent was removed by drying at 90° C. for 90 seconds. A coating film having a film thickness of 2.4 μm was obtained. Next, the film was irradiated with ultraviolet rays of 100 mJ/cm ² using an ultra-high pressure mercury lamp through a photomask having a predetermined pattern, and developed by spraying with an alkaline developer consisting of a 0.2% by mass aqueous sodium carbonate solution. The uncured portion was removed to form a desired pattern. The resulting coating film was heat-treated in an oven at 230° C. for 20 minutes to form filter segments. The thickness of the coating film was measured using Dektak3030 (manufactured by Nihon Shinku Gijutsu Co., Ltd.).

<Development residue>
The obtained filter segment was checked for the presence of development residue using a microscope ("BX-51" manufactured by Olympus Optical Co., Ltd.). The evaluation was made by calculating the remaining area of the residue in a square pixel with a 50 μm x 50 μm hollow, and making the evaluation as follows.
◎: No remaining ○: Less than 100 μm ² △: 100 μm ² or more and less than 500 μm ² ×: 500 μm ² or more

<Evaluation of comparative high refractive index resin solution 1>
Comparative high refractive index resin solution 1 was applied onto a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70° C. for 20 minutes, and then heated at 230° C. for 30 minutes. .
In the above procedure, the rotation speed of spin coating was adjusted to obtain a substrate on which a film with a thickness of 1.0 μm was formed, and spectroscopic ellipsometry was performed to determine the refractive index at 850 nm, 940 nm, and 1550 nm. The refractive index was 1.63, the refractive index at 940 nm was 1.62, and the refractive index at 1550 nm was 1.60.

From the above, the photosensitive composition of the present invention has a particularly high refractive index in the wavelength region of 800 to 1600 nm, and can be used as a film with excellent transparency, heat resistance, and light resistance, and therefore can be used for infrared sensors or infrared communication devices. It is useful as an optical lens or an optical waveguide for an infrared sensor or an infrared communication device.

Claims (11)

A photosensitive composition for use in an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device, comprising:
The ink contains an isoindoline pigment, an acidic resin, a dispersant, a photopolymerizable monomer, and a photopolymerization initiator,
the acidic resin has an acid value of 30 to 140 mgKOH/g, and the content of the acidic resin is 2 mass% or more based on the total mass of the solid content in the photosensitive composition;
The dispersant contains a basic resin-type dispersant,
A photosensitive composition having a refractive index of 1.65 or more at 23° C. and a wavelength of 850 nm. The photosensitive composition according to claim 1, wherein the isoindoline pigment has a structure represented by the following general formula (1).
General formula (1)


(X ₁ and X ₂ each independently represent the following general formula (2), (3) or (4). Y ₁ to Y ₄ each independently represent a hydrogen atom, a hydroxy group, a carboxy group , cyano group, nitro group, sulfo group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 4 carbon atoms, alkylcarboxy group having 2 to 4 carbon atoms, halogen atom , an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, -SO ₂ -O-R ₁₁₁ , or -SO ₂ -NH-R represents ₁₁₂ , and two of these may form a ring by removing hydrogen atoms, or a divalent organic group may be inserted between them when forming the ring.R ₁₁₁ and R ₁₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

General formula (2)


(Y ₅ and Y ₆ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cyclo Represents an alkyl group or an aryl group having 6 to 12 carbon atoms, and * represents a bond.)

General formula (3)


(Y ₇ is each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or represents an aryl group having 6 to 12 carbon atoms, and * represents a bond.)

General formula (4)
The photosensitive composition according to claim 1, wherein the pigment content is 30% by mass or more based on the total mass of the solid content in the photosensitive composition. The photosensitive composition according to claim 1, wherein the photopolymerization initiator is an oxime ester compound. The photosensitive composition according to claim 1, which is used as a high refractive index material at 800 nm to 1600 nm. A film comprising the photosensitive composition according to claim 1. An optical material comprising the photosensitive composition according to claim 1. An optical lens comprising the photosensitive composition according to claim 1. An optical waveguide comprising the photosensitive composition according to claim 1. An infrared sensor comprising the film according to claim 6, the optical material according to claim 7, the optical lens according to claim 8, or the optical waveguide according to claim 9. An infrared communication device comprising the film according to claim 6, the optical material according to claim 7, the optical lens according to claim 8, or the optical waveguide according to claim 9.