TW201809870A - Composition, film, optical filter, laminate, solid-state imaging device, image display device, infrared sensor, and compound - Google Patents

Abstract

The present invention provides a composition capable of producing a film or the like having excellent spectral characteristics. In addition, a film, an optical filter, a laminated body, a solid-state imaging device, an image display device, an infrared sensor, and a compound are provided. The composition contains a compound represented by Formula (1), a resin, and a solvent. In formula (1), R ¹ and R ² each independently represent a halogen atom, a cyano group, a nitro group, a fluoroalkyl group, -OCOR ¹¹ , -SOR ¹² or -SO ₂ R ¹³ , and R ¹¹ to R ¹³ are each independently Ground represents a hydrocarbon group or a heteroaryl group, n represents an integer of 1 to 3, R ³ to R ¹⁰ each independently represent a hydrogen atom or a substituent, and X ¹ and X ² each independently represent a hydrogen atom or -BR ^21a R ^22a , R ^21a and R ^22a each independently represent a substituent. The film includes the above-mentioned composition, and the optical filter, a solid-state imaging element, an image display device, and an infrared sensor have the above-mentioned film. The laminated body has the above-mentioned film and a color filter.

Description

Composition, film, optical filter, multilayer body, solid-state imaging device, image display device, infrared sensor, and compound

The present invention relates to a composition, a film, an optical filter, a laminated body, a solid-state imaging element, an image display device, an infrared sensor, and a compound.

CCD (Charge Coupled Device), CMOS (Complementary Metal Oxide Film Semiconductor) used as solid-state imaging elements for color images in cameras, digital still cameras, and mobile phones with camera functions. In these solid-state imaging devices, a silicon photodiode having sensitivity to infrared rays is used in a light receiving portion thereof. Therefore, the near-infrared cut-off filter is sometimes used to perform visual sensitivity correction.

As a near-infrared absorbing compound, a pyrrolopyrrole compound and the like are known (for example, Patent Documents 1 and 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent Laid-Open No. 2009-263614 [Patent Document 2]: International Publication No. WO2016 / 031810

In recent years, in a film including a near-infrared absorbing compound such as a near-infrared cut filter, further improvement in visible transparency is expected. Therefore, it is expected to further improve the visible transparency of the near-infrared absorbing compound itself.

Therefore, an object of the present invention is to provide a composition capable of producing a film or the like having excellent spectral characteristics. The present invention also provides a film, an optical filter, a laminated body, a solid-state imaging device, an image display device, an infrared sensor, and a compound.

As a result of intensive studies based on the above-mentioned conditions, the inventors found that the compound represented by the formula (1) described later has absorption in the near-infrared region and is excellent in visible transparency. Furthermore, it was found that by using this compound, a film or the like having excellent spectral characteristics can be produced, and the present invention has been completed. The present invention provides the following. <1> A composition containing a compound represented by the following formula (1), a resin, and a solvent, [Chemical Formula 1] In formula (1), R ¹ and R ² each independently represent a halogen atom, a cyano group, a nitro group, a fluoroalkyl group, -OCOR ¹¹ , -SOR ¹² or -SO ₂ R ¹³ , and R ¹¹ to R ¹³ are each independently Ground represents a hydrocarbon group or a heteroaryl group, n represents an integer of 1 to 3, R ³ to R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring, R ⁷ to R ¹⁰ each independently represent a hydrogen atom or a substituent, X ¹ and X ² each independently represent a hydrogen atom or -BR ^21a R ^22a , R ^21a and R ^22a each independently represent a substituent, and R ^21a and R ^22a They may be bonded to each other to form a ring. <2> The composition according to <1>, wherein R ⁷ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group. <3> The composition according to <1>, wherein at least one of R ⁷ to R ¹⁰ represents a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group. <4> The composition according to <1>, wherein R ⁷ and R ⁹ each independently represent a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group, and R ⁸ and R ^{10 each} represent a hydrogen atom. <5> The composition according to any one of <1> to <4>, wherein the compound represented by the formula (1) has a maximum absorption wavelength in a range of 700 to 1000 nm, and the absorbance A ₄₅₀ at a wavelength of 450 nm is divided by The value A ₄₅₀ / A _max of the absorbance A _max of the maximum absorption wavelength is 0.015 or less. <6> The composition according to any one of <1> to <5>, further comprising a coloring agent. <7> The composition according to any one of <1> to <5>, further comprising a color material that transmits infrared rays and blocks visible light. <8> The composition according to any one of <1> to <7>, further comprising a radical polymerizable compound and a photopolymerization initiator. <9> A film including the composition according to any one of <1> to <8>. <10> An optical filter having the film according to <9>. <11> The optical filter according to <10>, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter. <12> The optical filter according to <10> or <11>, which has the pixels of the film described in <9>, and is selected from the group consisting of red, green, blue, magenta, yellow, cyan, black, and colorless. Of at least one pixel. <13> A laminated body comprising the film according to <9> and a color filter including a colorant. <14> A solid-state imaging device having the film according to <9>. <15> An image display device having the film according to <9>. <16> An infrared sensor having the film according to <9>. <17> A compound represented by the following formula (1), [Chemical formula 2] In formula (1), R ¹ and R ² each independently represent a halogen atom, a cyano group, a nitro group, a fluoroalkyl group, -OCOR ¹¹ , -SOR ¹² or -SO ₂ R ¹³ , and R ¹¹ to R ¹³ are each independently Ground represents a hydrocarbon group or a heteroaryl group, n represents an integer of 1 to 3, R ³ to R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring, R ⁷ to R ¹⁰ each independently represent a hydrogen atom or a substituent, X ¹ and X ² each independently represent a hydrogen atom or -BR ^21a R ^22a , R ^21a and R ^22a each independently represent a substituent, and R ^21a and R ^22a They may be bonded to each other to form a ring. [Inventive effect]

According to the present invention, it is possible to provide a composition capable of producing a film or the like having excellent spectral characteristics. In addition, a film, an optical filter, a laminated body, a solid-state imaging device, an image display device, an infrared sensor, and a compound can be provided.

Hereinafter, the content of this invention is demonstrated in detail. In this specification, "~" means using the numerical value described before and after "~" as a lower limit value and an upper limit value. Regarding the label of a group (atomic group) in this specification, it is not recorded that both the substituted and unsubstituted labels include a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. As long as "exposure" is not specifically limited in this specification, in addition to exposure using light, the drawing using a particle beam such as an electron beam and an ion beam is also included in the exposure. In addition, as the light used for the exposure, actinic rays such as bright line spectrum of a mercury lamp, excimer laser, extreme ultraviolet (EUV light), X-rays, and electron beams, or radiation are generally mentioned. In this specification, "(meth) acrylate" means both or any one of acrylate and methacrylate, and "(meth) acrylic" means both or any of acrylic and methacrylic acid, "(formaldehyde "Acryl)" means either or both "acryl" and "methacryl". In this specification, a weight average molecular weight and a number average molecular weight are defined as the styrene conversion value measured by the gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and TSKgel Super AWM-H (manufactured by TOSOH CORPORATION, 6.0 mm ID (inner diameter)) can be used as a column. × 15.0 cm) was determined using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution as the eluent. In the present specification, Me in the chemical formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, near-infrared light refers to light (electromagnetic waves) having a maximum absorption wavelength range of 700 to 2500 nm. In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In this specification, the term "process" not only means an independent process, but even if it cannot be clearly distinguished from other processes, if the desired effect of the process can be achieved, it is also included in this term.

<Composition> The composition of the present invention is characterized by containing a compound (hereinafter, also referred to as "compound (1)") represented by the formula (1) described later, a resin, and a solvent.

The compound (1) is excellent in infrared shielding properties and is also excellent in visible transparency. In particular, the transmittance in the vicinity of a wavelength of 450 nm is high. Therefore, the composition of the present invention containing the compound (1) can produce a film having excellent spectral characteristics. For example, by using the composition of the present invention, it is possible to produce a near-infrared cut-off filter or the like that is excellent in visible transparency and excellent in infrared shielding properties. In addition, the composition also contains a color material that transmits infrared rays and blocks visible light, whereby an infrared transmission filter having excellent spectral characteristics and selectively transmitting specific infrared rays can be manufactured. In the infrared transmission filter, the compound (1) has a function of restricting the transmitted light (near infrared) to a longer wavelength side. Furthermore, since the compound (1) is excellent in visible transparency and infrared shielding properties, it is possible to easily control the spectrum of the visible region to be shielded and the spectrum of the infrared region to be transmitted within an appropriate range.

The reason why the compound (1) has excellent infrared shielding properties and excellent visible transparency is presumed to be based on the following. The compound (1) is presumed to be able to reduce visible light originating from the pyrrolopyrrole ring by introducing specific substituents described later as the substituents R ¹ and R ² on the benzene ring bonded to the pyrrolopyrrole ring. As a result, it has excellent infrared shielding properties and can further improve visible transparency. Since these substituents are excellent in electron-attracting property, it is estimated that the amount of visible light derived from a pyrrolopyrrole ring can be effectively reduced. In addition, since the pyrrolopyrrole compound into which these substituents are introduced can be easily synthesized, it is difficult to generate by-products of colored impurities, and as a result, improvement in visible transparency can be expected. Furthermore, the purity of the obtained pyrrolopyrrole compound can be improved, and infrared shielding properties are also excellent. Hereinafter, each component of the composition of the present invention will be described.

<< Compound (1)> The composition of the present invention contains a compound (compound (1)) represented by the following formula (1). Compound (1) is also a compound of the present invention. Compound (1) has a maximum absorption wavelength in the near-infrared region, so it is also a near-infrared absorbing compound. [Chemical Formula 3] In formula (1), R ¹ and R ² each independently represent a halogen atom, a cyano group, a nitro group, a fluoroalkyl group, -OCOR ¹¹ , -SOR ¹² or -SO ₂ R ¹³ , and R ¹¹ to R ¹³ are each independently Ground represents a hydrocarbon group or a heteroaryl group, n represents an integer of 1 to 3, R ³ to R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring, R ⁷ to R ¹⁰ each independently represent a hydrogen atom or a substituent, X ¹ and X ² each independently represent a hydrogen atom or -BR ^21a R ^22a , R ^21a and R ^22a each independently represent a substituent, and R ^21a and R ^22a They may be bonded to each other to form a ring.

In formula (1), R ¹ and R ² each independently represent a halogen atom, a cyano group, a nitro group, a fluoroalkyl group, -OCOR ¹¹ , -SOR ¹² or -SO ₂ R ¹³ , and R ¹¹ to R ¹³ are each independently Ground means a hydrocarbyl or heteroaryl.

Examples of the halogen atom in R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. It is preferable that the fluoroalkyl group in R ¹ and R ² is a perfluoroalkyl group. The carbon number of the fluoroalkyl group is preferably 1 to 10, and more preferably 1 to 5. The fluoroalkyl group may be any of linear, branched, and cyclic, and linear or branched is more preferable, and linear is more preferable.

The hydrocarbon group in R ¹¹ to R ¹³ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. It is preferable that R ¹¹ to R ¹³ are each independently a hydrocarbon group. The carbon number of the alkyl group is preferably 1 to 40. The lower limit is more preferably 3 or more, 5 or more is further preferable, 8 or more is further preferable, and 10 or more is particularly preferable. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkyl group may be any of a straight chain, a branch, and a cyclic ring. A straight chain or a branch is preferred, and a branch is particularly preferred. The branched alkyl group preferably has 3 to 40 carbon atoms. The lower limit is, for example, more preferably 5 or more, 8 or more is more preferable, and 10 or more is more preferable. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of branches of the branched alkyl group is preferably 2 to 10, and more preferably 2 to 8. As long as the number of branches is within the above range, the solvent solubility is good. The cyclic alkyl group may be a monocyclic ring or a fused ring. The cyclic alkyl group may have a crosslinked structure. Examples of the cyclic alkyl group having a crosslinked structure include adamantyl and the like. The carbon number of the alkenyl group is preferably 2 to 40. The lower limit is, for example, more preferably 3 or more, 5 or more is more preferable, 8 or more is more preferable, and 10 or more is particularly preferable. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkenyl group may be any of a straight chain, a branch, and a cyclic ring. A straight chain or a branch is preferred, and a branch is particularly preferred. The number of carbon atoms of the branched alkenyl group is preferably 3 to 40. The lower limit is, for example, more preferably 5 or more, 8 or more is more preferable, and 10 or more is more preferable. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of branches of the branched alkenyl group is preferably 2 to 10, and more preferably 2 to 8. As long as the number of branches is within the above range, the solvent solubility is good. The cyclic alkenyl group may be a monocyclic ring or a fused ring. The cyclic alkenyl group may have a crosslinked structure. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 12.

It is preferable that the heteroaryl group in R ¹¹ to R ¹³ is a monocyclic or fused ring, a monocyclic or fused ring having a condensation number of 2 to 8 is more preferable, and a monocyclic or fused ring having a condensation number of 2 to 4 is further Better. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, even more preferably 3 to 12, and particularly preferably 3 to 10. Heteroaryl is preferably a 5-membered ring or a 6-membered ring.

The hydrocarbon group and heteroaryl group represented by R ¹¹ to R ¹³ may have a substituent or may be unsubstituted. Examples of the substituent include a substituent T described later, a halogen atom, an alkyl group (including a halogenated alkyl group such as a fluoroalkyl group), an alkoxy group, a cyano group, an amine group, a fluorenylamino group, an aminesulfonyl group, a nitrate Basic is preferred. When the hydrocarbon group and heteroaryl group represented by R ¹¹ to R ¹³ have two or more substituents, the substituents may be bonded to each other to form a ring.

When R ¹¹ to R ¹³ are a group having a long-chain alkyl group (preferably an alkyl group having 7 to 30 carbon atoms), the solvent solubility of the compound (1) is good, and the compound can be preferably used as a dye . The long-chain alkyl group may be any of linear and branched groups, and branched alkyl groups are preferred. Examples of the group having a long-chain alkyl group (preferably an alkyl group having 7 to 30 carbon atoms) include an alkoxy group having 7 to 30 carbon atoms, a hydrocarbon group having an alkoxy group having 7 to 30 carbon atoms, and carbon having Heteroaryl groups of alkoxy groups of 7 to 30 and the like. When R ¹¹ to R ¹³ are a hydrocarbon group having a small carbon number (preferably a hydrocarbon group having 1 to 6 carbon atoms) or a heteroaryl group, they can be preferably used as a pigment.

In formula (1), R ¹ and R ² are each independently preferably a nitro group, a fluoroalkyl group, -OCOR ¹¹ , or -SO ₂ R ¹³ , and a nitro group, a fluoroalkyl group, and -OCOR ¹¹ are further preferred. Preferably, -OCOR ¹¹ is particularly preferred. R ¹¹ is preferably an unsubstituted alkyl group, an alkyl group having a substituent, an unsubstituted aryl group, or an aryl group having a substituent. According to this aspect, visible transparency can be further improved. Furthermore, heat resistance can also be improved. In particular, when R ¹¹ is an aryl group having a substituent or an unsubstituted aryl group (preferably a phenyl group having an substituent or an unsubstituted phenyl group), the synthesis yield can be improved and the cost can be reduced. . When R ¹¹ is an aryl group having two or more substituents, and two or more substituents are bonded to each other to form a ring, more excellent visible transparency can be easily obtained. Examples of the group in which the substituents of the aryl group are bonded to each other to form a ring include the following groups. In the following, a wavy line represents a bonding bond, and R represents a hydrogen atom or a substituent. Examples of the substituent include a substituent T described later. [Chemical Formula 4]

In the formula (1), n represents an integer of 1 to 3, 1 or 2 is preferable, and 1 is more preferable. In particular, as shown by the following formula (1a), it is preferable that n is 1 and R ¹ and R ² are introduced into the para position with respect to the pyrrolopyrrole ring. According to this aspect, the crystallinity of the compound is improved, and the heat resistance and light resistance are improved. [Chemical Formula 5]

As shown by the following formula (1b-1) or (1b-2), when R ¹ and R ² are introduced into the meta position with respect to the pyrrolopyrrole ring, excellent solvent dissolution can be easily obtained. And excellent visible transparency. In addition, in formula (1b-2), two R ¹ and R ² may be the same as or different from each other. [Chemical Formula 6]

In addition, as represented by the following formula (1c), R ¹ and R ² may be introduced into the meta and para positions with respect to the pyrrolopyrrole ring. In this case, excellent visible transparency can be easily obtained. In addition, in formula (1c), two R ¹ and R ² may be the same as or different from each other. [Chemical Formula 7]

In Formula (1), R ⁷ to R ¹⁰ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent T described later. It is preferable that R ⁷ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group. The halogen atom and the hydrocarbon group are the same as the halogen atom and the hydrocarbon group described in the above R ¹¹ to R ¹³ .

As a preferable aspect of Formula (1), the following aspects (A) and (B) are mentioned. (A): R ⁷ to R ¹⁰ are all hydrogen atoms. (B): At least one of R ⁷ to R ¹⁰ represents a state of a substituent (preferably a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group).

According to the aspect (A), an effect that the crystallinity is excellent and the heat resistance is improved can be expected.

According to the aspect (B), the effect of reducing the visible absorption derived from the pyrrolopyrrole ring and further improving the transparency can be expected. In the aspect (B), R ⁷ and R ⁹ each independently represent a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group (preferably a halogen atom or a hydrocarbon group, more preferably a fluorine atom, a chlorine atom, and The alkyl group is more preferably a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ⁸ and R ^{10 each} preferably represent a hydrogen atom. According to this aspect, the above effect is more obvious.

In the formula (1), examples of the substituents represented by R ³ to R ⁶ include the following substituent T.

(Substituent T) alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, Fluorenyloxy, amine, sulfonylamino, alkoxycarbonylamino, aryloxycarbonylamino, heteroaryloxycarbonylamino, sulfonylamino, aminesulfonyl, aminoformamidine , Alkylthio, arylthio, heteroarylthio, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, heteroaryl Sulfenyl, urea, phosphonium amine, thiol, sulfo, carboxyl, nitro, hydroxamate, sulfinyl, hydrazine, imino, silyl, hydroxyl, halogen atom, cyanide Base etc.

It is preferable that one of R ³ and R ⁴ represents an electron withdrawing group, and the other represents a heteroaryl group. It is more preferable that one of R ⁵ and R ⁶ represents an electron withdrawing group, and the other represents a heteroaryl group.

Hammett's positive σp (sigma value) substituent acts as an electron withdrawing group. In the present invention, as the electron-withdrawing group, a substituent having a σp value of 0.2 or more of Hammett can be exemplified. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (σp value = 0.66), a carboxyl group (-COOH: σp value = 0.45), an alkoxycarbonyl group (for example, -COOMe: σp value = 0.45), and an aryloxycarbonyl group. (For example, -COOPh: σp value = 0.44), aminomethyl (for example, -CONH ₂ : σp value = 0.36), alkyl carboxyl group (for example, -COMe: σp value = 0.50), aryl carboxyl group (for example , -COPh: σp value = 0.43), alkylsulfonyl (for example, -SO ₂ Me: σp value = 0.72), arylsulfonyl (for example, -SO ₂ Ph: σp value = 0.68), and the like. A cyano group, an alkylcarboxyl group, an alkylsulfonyl group, and an arylsulfonyl group are more preferable, and a cyano group is more preferable. Here, Me represents a methyl group and Ph represents a phenyl group. Regarding the σp value of Hammett, refer to paragraphs 0024 to 0025 of Japanese Patent Application Laid-Open No. 2009-263614, and the contents are incorporated into this specification.

As the heteroaryl group represented by R ³ to R ⁶ , a monocyclic or fused ring is preferred, a monocyclic or fused ring having a condensation number of 2 to 8 is more preferred, and a monocyclic or fused ring having a condensation number of 2 to 4 is more preferred. Is even better. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, even more preferably 3 to 12, and particularly preferably 3 to 10. Heteroaryl is preferably a 5-membered ring or a 6-membered ring.

The heteroaryl group is preferably a group represented by the following formula (A-1) and a group represented by (A-2). [Chemical Formula 8]

In the formula (A-1), A ¹ represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 to R ^X3 each independently represent a hydrogen atom or a substituent, and R ^a1 and R ^a2 each independently represent a hydrogen atom or As a substituent, R ^a1 and R ^a2 may be bonded to each other to form a ring. * Indicates a bonding position in the formula (1). Examples of the substituents represented by R ^a1 , R ^a2, and R ^X1 to R ^X3 include a substituent T, and an alkyl group, an aryl group, and a halogen atom are preferred.

The ring formed by bonding R ^a1 and R ^a2 is preferably an aromatic ring. When R ^a1 and R ^a2 form a ring, examples of (A-1) include a group represented by the following (A-1-1), a group represented by (A-1-2), and the like. [Chemical Formula 9] In the formula, A ¹ represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 to R ^X3 each independently represent a hydrogen atom or a substituent, and R ^101a to R ^110a each independently represent a hydrogen atom or a substituent. * Indicates a bonding position in the formula (1). Examples of the substituents represented by R ^101a to R ^110a include a substituent T.

In formula (A-2), Y ¹ to Y ⁴ each independently represent N or CR ^Y1 , at least two of Y ¹ to Y ⁴ are CR ^Y1 , R ^Y1 represents a hydrogen atom or a substituent, and adjacent R ^Y1 They may be bonded to each other to form a ring. * Indicates a bonding position in the formula (1). Examples of the substituent represented by R ^Y1 include a substituent T. An alkyl group, an aryl group, and a halogen atom are preferred.

At least two of Y ¹ to Y ⁴ are CR ^Y1 , and adjacent R ^Y1s may be bonded to each other to form a ring. It is preferable that the ring formed by the adjacent R ^Y1 bonds to each other is an aromatic ring. When adjacent R ^Y1 forms a ring with each other, examples of (A-2) include a group represented by the following (A-2-1) and a group represented by (A-2-2). [Chemical Formula 10] In the formula, R ^201a to R ^227a each independently represent a hydrogen atom or a substituent, and * represents a bonding position in formula (1). Examples of the substituents represented by R ^201a to R ^227a include the substituent T.

Specific examples of the heteroaryl group represented by R ³ to R ⁶ include the following. In the following, Bu represents butyl. [Chemical Formula 11]

In Formula (1), X ¹ and X ² each independently represent a hydrogen atom or -BR ^21a R ^22a , R ^21a and R ^22a each independently represent a substituent, and R ^21a and R ^22a may be bonded to each other to form a ring. Examples of the substituent include the above-mentioned substituent T. A halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferable, a halogen atom, an aryl group, or a heteroaryl group is more preferable. Or heteroaryl is further preferred. R ^21a and R ^22a may be the same group or different groups. It is preferred that R ^21a and R ^22a are the same group. X ¹ and X ² may be the same group or different groups. It is preferable that X ¹ and X ² are the same group.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferred, and a fluorine atom is particularly preferred. The carbon number of the alkyl group is preferably 1 to 40. The lower limit is more preferably 3 or more, for example. The upper limit is, for example, preferably 30 or less, and more preferably 25 or less. The alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the alkenyl group is preferably 2 to 40. The lower limit is, for example, more preferably 3 or more, 5 or more is more preferable, 8 or more is more preferable, and 10 or more is particularly preferable. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkenyl group may be any of linear, branched, and cyclic. The carbon number of the alkoxy group is preferably 1 to 40. The lower limit is more preferably 3 or more, for example. The upper limit is, for example, preferably 30 or less, and more preferably 25 or less. The alkoxy group may be any of linear, branched, and cyclic. The carbon number of the aryl group is preferably 6 to 20, and more preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. Heteroaryl may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably from 3 to 30, more preferably from 3 to 18, even more preferably from 3 to 12, and particularly preferably from 3 to 5. Heteroaryl is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.

R ^21a and R ^22a of the group represented by -BR ^21a R ^22a may be bonded to each other to form a ring. For example, the structure shown by following (B-1)-(B-4) etc. is mentioned. Hereinafter, R represents a substituent, R ^b1 to R ^b4 each independently represent a hydrogen atom or a substituent, m1 to m3 each independently represent an integer of 0 to 4, and * represents a bonding position in formula (1). Examples of the substituents represented by R and R ^b1 to R ^b4 include the above-mentioned substituent T, and a halogen atom and an alkyl group are preferred. [Chemical Formula 12]

Specific examples of X ¹ and X ² include the following. Hereinafter, Me represents a methyl group and Bu represents a butyl group. [Chemical Formula 13]

Specific examples of the compound (1) include the following compounds. In the following structural formulas, Ph represents a phenyl group, Me represents a methyl group, and Bu represents a butyl group. [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] [Chemical Formula 18] [Chemical Formula 19] [Chemical Formula 20] [Chemical Formula 21] [Chemical Formula 22]

The compound (1) may be a pigment or a dye. When the compound (1) is a pigment, an effect excellent in heat resistance and light resistance can be expected. When the compound (1) is a dye, an effect excellent in visible transparency can be expected. In the present invention, the pigment refers to a compound that is not easily dissolved in a solvent. For example, the solubility of the pigment in 100 g of water at 23 ° C. and the solubility of 100 g of propylene glycol monomethyl ether acetate at 23 ° C. are each preferably 0.1 g or less, and more preferably 0.01 g or less. In the present invention, the dye refers to a compound that is easily soluble in a solvent. For example, the solubility of the dye in 100 g of water at 23 ° C. or the solubility of 100 g of propylene glycol monomethyl ether acetate at 23 ° C. is preferably greater than 0.1 g, and more preferably greater than 1 g. The compound (1) can be used as a pigment or a pigment derivative.

It is preferable that the maximum absorption wavelength of the compound (1) is in the range of 700 to 1000 nm. In addition, in the present specification, “having a maximum absorption wavelength in a range of 700 to 1000 nm” means a wavelength exhibiting a maximum absorbance in a range of 700 to 1000 nm in an absorption spectrum in a solution of the compound (1). Examples of the measurement solvent used in the measurement of the absorption spectrum of the compound (1) include chloroform, ethyl acetate, and tetrahydrofuran. When the compound (1) is a compound dissolved in chloroform, chloroform is used as a measurement solvent.

The value of A ₄₅₀ / A _max (hereinafter, also referred to as "absorbance ratio (450)"), which is the value obtained by dividing the absorbance A ₄₅₀ at 450 nm of the compound (1) by the absorbance A _max at the maximum absorption wavelength, is 0.015 or less. good. As long as the absorbance ratio (450) is 0.015 or less, the infrared shielding properties are excellent, and the visibility and transparency are also excellent. When the absorbance ratio (450) is to be 0.015 or less, it can be achieved by introducing the above-mentioned substituents as R ¹ and R ² as the formula (1).

In the composition of the present invention, the content of the compound (1) is preferably 0.01 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less.

<< Other Near-Infrared Absorbing Compounds >> The composition of the present invention may contain near-infrared-absorbing compounds (hereinafter, also referred to as "other near-infrared-absorbing compounds") other than the above-mentioned compound (1). Examples of other near-infrared absorbing compounds include pyrrolopyrrole compounds, cyanine compounds, squaric acid compounds, phthalocyanine compounds, naphthalocyanine compounds, rylene compounds, merocyanine compounds, and ketoacid compounds , Oxacyanine compound, diimmonium compound, dithiol compound, triarylmethane compound, pyrrolidine compound, azomethine compound, anthraquinone compound, dibenzofuranone compound, copper compound, and the like. Examples of the pyrrolopyrrole compounds include compounds D-100 to D-104 having the following structures. In addition, the compounds described in paragraphs 0016 to 0058 of Japanese Patent Laid-Open No. 2009-263614, the compounds described in paragraphs 0037 to 0052 of Japanese Patent Laid-Open No. 2011-68731, and International Publication No. WO2015 / 166873 can be cited. The compounds described in paragraphs 0010 to 0033 are incorporated into this specification. Examples of the cubic acid compound include compounds described in paragraphs 0044 to 0049 of Japanese Patent Application Laid-Open No. 2011-208101, and the contents are incorporated into this specification. Examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of JP 2009-108267, and compounds described in paragraphs 0026 to 0030 of JP 2002-194040. The contents are incorporated into this manual. Examples of the diimmonium compound include compounds described in Japanese Patent Application Publication No. 2008-528706, and the contents are incorporated into this specification. Examples of the phthalocyanine compound include compounds described in paragraph 0093 of Japanese Patent Application Laid-Open No. 2012-77153, titanium oxyphthalocyanine described in Japanese Patent Laid-Open No. 2006-343631, and Japanese Patent Laid-Open No. 2013-195480. The compounds described in paragraphs 0013 to 0029 are incorporated into this specification. Examples of the naphthalocyanine compound include compounds described in paragraph 093 of Japanese Patent Application Laid-Open No. 2012-77153, and the contents are incorporated into this specification. For the cyanine compound, phthalocyanine compound, naphthalocyanine compound, diimmonium compound, and cubic acid compound, the compounds described in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-111750 can be used, and the contents are incorporated herein In the manual. The cyanine compound can be referred to, for example, "functional pigments, Ogawara Shinzo / Matsuoka Ken / Hiro Kitahiro / Hiroshi Hirata, Kodansha Ltd.", and the contents are incorporated into this specification. Examples of copper complexes include the copper complexes described in paragraphs 0009 to 0049 of International Publication No. WO2016 / 068037, and the phosphate copper complexes described in paragraphs 0022 to 0042 of Japanese Patent Application Laid-Open No. 2014-41318. Compounds, copper sulfonate complexes described in paragraphs 021 to 0039 of Japanese Patent Application Laid-Open No. 2015-43063, and the like are incorporated into this specification. [Chemical Formula 23]

In addition, as other near-infrared absorbing compounds, inorganic particles can be used. It is preferable that the inorganic particles are metal oxide particles or metal particles from the viewpoint that the infrared shielding properties are more excellent. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, and aluminum-doped ZnO. Particles, fluorine-doped tin dioxide (F-doped SnO 2) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. As the inorganic fine particles, a tungsten oxide-based compound can be used. The tungsten oxide-based compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, refer to paragraph 0080 of Japanese Patent Application Laid-Open No. 2016-006476, and this content is incorporated into this specification. The shape of the inorganic particles is not particularly limited, and has no relation to the spherical shape and the non-spherical shape, and may be a sheet shape, a linear shape, or a tubular shape.

The average particle diameter of the inorganic particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. The average particle diameter of the inorganic particles is in such a range, whereby it can be seen that the transparency is good. From the standpoint of avoiding light scattering, the smaller the average particle diameter is, the better, but for reasons such as ease of handling, the average particle diameter of the inorganic particles is usually 1 nm or more.

When the composition of the present invention further contains other near-infrared absorbing compounds, the content of the other near-infrared absorbing compounds is preferably 0.01 to 50% by mass relative to the total solid content of the composition of the present invention. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less. The total content of the compound (1) and other near-infrared absorbing compounds is preferably 0.01 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less. The content of the other near-infrared absorbing compound in the total mass of the compound (1) and the other near-infrared absorbing compound is preferably 1 to 99% by mass. The upper limit is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

<<< Coloring agent> The composition of this invention can contain a coloring agent. In the present invention, a coloring agent refers to a coloring agent other than a white coloring agent and a black coloring agent. The coloring agent is preferably a coloring agent having absorption in a wavelength range of 400 nm or more and less than 650 nm.

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

The dye is not particularly limited, and a known dye can be used. As the chemical structure, a pyrazole azo-based, aniline azo-based, triarylmethane-based, anthraquinone-based, anthrapyridone-based, benzylidene-based, oxacyanine-based, or pyrazolotriazole azo-based , Pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azo-based, dibenzopiperan-based, phthalocyanine-based, benzopyran-based, indigo-based, methylene Pyrroles and other dyes. A multimer of these dyes can also be used. The dyes described in Japanese Patent Application Laid-Open No. 2015-028144 and Japanese Patent Application Laid-Open No. 2015-34966 can also be used.

When the composition of the present invention contains a coloring agent, the content of the coloring agent is preferably 0.1 to 70% by mass based on the total solid content of the composition of the present invention. The lower limit is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. The content of the coloring agent is preferably 10 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass with respect to 100 parts by mass of the compound (1). The total amount of the colorant and the compound (1) is preferably 1 to 80% by mass based on the total solid content of the composition of the present invention. The lower limit is preferably 5 mass% or more, and more preferably 10 mass% or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less. When the composition of the present invention contains two or more colorants, the total amount thereof is preferably within the above range.

<<< Color material that transmits infrared rays and blocks visible light >> The composition of the present invention may further contain a color material that blocks infrared rays and block visible light (hereinafter, also referred to as "color material that blocks visible light"). In the present invention, the color material that shields visible light is preferably a color material that absorbs light in the purple to red wavelength region. In the present invention, the color material that shields visible light is preferably a color material that shields light in a wavelength range of 450 to 650 nm. The color material that shields visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm. In the present invention, it is preferable that the color material that shields visible light satisfies at least one of the following (1) and (2). (1): Two or more coloring agents are included, and a black color is formed by a combination of two or more coloring agents. (2): Contains organic black colorants. In the aspect (2), it is also preferable to further contain a coloring agent.

In the present invention, the organic black colorant as a color material that shields visible light is a material that absorbs visible light but transmits at least a part of infrared rays. Accordingly, in the present invention, the organic black colorant, which is a color material that blocks visible light, does not contain a black colorant that absorbs both visible light and infrared light, and does not include, for example, carbon black or titanium black.

Examples of the coloring agent include the above. Examples of the organic black colorant include a dibenzofuranone compound, an azomethine compound, a fluorene compound, an azo compound, and the like, and a dibenzofuranone compound and a fluorene compound are preferable. Examples of the dibenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, and the like, and can be used, for example, by BASF Corporation " Irgaphor Black ". Examples of the sulfonium compounds include C.I. Pigment Black (Pigment Black) 31, 32, and the like. Examples of the azomethine compound include compounds described in Japanese Patent Application Laid-Open No. 1-170601 and Japanese Patent Application Laid-Open No. 2-34664. For example, the compounds can be used as "CHROMOFINE" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. BLACK A1103 ".

In the present invention, regarding a color material that shields visible light, for example, the ratio A / B of the ratio A / B of the minimum value A of the absorbance in the range of 450 to 650 nm to the minimum value B of the absorbance in the range of 900 to 1300 nm is 4.5 or more. Better. The above characteristics can be satisfied by one kind of material or a combination of plural kinds of materials. For example, in the aspect (1), it is preferable that a plurality of color colorants are combined to satisfy the above-mentioned spectral characteristics. In the aspect (2), the organic black colorant can satisfy the above-mentioned spectral characteristics. The above-mentioned spectral characteristics can be satisfied by a combination of an organic black colorant and a colorant.

When black is formed from a combination of two or more colorants, examples of the combination of colorants include the following. (1) A state containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant. (2) A state containing a yellow colorant, a blue colorant, and a red colorant. (3) A state containing a yellow colorant, a purple colorant, and a red colorant. (4) A state containing a yellow colorant and a purple colorant. (5) A state containing a green colorant, a blue colorant, a purple colorant, and a red colorant. (6) A state containing a purple colorant and an orange colorant. (7) A state containing a green colorant, a purple colorant, and a red colorant. (8) A state containing a green colorant and a red colorant.

Examples of the ratio (mass ratio) of each colorant include the following. [Table 1]

When the composition of the present invention contains a color material that blocks visible light, the content of the color material that blocks visible light is preferably 30% by mass or less, more preferably 20% by mass or less, and 15% by mass or less with respect to the total solid content of the composition. Is even better. The lower limit can be, for example, 0.01% by mass or more, and can be 0.5% by mass or more. Moreover, the composition of this invention can be set as the state which does not contain the color material which blocks visible light substantially. The color material that does not substantially block visible light means that the content of the color material that blocks visible light is preferably 0.005 mass% or less in the total solid content of the composition of the present invention, and 0.001 mass% or less is more preferred, and does not contain A color material that shields visible light is further preferred.

<< Pigment derivative >> When the composition of this invention contains a pigment, it can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a group having a salt structure, or a phthalimide methyl group, and a pigment derivative represented by the formula (B1) Is better.

[Chemical Formula 24] In the formula (B1), P represents a pigment structure, L represents a single bond or a linking group, X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide methyl group, and m represents 1 or more Integer, n represents an integer of 1 or more, when m is 2 or more, the plural L and X may be different from each other, and when n is 2 or more, the plural X may be different from each other.

In formula (B1), P represents a pigment structure selected from the group consisting of pyrrolopyrrole pigment structures, diketopyrrolopyrrole pigment structures, quinacridone pigment structures, anthraquinone pigment structures, dianthraquinone pigment structures, and benzoisoindole Indole pigment structure, thiazine indigo pigment structure, azo pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, pyrene pigment structure, perionone pigment structure, benzo At least one of an imidazolinone pigment structure, a benzothiazole pigment structure, a benzimidazole pigment structure, and a benzoxazole pigment structure is preferably selected from the group consisting of a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, quine At least one of an acridone pigment structure and a benzimidazolinone pigment structure is further preferred, and a pyrrolopyrrole pigment structure is particularly preferred.

In formula (B1), L represents a single bond or a linking group. As the linking group, a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms is preferred, and may be Substitution may also have a substituent.

In the formula (B1), X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide methyl group.

Specific examples of the pigment derivative include the following compounds. Ph in the following structural formula is phenyl. The following compounds are different from the above-mentioned compound (1). The following compounds do not have the above-mentioned specific substituents at the positions corresponding to R ¹ and R ² in formula (1). [Chemical Formula 25]

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment contained in the composition. The lower limit value is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. As long as the content of the pigment derivative is within the above range, the dispersibility of the pigment can be improved, and aggregation of the pigment can be effectively suppressed. The pigment derivative may be only one type, or may be two or more types. When there are two or more types, the total amount is preferably in the above range.

<< Resin> The composition of the present invention contains a resin. The resin is prepared, for example, for use in dispersing a pigment or the like in a composition, or for use in a binder. A resin mainly used for dispersing pigments and the like is referred to as a "dispersant". However, an application such as a resin is an example, and the resin can also be used for purposes other than this application.

Examples of the resin include a (meth) acrylic resin, an epoxy resin, an olefin-thiol resin, a polycarbonate resin, a polyether resin, a polyarylate resin, a polyfluorene resin, a polyetherfluorene resin, a polybenzene resin, and a polystyrene resin. Aryl ether phosphine oxide resin, polyfluorene imide resin, polyfluorene-fluorene imine resin, polyolefin resin, cycloolefin resin, polyester resin, styrene resin. One type of these resins may be used alone, or two or more types may be mixed and used.

When it is an epoxy resin, the weight average molecular weight (Mw) of the resin is preferably 100 or more, and more preferably 200 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 100 or more, and more preferably 200 or more. When it is a resin other than an epoxy resin, 2,000 to 2,000,000 is preferable. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

Examples of the (meth) acrylic resin include a polymer containing a repeating unit derived from (meth) acrylic acid and / or an ester thereof. Specifically, a polymer obtained by polymerizing at least one selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamide, and (meth) acrylonitrile.

Examples of the polyester resin include polyhydric alcohols (for example, ethylene glycol, propylene glycol, glycerol, and trimethylolpropane) and polybasic acids (for example, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid). Carbon numbers such as aromatic dicarboxylic acids, aromatic dicarboxylic acids, adipic acid, sebacic acid, dodecane dicarboxylic acid and the like, wherein the hydrogen atoms of their aromatic rings are replaced by methyl, ethyl, phenyl, etc. A polymer obtained by the reaction of 2 to 20 aliphatic dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc., obtained by ring-opening polymerization of a cyclic ester compound such as a caprolactone monomer Polymers (such as polycaprolactone).

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, and aliphatic epoxy resin. As a commercial item, the following are mentioned, for example. Examples of the bisphenol A epoxy resin include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (the above are manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051 , EPICLON1055 (the above is made by DIC Corporation) and so on. Examples of the bisphenol F-type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (the above are manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON830, EPICLON835 (the above are manufactured by DIC Corporation), LCE-21, RE-602S (the above are manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of the novolac epoxy resin include jER152, jER154, jER157S70, jER157S65 (the above are manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, and EPICLON N-775 (the above are manufactured by DIC Corporation) )Wait. Examples of the cresol novolac epoxy resin include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (the above is DIC Corporation), EOCN-1020 (Nippon Kayaku Co., Ltd.) and others. Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (the above are manufactured by ADEKA CORPORATION), CELOXIDE 2021P, CELOXIDE 2081, CELOXIDE 2083, CELOXIDE 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above manufactured by Nagase ChemteX Corporation), etc. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (the above are made by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (the above are manufactured by ADEKA CORPORATION), jER1031S (made by Mitsubishi Chemical Co., Ltd.), and the like. As the epoxy resin, MARPROOF G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (manufactured by NOF Corporation) were used. , Epoxy-containing polymers) are also preferred.

The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group. These acid groups may be only one kind, or two or more kinds. A resin having an acid group can be used as an alkali-soluble resin. It can also be used as a dispersant.

As the resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples include a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, a novolac resin, and the like Alkali-soluble phenolic resin, acidic cellulose derivative having a carboxyl group in a side chain, and resin having an acid anhydride added to a polymer having a hydroxyl group. In particular, as the alkali-soluble resin, a copolymer of (meth) acrylic acid and a monomer capable of being copolymerized therewith is preferable. Examples of other monomers that can be copolymerized with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and ethylene compounds. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Butyl, isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Esters, toluene (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, and methyl Glycidyl acrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer, and the like. In addition, for other monomers, the N-substituted cis-butenedifluorene imine monomer described in Japanese Patent Application Laid-Open No. 10-300922 can be used, for example, N-phenylcis butadieneimine, N-cyclohexyl Maleimide and the like. In addition, the other monomers that can be copolymerized with these (meth) acrylic acids may be only one kind, or two or more kinds.

As the resin having an acid group, benzyl (meth) acrylate / (meth) acrylic copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate can be preferably used. Copolymer, multi-component copolymer containing benzyl (meth) acrylate / (meth) acrylic acid / other monomers. In addition, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate / polybenzene described in Japanese Patent Application Laid-Open No. 7-140654 can also be preferably used. Ethylene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methyl Acrylic copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer and the like.

It is also preferable that the resin having an acid group contains a polymer represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, the polymer These compounds are called "ether dimers") by polymerizing monomer components.

[Chemical Formula 26]

In the formula (ED1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent. [Chemical Formula 27] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), reference can be made to the description in Japanese Patent Application Laid-Open No. 2010-168539.

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

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

The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X). [Chemical Formula 28] In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer from 1 to 15.

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

As the resin having an acid group, refer to the description of paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of US Patent Application Publication No. 2012/0235099), and Japanese Patent Laid-Open No. 2012- The descriptions in paragraphs 0076 to 0099 of 198408 are incorporated into this specification. As the resin having an acid group, ACRYBASE FF-426 (manufactured by NIPPON SHOKUBAI CO., LTD.) Can be used.

The acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.

The resin may have a hardenable group. Examples of the curable group include a group having an ethylenically unsaturated bond, an epoxy group, a methylol group, and an alkoxysilyl group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acrylfluorenyl group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. Examples of the repeating unit having a curable group include the following formulae (A2-1) to (A2-4). [Chemical Formula 29]

R ¹ represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, 1 to 3 is more preferable, and 1 is particularly preferable. R ¹ is preferably a hydrogen atom or a methyl group.

L ⁵¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene, arylene, -O-, -S-, -CO-, -COO-, -OCO-, -SO _2- , and -NR- (R represents a hydrogen atom or An alkyl group or a hydrogen atom is preferred) or a group including a combination thereof, and a group including a combination of at least one of an alkylene group, an alkylene group, and an alkylene group with -O- is preferable. The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 15 and even more preferably 1 to 10. The alkylene group may have a substituent, but unsubstituted is preferred. The alkylene group may be any of linear, branched, and cyclic. The cyclic alkylene group may be any of a monocyclic ring and a polycyclic ring. The carbon number of the arylene is preferably from 6 to 18, more preferably from 6 to 14, and even more preferably from 6 to 10.

P ¹ represents a hardening group. Examples of the curable group include a group having an ethylenically unsaturated bond, an epoxy group, a methylol group, and an alkoxysilyl group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acrylfluorenyl group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group.

Examples of the resin containing a hardening group include DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (COOH contains polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), VISCOTE R-264, and KS RESIST106 (All made by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all made by Daicel Corporation.), Ebecryl 3800 (made by Daicel UCB Co., Ltd), AKURIKYUA RD-F8 (NIPPON SHOKUBAI CO., LTD.) And so on. Moreover, the products etc. demonstrated with the said epoxy resin are mentioned.

When the composition of the present invention contains a pigment, it is preferable that the resin contains a dispersant. The resin that functions as a dispersant is preferably an acidic resin and / or a basic resin. Here, the acidic resin means a resin having a larger amount of acid groups than a basic group. In the acid type resin, when the total amount of the acid group and the amount of the basic group in the resin is set to 100 mol%, a resin having an acid group amount of 70 mol% or more is preferable, and substantially only includes Acid-based resins are more preferred. It is preferable that the acid group of the acidic resin is a carboxyl group. The acid value of the acidic resin is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g. The basic resin means a resin having a larger amount of basic groups than an acid group. Among the basic resins, when the total amount of the acid group and the amount of the basic group in the resin is 100 mol%, a resin having an amount of the basic group greater than 50 mol% is preferred. It is preferable that the basic group having a basic resin is an amine group.

Examples of the dispersant include a polymer dispersant [for example, a resin having an amine group (a polyamidoamine group and a salt thereof), an oligoimide resin, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated ester, and a modified Modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, formalin naphthalenesulfonic acid] and the like. The polymer dispersant can be classified into a linear polymer, a terminally modified polymer, a graft polymer, and a block polymer according to its structure.

Examples of the terminally modified polymer include a polymer having a phosphate group at the terminal described in Japanese Patent Application Laid-Open No. 3-112992, Japanese Patent Application No. 2003-533455, and Japanese Patent Application Laid-Open No. 2002-273191. A polymer having a sulfo group at the terminal, a polymer having a partial skeleton or a heterocyclic ring having an organic pigment described in Japanese Patent Application Laid-Open No. 9-77994, etc., etc. In addition, as described in Japanese Patent Application Laid-Open No. 2007-277514, two or more anchor sites (acid groups, basic groups, partial skeletons or heterocyclic rings of organic pigments, etc.) on the surface of the pigment are introduced into the polymer end. Molecules are also excellent in dispersion stability.

Examples of the block polymer include those disclosed in Japanese Patent Application Laid-Open No. 2003-49110 and Japanese Patent Application Laid-Open No. 2009-52010.

Examples of the graft polymer include poly (lower alkylene imine) described in Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application No. 8-507960, and Japanese Patent Application Laid-Open No. 2009-258668. ) Reaction products with polyesters, reaction products of polyacrylamine groups and polyesters described in JP 9-169821 and other publications, JP 10-339949, JP 2004-37986 Copolymers of macromonomers and monomers having nitrogen atom-containing groups described in publications, etc., Japanese Patent Application Laid-Open No. 2003-238837, Japanese Patent Application Laid-Open No. 2008-9426, Japanese Patent Application Laid-Open No. 2008-81732 A graft polymer having a partial skeleton or a heterocyclic ring having an organic pigment as described in Japanese Patent Application Publication No. 2010-106268 and the like, and a copolymer of a macromonomer and an acid group-containing monomer described in Japanese Patent Application Laid-Open No. 2010-106268.

As the dispersant, a graft copolymer described in paragraphs 0025 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128, and an oligoimide system described in paragraphs 0102 to 0174 of Japanese Patent Laid-Open No. 2012-255128 can be used. Resin, and incorporate those into this manual.

As the dispersant, a resin including a repeating unit represented by the formula (P1) can be used. [Chemical Formula 30] In the formula (P1), R ¹ represents hydrogen or methyl, R ² represents an alkylene group, and Z represents a nitrogen-containing heterocyclic structure.

The alkylene group represented by R ² is not particularly limited. For example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a 2-hydroxyalkylene group, Methyleneoxy, ethoxy, methoxycarbonyl, methylenethio and the like are more preferably methylene, methyleneoxy, methyleneoxycarbonyl and methylenethio.

Examples of the nitrogen-containing heterocyclic structure represented by Z include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a quinoline ring, and an acridine ring. , Phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amidine structure, cyclic urea structure, and cyclic fluorene Those with imine structure.

Specific examples of the repeating unit represented by the formula (P1) include the followings. In addition, reference can be made to the description in paragraph 023 of Japanese Patent Application Laid-Open No. 2008-009426, and the contents can be incorporated into this specification. [Chemical Formula 31]

Specific examples of the resin including a repeating unit represented by the formula (P1) include the following. [Chemical Formula 32]

The resin can also be obtained as a commercial product, and the product described in paragraph 092 of Japanese Patent Application Laid-Open No. 2015-200878 can be used.

The content of the resin in the composition of the present invention is preferably 1 to 80% by mass based on the total solid content of the composition of the present invention. The lower limit is preferably 5 mass% or more, and more preferably 7 mass% or more. The upper limit is preferably 50% by mass or less, and more preferably 30% by mass or less. When a dispersant is contained as a resin, the content of the dispersant is preferably 0.1 to 40% by mass based on the total solid content of the composition. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The content of the dispersant is preferably 1 to 100 parts by mass based on 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.

<< Polymerizable Compound> The composition of the present invention preferably contains a polymerizable compound. The polymerizable compound is preferably a compound that can be polymerized by the action of a radical. That is, it is preferable that the polymerizable compound is a radical polymerizable compound. The polymerizable compound is preferably a compound having one or more ethylenically unsaturated groups, and a compound having two or more ethylenically unsaturated groups is more preferred, having three or more ethylenically unsaturated groups. Compounds of bonded groups are further preferred. The upper limit of the number of groups having an ethylenically unsaturated bond is, for example, preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth) allyl group, and a (meth) acrylfluorenyl group. A (meth) acrylfluorenyl group is preferred. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound.

The polymerizable compound may be in any form of a monomer and a polymer, and a monomer is preferred. The molecular weight of the polymerizable compound of the monomer type is preferably 100 to 3000. The upper limit is preferably below 2,000, and even more preferably below 1500. The lower limit is preferably 150 or more, and more preferably 250 or more. It is also preferable that the polymerizable compound is a compound having substantially no molecular weight distribution. Among them, having substantially no molecular weight distribution means that the degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the compound is preferably 1.0 to 1.5, and more preferably 1.0 to 1.3.

As examples of the polymerizable compound, the descriptions in paragraphs 0033 to 0034 of Japanese Patent Application Laid-Open No. 2013-253224 can be referred to, and the contents are incorporated into this specification. As the polymerizable compound, ethoxylated pentaerythritol tetraacrylate (as a commercially available product, NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd), dipentaerythritol penta (meth) acrylate (as Commercially available products: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd .; dipentaerythritol hexa (meth) acrylate (as commercially available products: KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd .; A-DPH-12E; The structure manufactured by Shin-Nakamura Chemical Co., Ltd.) and their (meth) acrylfluorenyl groups are preferably bonded via ethylene glycol residues and / or propylene glycol residues. Moreover, these oligomer types can also be used. In addition, it is possible to refer to the descriptions in paragraphs 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224 and incorporate the contents into this specification. In addition, the polymerizable monomers and the like described in paragraph 0477 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to paragraph 0585 of the specification of U.S. Patent Application Publication No. 2012/0235099) are incorporated in this specification. . In addition, diglycerol EO (ethylene oxide) modified (meth) acrylate (as a commercial product, M-460; manufactured by TOAGOSEI CO., LTD.), Pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferred. It is also possible to use their oligo type. Examples include RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).

The polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphate group. Examples of the polymerizable compound having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A polymerizable compound that reacts an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride and has an acid group is particularly preferred. The aliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol. . Examples of commercially available products include polyacid modified acrylic oligomers made by TOAGOSEI CO., LTD., And examples thereof include M-305, M-510, and M-520 of the ARONIX series. The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

It is also preferable that the polymerizable compound is a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, di-trimethylolethane, and trimethylol. Polyols such as propane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylol melamine, etc., obtained by esterification with (meth) acrylic acid and -Caprolactone modified polyfunctional (meth) acrylate. As the polymerizable compound having a caprolactone structure, reference can be made to the descriptions in paragraphs 042 to 0045 of Japanese Patent Application Laid-Open No. 2013-253224, and the contents are incorporated into this specification. The compound having a caprolactone structure includes, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. commercially available as KAYARAD DPCA series by Nippon Kayaku Co., Ltd., manufactured by Sartomer Company, Inc. SR-494, which is a 4-functional acrylate having 4 ethoxylated chains, TPA-330, which is a trifunctional acrylate with 3 isobutynyl chains.

As the polymerizable compound, the urethanes described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Acrylates have an ethylene oxide skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Urethane compounds are also preferred. Moreover, the addition described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238 can be used to have an amine structure or a sulfide structure in the molecule. Polymerizable compounds. Examples of commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and DPHA -40H (manufactured by Nippon Kayaku Co., Ltd), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), and the like.

When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, and more preferably 20% by mass or less. The polymerizable compound may be used singly or in combination of two or more kinds. When two or more polymerizable compounds are used simultaneously, it is preferable that the total amount falls within the above range. When the composition contains an epoxy resin and a polymerizable compound, the mass ratio of the polymerizable compound to the epoxy resin is a polymerizable compound: epoxy resin = 100: 1 to 100: 400 is preferable, and 100: 1 to 100 : 100 is better.

<<< Photopolymerization initiator> The composition of this invention can contain a photopolymerization initiator. In particular, when the composition of the present invention contains a radical polymerizable compound, it is preferable to include a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a compound having sensitivity to light from the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton and compounds having an oxadiazole skeleton), fluorenyl phosphine compounds such as fluorenylphosphine oxide, hexaarylbiimidazole, and oxime Derivatives such as oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include Wulin, et al., Compounds described in Bull.Chem.Soc.Japan (Japanese Chemical Society), 42, 2924 (1969), and British Patent No. 1384492. Compounds described, compounds described in Japanese Patent Application Laid-Open No. 53-133428, compounds described in German Patent No. 3370024, J. Org. Chem. (Journal of Organic Chemistry) based on FC Schaefer, etc .; 29, 1527 (1964), the compound described in Japanese Patent Application Laid-Open No. 62-58241, the compound described in Japanese Patent Application Laid-Open No. 5-281728, and the compound described in Japanese Patent Application Laid-Open No. 5-34920 Compounds, compounds described in US Pat. No. 4,212,976 and the like.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyltriazine compounds, benzophenone dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and fluorenyl groups. Phosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron Compounds, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-amino ketone compound, and a fluorenylphosphine compound can also be preferably used. For example, an α-amino ketone compound described in Japanese Patent Application Laid-Open No. 10-291969 and a phosphonium phosphine compound described in Japanese Patent No. 4225898 can also be used. As the α-hydroxy ketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (the above are manufactured by BASF) can be used. As the α-amino ketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (the above are manufactured by BASF) can be used. As the α-amino ketone compound, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 can be used. As the fluorenylphosphine compound, IRGACURE-819 or DAROCUR-TPO (above manufactured by BASF) can be used as a commercially available product.

The photopolymerization initiator is preferably an oxime compound. Specific examples of the oxime compound include a compound described in Japanese Patent Laid-Open No. 2001-233842, a compound described in Japanese Patent Laid-Open No. 2000-80068, and a compound described in Japanese Patent Laid-Open No. 2006-342166. Compounds described in Japanese Patent Application Laid-Open No. 2016-21012. Examples of the oxime compound that can be preferably used in the present invention include 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, and 3 -Propanyloxyiminobutane-2-one, 2-Ethyloxyiminopentane-3-one, 2-Ethyloxyimino-1-phenylpropane-1-one , 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Imino-1-phenylpropane-1-one and the like. In addition, JCSPerkin II (Journal of the British Chemical Society, Perkin Journal II) (1979, pages 1653-1660), JCSPerkin II (Journal of the British Chemical Society, Perkin Journal II) (1979) 156-162), Journal of Photopolymer Science and Technology (1995, 202-232), Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Compounds described in Japanese Patent Application Publication No. 2004-534797 and Japanese Patent Application Publication No. 2006-342166. Among commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (the above are manufactured by BASF) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION), ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), ADEKA OPTOME N-1919 (ADEKA) Photopolymerization initiator 2) manufactured by CORPORATION and described in Japanese Patent Application Publication No. 2012-14052.

In addition, as the oxime compound other than the above, the compound described in Japanese Patent Publication No. 2009-519904 in which the oxime is linked to the N position of the carbazole ring, and the United States with a heterosubstituent introduced into a benzophenone site can be used. The compound described in Patent No. 7626957, the compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into a pigment part, and International Publication No. WO2009 / 131189 The ketoxime compound described in the above, the compound described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule, Japanese Patent Laid-Open No. 2009 has the maximum absorption at 405 nm and good sensitivity to a g-ray light source Compounds described in Japanese Patent No. -221114.

As the oxime compound, a compound represented by the following formula (OX-1) can be preferably used. Among the oxime compounds, the N-O bond of the oxime may be the oxime compound of the (E) form, and the N-O bond of the oxime may be the oxime compound of the (Z) form or a mixture of the (E) form and the (Z) form.

[Chemical Formula 33]

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. For details of the formula (OX-1), reference can be made to the description in paragraphs 0276 to 0304 of Japanese Patent Application Laid-Open No. 2013-029760, and the contents are incorporated into this specification.

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this manual.

In the present invention, as the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds described in Japanese Patent Application No. 2014-500852, and Japanese Patent Laid-Open No. 2013 Compound (C-3) and the like described in JP-164471. This content is incorporated into this manual.

In the present invention, as the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferred that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Laid-Open No. 2013-114249, paragraphs 0008 to 0012, 0070-0079 of Japanese Patent Laid-Open No. 2014-137466, The compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

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

[Chemical Formula 34] [Chemical Formula 35]

The oxime compound is preferably a compound having a maximum absorption in a wavelength region of 350 nm to 500 nm, and more preferably a compound having a maximum absorption in a wavelength region of 360 nm to 480 nm. The oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of a compound can be measured using a well-known method. For example, a UV-visible spectrophotometer (Cary-5 spectrophotometer (manufactured by Varian) is used) and an ethyl acetate solvent is used to measure at a concentration of 0.01 g / L.

It is also preferable that the photopolymerization initiator contains an oxime compound and an α-amino ketone compound. By using both, the developability is improved, and a pattern with excellent rectangularity is easily formed. When the oxime compound and the α-amino ketone compound are used together, the α-amino ketone compound is preferably 50 to 600 parts by mass, and more preferably 150 to 400 parts by mass, relative to 100 parts by mass of the oxime compound.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass relative to the total solid content of the composition, more preferably 0.5 to 30% by mass, and even more preferably 1 to 20% by mass. As long as the content of the photopolymerization initiator is within the above range, more favorable sensitivity and pattern formation properties can be obtained. The composition of the present invention may contain one kind of photopolymerization initiator, or may contain two or more kinds. When two or more photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

<<< Compound which has alkoxysilyl group> It is also preferable that the composition of this invention contains the compound which has an alkoxysilyl group. The carbon number of the alkoxy group in the alkoxysilyl group is preferably from 1 to 5, more preferably from 1 to 3, and particularly preferably from 1 or 2. As for the alkoxysilyl group, it is more preferable to have two or more in one molecule, and it is more preferable to have two to three. Specific examples of the compound having an alkoxysilyl group include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and dimethyl Diethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxy Silane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, ethylene Triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methylpropene Methoxypropylmethyldimethoxysilane, 3-methacrylic acid methoxypropyltrimethoxysilane, 3-methacrylic acid methoxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silyl, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (ethylene Benzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tri- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltriyl Ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltrisiloxane Ethoxysilane and so on. In addition to the above, an alkoxy oligomer can be used. The following compounds can also be used. [Chemical Formula 36]

Commercially available products include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM manufactured by Shin-Etsu Silicone Co., Ltd. -3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303 , KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM -903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X -41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR -500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X -40-2308, X-40-9238, etc.

When the composition of the present invention contains a compound having an alkoxysilyl group, the content of the compound having an alkoxysilyl group is preferably 0.1 to 40% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, and more preferably 20% by mass or less. The compound having an alkoxysilyl group may be used singly or in combination of two or more kinds. When two or more compounds having an alkoxysilyl group are used simultaneously, it is preferable that the total amount falls within the above range.

<<< catalyst> The composition of this invention can also contain a catalyst. In particular, when a compound having an alkoxysilyl group is contained, a sol-gel reaction is promoted by containing a catalyst, and a strong cured film can be obtained. Examples of the catalyst include an acid catalyst and an alkali catalyst. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, formic acid, or acetic acid, and the like. R is a substituted carboxylic acid, sulfonic acid such as benzenesulfonic acid, or phosphoric acid. Further, Lewis acids such as aluminum chloride, aluminum acetoacetone, zinc chloride, tin chloride, boron trifluoride diethyl ether complex, and trimethyliodosilane can be used. Examples of the alkali catalyst include ammonia base compounds such as aqueous ammonia, and organic amines such as ethylamine and aniline. As the catalyst, the catalyst described in paragraphs 0070 to 0076 of Japanese Patent Application Laid-Open No. 2013-201007 can be used. The content of the catalyst is preferably 0.1 to 100 parts by mass relative to 100 parts by mass of the compound having an alkoxysilyl group, more preferably 0.1 to 50 parts by mass, and still more preferably 0.1 to 20 parts by mass. The composition of the present invention may contain only one type of catalyst, or may contain two or more types. When two or more catalysts are included, the total amount thereof is preferably in the above range.

<< Solvent> The composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the composition, and is preferably selected in consideration of the coatability and safety of the composition.

Examples of the organic solvent include the following organic solvents. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate , Butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate) Esters, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g. 3-alkoxy Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, etc.)), alkyl 2-alkoxypropionate (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, 2-alkoxypropionate Propyl ester, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy-2-methylpropionic acid Ethyl esters (eg methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate , Ethyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl ether. Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters, propylene glycol monopropyl ether acetate, and the like. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylene. However, the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the solvent may be preferably reduced for environmental reasons (for example, it may be 50 ppm by mass relative to the total amount of the organic solvent). (Parts per million) or less, can be set to 10 mass ppm or less, and can be set to 1 mass ppm or less).

The organic solvents may be used singly or in combination of two or more. When two or more organic solvents are used in combination, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and A mixed solution of two or more of propylene glycol methyl ether acetate is preferred.

In the present invention, it is preferable to use a solvent with a small metal content, and the metal content of the solvent is, for example, 10 mass ppb (parts per billion) or less. A solvent of mass ppt (parts per trillion) grade may be used as required, and such a high-purity solvent is provided by, for example, Toyo Gosei Co., Ltd (Chemical Industry Daily, November 13, 2015).

Examples of a method for removing impurities such as metals from a solvent include distillation (molecular distillation, thin film distillation, and the like) or filtration using a filter. As the pore size of the filter used for filtration, 10 nm or less is preferable, 5 nm or less is more preferable, and 3 nm or less is more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). The isomers may include only one kind or plural kinds.

In the present invention, it is preferable that the peroxide content of the organic solvent is 0.8 mmol / L or less, and it is more preferable that the peroxide is not substantially contained.

The content of the solvent with respect to the total amount of the composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass.

<<< Polymerization Inhibitor> The composition of the present invention may contain a polymerization inhibitor in order to suppress unnecessary thermal polymerization of the polymerizable compound during production or storage of the composition. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4 '-Thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), N-nitrosobenzene Hydroxyamine (ammonium salt, cerium salt, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the composition.

<<< Surfactant >> From the viewpoint of further improving the coating property, the composition of the present invention may contain various surfactants. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

The composition of the present invention contains a fluorine-based surfactant, thereby improving the liquid characteristics (especially, the fluidity) when the coating liquid is prepared, and can further improve the uniformity of the coating thickness or the liquid saving property. When a coating liquid using a composition containing a fluorine-based surfactant is used for film formation, the interfacial tension between the coated surface and the coating liquid is reduced, the wettability of the coated surface is improved, and the coated surface is improved. The coatability of the coated surface is improved. Therefore, it is possible to more preferably form a uniform thickness film having a small thickness unevenness.

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

Specific examples of the fluorine-based surfactant include those described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No. 2014-41318 (paragraphs 0060 to 0064 of International Publication No. 2014/17669) and the like. And the surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 2011-132503, and these contents are incorporated into this specification. Examples of commercially available fluorine-based surfactants include MAGAFAC F171, MAGAFAC F172, MAGAFAC F173, MAGAFAC F176, MAGAFAC F177, MAGAFAC F141, MAGAFAC F142, MAGAFAC F143, MAGAFAC F144, MAGAFAC R30, MAGAFAC F437, MAGAFAC F475, MAGAFAC F479, MAGAFAC F482, MAGAFAC F554, MAGAFAC F780 (above manufactured by DIC CORPORATION), FLUORAD FC430, FLUORAD FC431, FLUORAD FC171 (above manufactured by Sumitomo 3M Limited), SURFLON S-382, SURFLON SC-101, SURFLON SC-103 , SURFLON SC-104, SURFLON SC-105, SURFLON SC-1068, SURFLON SC-381, SURFLON SC-383, SURFLON S-393, SURFLON KH-40 (the above are manufactured by ASAHI GLASS CO., LTD.), POLYFOX PF636 , PF656, PF6320, PF6520, PF7002 (the above are made by OMNOVA SOLUTIONS INC.) And so on.

Further, as the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and a part of the functional group containing a fluorine atom being cut off when the fluorine atom is volatilized can be preferably used. Examples of such fluorine-based surfactants include MAGAFAC DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Industry News, February 23, 2016), such as MAGAFAC DS-21, And be able to use those.

As the fluorine-based surfactant, a block polymer can be used. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2011-89090. As the fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which contains a repeating unit derived from a (meth) acrylate compound having a fluorine atom and is derived from having 2 or more (preferably 5 or more) Repeating units of (meth) acrylate compounds of alkoxy (preferably ethoxy and propoxy). The following compounds are exemplified as the fluorine-based surfactant used in the present invention. [Chemical Formula 37] The weight average molecular weight of the compound is preferably 3,000 to 50,000, and is, for example, 14,000. In the above-mentioned compound, the percentage representing the proportion of the repeating unit is mass%.

Moreover, a fluorosurfactant can also be used for the fluoropolymer which has an ethylenically unsaturated group in a side chain. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, for example, MAGAFAC RS-101, RS-102, RS-718K, and RS-72 manufactured by DIC Corporation. -K and so on. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327 can also be used.

As nonionic surfactants, glycerol, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, propoxylated glycerol, ethoxylated glycerol, etc.) , Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, Polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (made by BASF), TETRONIC304, 701, 704, 901, 904, 150R1 (BASF Company), SOLSPERSE20000 (manufactured by Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd), PIONIN D-6112, D-6112-W, D-6315 (Takemoto Oil & (Made by Fat Co., Ltd.), ALFINE E1010, SURFYNOL 104, 400, 440 (made by Nissin Chemical Co., Ltd.) and the like.

Examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth) acrylic (co) polymer POLYFLOW No. 75, No. 90, and No. .95 (manufactured by Kyoeisha chemical Co., Ltd.), W001 (Yusho Co., Ltd.), etc.

Examples of the anionic surfactant include W004, W005, W017 (Yusho Co., Ltd.), SANDET BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

Examples of the silicone-based surfactants include TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (the above is Dow Corning Toray Co. , Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (the above are Shin-Etsu Silicone Co. , Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Co, .LTD), etc.

The surfactant may be used singly or in combination of two or more kinds. The content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the composition, and more preferably 0.005 to 1.0% by mass.

<<< ultraviolet absorber> The composition of this invention may contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an amino diene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, or the like can be used. These details can be referred to the descriptions in paragraphs 0052 to 0072 of Japanese Patent Application Laid-Open No. 2012-208374 and the paragraphs 0317 to 0334 of Japanese Patent Laid-Open No. 2013-68814, and these contents are incorporated into this specification. As a commercial item of a conjugated diene compound, UV-503 (made by DAITO CHEMICAL CO., LTD.) Etc. are mentioned, for example. As the benzotriazole compound, MYUA series manufactured by Miyoshi Oil & Fat Co., Ltd. (Chemical Industry Daily, February 1, 2016) can be used. Content of an ultraviolet absorber is 0.01-10 mass% with respect to the total solid content of the composition of this invention, More preferably, it is 0.01-5 mass%.

<< Other Ingredients >> The composition of the present invention may contain a sensitizer, a hardening accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, and other auxiliary agents (for example, if necessary) , Conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension regulators, chain transfer agents, etc.). These components can be referred to the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of Japanese Patent Application Laid-Open No. 2008-250074, and the contents are incorporated into this specification. Examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. As the antioxidant, a phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a sulfide compound having a molecular weight of 500 or more is more preferable. These can be used in combination of two or more. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. In particular, a compound having a substituent at a position (ortho position) adjacent to the phenolic hydroxyl group is preferable. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred, and methyl, ethyl, propionyl, isopropylfluorenyl, butyl, isobutyl, third butyl, Amyl, isopentyl, tertiary amyl, hexyl, octyl, isooctyl, 2-ethylhexyl are more preferred. It is also preferable that the antioxidant has a phenol group and a phosphite group in the same molecule. As the antioxidant, a phosphorus-based antioxidant can be preferably used. Examples of the phosphorus-based antioxidant include tri [2-[[2,4,8,10-tetra (1,1-dimethylethyl) dibenzo [d, f] [1,3, 2] Dioxocycloheptane-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [ 1,3,2] Dioxocycloheptane-2-yl] oxy] ethyl] amine and phosphite ethylbis (2,4-di-third-butyl-6-methylphenyl) At least one compound in the group. These can be obtained as commercially available products. For example, ADEKASTAB AO-20, ADEKASTAB AO-30, ADEKASTAB AO-40, ADEKASTAB AO-50, ADEKASTAB AO-50F, ADEKASTAB AO- 60. ADEKASTAB AO-60G, ADEKASTAB AO-80, ADEKASTAB AO-330 (ADEKA CORPORATION), etc. The content of antioxidant is preferably 0.01 to 20% by mass relative to the total solid content of the composition, and 0.3 to 15% by mass is More preferably, the antioxidant may be only one kind, or two or more kinds. When it is two or more kinds, the total amount is preferably in the above range.

Regarding the viscosity (23 ° C.) of the composition of the present invention, for example, when a film is formed by coating, it is preferably in a range of 1 to 3000 mPa ･ s. The lower limit is preferably 3 mPa ･ s or more, and more preferably 5 mPa ･ s or more. The upper limit is preferably 2000 mPa ･ s or less, and more preferably 1000 mPa ･ s or less.

The composition of the present invention can be preferably used for forming a near-infrared cut filter or an infrared transmission filter.

<Method for preparing composition> The composition of the present invention can be prepared by mixing the aforementioned components. When preparing a composition, you may mix | blend each component together, or you may mix | blend each component after dissolving or dispersing in a solvent. In addition, the order of placing or operating conditions during deployment are not particularly limited. For example, all components can be dissolved or dispersed in a solvent at the same time to prepare a composition. If necessary, two or more solutions or dispersions of each component can be prepared in advance, and these components can be mixed during use (during coating). It is prepared as a composition.

When the composition of the present invention contains particles such as pigments, it is preferable to include a process for dispersing the particles. In the process of dispersing particles, examples of the mechanical force used for dispersing the particles include compression, extrusion, impact, shearing, and pitting. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microjet homogenizers, high-speed impellers, sand mills, jet mixers, high-pressure wet-type micronization, Ultrasonic dispersion, etc. In addition, in the pulverization of particles in a sand mill (bead mill), it is preferable to perform the treatment under the condition that the pulverization efficiency is increased by using microbeads having a smaller diameter and increasing the bead filling rate. In addition, after the pulverization treatment, it is preferable to remove coarse particles by filtration, centrifugation, or the like. In addition, the process for dispersing particles and the dispersing machine can better use "Encyclopedia of Dispersion Technology, issued by JOHOKIKO Co., Ltd., July 15, 2005" and "suspension (solid / liquid dispersion system) as The central comprehensive collection of decentralized technologies and industrial applications, issued by the Management Development Center Publishing Department, October 10, 1978 ", the process and disperser described in paragraph 0022 of Japanese Patent Application Laid-Open No. 2015-157893. In the process of dispersing the particles, the particles can be refined by a salt milling process. The materials, equipment, and processing conditions used in the salt milling process can be found in, for example, Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Laid-Open No. 2012-046629.

When preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing impurities or reducing defects. The filter is not particularly limited and can be used as long as it is a filter conventionally used for filtering applications and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) can be used. Filters containing materials such as high density, ultra high molecular weight polyolefin resins). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. As long as the pore diameter of the filter is within the above range, fine impurities can be reliably removed. It is also preferable to use a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fibers, nylon fibers, and glass fibers. Specifically, filter elements of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by ROKI GROUP CO., LTD.

When using filters, you can combine different filters (for example, the first filter and the second filter, etc.). At this time, filtration by each filter may be performed only once, or may be performed twice or more. Filters with different pore diameters within the above range can be combined. Here, the pore size can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, various filters provided by Pall Corporation (DFA4201NXEY, etc.), ADVANTEC TOYO KAISHA, LTD., Nihon Entegris KK, Nihon Entegris KK (formerly Nippon Mykrolis Corporation), or KITZ MICRO FILTER CORPORATION can be selected. . The second filter can be formed using the same material as the first filter. In addition, the filtration by the first filter can be performed only on the dispersion, and after mixing the other components, the filtration can be performed by the second filter.

<Film> Next, the film of this invention is demonstrated. The film of the present invention includes the composition of the present invention described above. The film of the present invention is excellent in infrared shielding properties and visible transparency, and can therefore be suitably used as a near-infrared cut filter and an infrared transmission filter. It can also be used as a heat ray shielding filter. The film of the present invention may have a pattern or a film (flat film) without a pattern. The film of the present invention can be used by being laminated on a support, and the film of the present invention can also be used after being peeled from the support. In addition, when the film of the present invention is used as an infrared transmission filter, for example, the infrared transmission filter includes a filter that blocks visible light and transmits light having a wavelength of 900 nm or more. In addition, when the film of the present invention is used as an infrared transmission filter, the filter uses a color material containing the above-mentioned compound (1) and shielding visible light (preferably a color material containing two or more color colorants or A filter containing a composition containing at least an organic black colorant), or a filter having a layer that blocks visible light alone in addition to the layer containing the compound (1) is preferred. When the film of the present invention is used as an infrared transmission filter, the compound (1) has a function of limiting the transmitted light (near infrared) to a longer long wavelength side.

The film thickness of the film of this invention can be adjusted suitably as needed. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.3 μm or more.

The film of the present invention can be used in combination with a color filter containing a colorant. A color filter can be manufactured using the coloring composition containing a coloring agent. As a coloring agent, the coloring agent demonstrated with the composition of this invention is mentioned. The coloring composition can further contain a resin, a radical polymerizable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. As for these details, the materials demonstrated by the composition of this invention are mentioned, and these can be used. The film of the present invention may be a filter having a function of a near-infrared cut-off filter and a color filter by containing a coloring agent.

In the present invention, the near-infrared cut filter refers to a filter that transmits light (visible light) with a wavelength in the visible region and shields at least a part of light (near infrared) with a wavelength in the near-infrared region. The near-infrared cut-off filter may be one that transmits light of all wavelengths in the visible region, or may transmit light of a specific wavelength region of light of wavelengths in the visible region and block light of a specific wavelength region. In addition, in the present invention, the color filter refers to a filter that transmits light in a specific wavelength region out of light in a visible region and blocks light in a specific wavelength region. The infrared transmission filter refers to a filter that shields light with a wavelength in the visible region and transmits at least a part of light with a wavelength in the near-infrared region (near infrared).

When the film of the present invention is used as a near-infrared cut filter, it is preferable that the film of the present invention has a maximum absorption wavelength in a range of 650 to 1000 nm. The average transmittance at a wavelength of 400 to 550 nm is preferably 70% or more, more preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. In addition, the transmittance in the entire range of the wavelength from 400 to 550 nm is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. In addition, the preferable range of the infrared shielding property of the near-infrared cut-off filter varies depending on the application. The transmittance in at least one point of the wavelength range of 700 to 1000 nm is preferably 20% or less, and more preferably 15% or less. Below 10% is more preferred.

When the film of the present invention is used as an infrared transmission filter, it is preferable to have the following spectral characteristics (1). According to this aspect, it can be set as a film which can transmit infrared rays in a state where there is less noise from visible light.

(1) The maximum value of the light transmittance in the thickness direction of the film in the range of 400 to 830 nm is 20% or less, and the minimum value of the light transmittance in the thickness direction of the film is in the range of 1000 to 1300 nm It's over 80%. The film having such a spectroscopic characteristic can be suitably used as an infrared transmission filter that shields light in a wavelength range of 400 to 750 nm and transmits light having a wavelength of 900 nm or more.

The spectroscopic characteristics of the film are values obtained by measuring transmittance in a wavelength range of 300 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

When the film of the present invention is used as a near-infrared cut filter, in addition to the film of the present invention, it may have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, and the like. The near-infrared cut-off filter also has a layer containing copper and / or a dielectric multilayer film, so that a near-infrared cut-off filter with a wide viewing angle and excellent infrared shielding properties can be easily obtained. In addition, the near-infrared cut-off filter further includes an ultraviolet absorbing layer, so that it can be a near-infrared cut-off filter having excellent ultraviolet shielding properties. As the ultraviolet absorbing layer, for example, the absorption layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. WO2015 / 099060 can be referred to, and the contents are incorporated into this specification. As the dielectric multilayer film, the descriptions in paragraphs 0255 to 0259 of Japanese Patent Application Laid-Open No. 2014-41318 can be referred to, and the contents are incorporated into this specification. As the copper-containing layer, a glass substrate (copper-containing glass substrate) composed of a copper-containing glass, and a copper complex-containing layer (copper complex-containing layer) can also be used. Examples of the copper-containing glass substrate include copper-containing phosphate glass and copper-containing fluorophosphate glass. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC TECHNO GLASS CO., LTD.), BG-60, BG-61 (the above are manufactured by SCHOTT AG), and CD5000 (manufactured by HOYA GROUP). Examples of the copper complex-containing layer include layers formed using a composition containing a copper complex. The copper complex is preferably a compound having a maximum absorption wavelength in a wavelength region of 700 to 1200 nm. The maximum absorption wavelength of the copper complex is more preferably in a wavelength region of 720 to 1200 nm, and more preferably in a wavelength region of 800 to 1100 nm.

When the film of the present invention is used as a near-infrared cut filter or an infrared transmission filter, a near-infrared cut filter and an infrared transmission filter can be used in combination. By using a near-infrared cut-off filter and an infrared transmission filter in combination, it can be preferably used for an infrared sensor that detects infrared light of a specific wavelength. When two types of filters are used in combination, both the near-infrared cut filter and the infrared transmission filter can be formed using the composition of the present invention, and only one of them can be formed using the composition of the present invention.

The film of the present invention can be used in various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Film Semiconductor), an infrared sensor, and an image display device.

<Optical filter> Next, the optical filter of this invention is demonstrated. The optical filter of the present invention includes the film of the present invention described above. The optical filter of the present invention can be preferably used as at least one selected from a near-infrared cut filter and an infrared transmission filter. In addition, a state in which a pixel using the film of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless are used is also a preferred state of the optical filter of the present invention.

<Laminate> The laminated body of the present invention includes the film of the present invention and a color filter containing a colorant. In the laminated body of the present invention, the film of the present invention and the color filter may be adjacent to each other in the thickness direction, or may not be adjacent to each other. When the film of the present invention and the color filter are not adjacent in the thickness direction, the film of the present invention may be formed on a substrate other than the substrate on which the color filter is formed, or the film of the present invention and the Between the color filters, other components (for example, microlenses, flattening layers, etc.) constituting the solid-state imaging element are sandwiched.

<Pattern formation method> Next, the pattern formation method using the composition of this invention is demonstrated. The pattern forming method includes a process of forming a composition layer on a support using the composition of the present invention and a process of forming a pattern on the composition layer by a photolithography method or a dry etching method.

When manufacturing a laminated body in which the film of the present invention and the color filter are laminated, the pattern formation of the film of the present invention and the pattern formation of the color filter can be performed separately. Moreover, the laminated body of the film and color filter of this invention can also be pattern-formed (namely, patterning of the film of this invention, and a color filter can be performed simultaneously).

The case where the pattern formation of the film and the color filter of the present invention is performed separately is as follows. Either the film or the color filter of the present invention is patterned. Then, another filter layer is formed on the patterned filter layer. Next, the filter layer not patterned is patterned.

The pattern formation method may be a pattern formation method by a photolithography method, or a pattern formation method by a dry etching method. In the case of a pattern formation method by a photolithography method, a dry etching process is not required, and therefore, the effect of reducing the number of processes can be obtained. In the case of a pattern forming method by a dry etching method, since the photolithography function is not required, the concentration of the compound (1) and the like can be increased.

When the pattern formation of the film of the present invention and the pattern formation of the color filter are performed separately, the pattern formation method of each filter layer can be performed only by a photolithography method or only by a dry etching method. In addition, one filter layer may be patterned by a photolithography method, and the other filter layer may be patterned by a dry etching method. When patterning is performed by both the dry etching method and the photolithography method, it is preferable that the first layer is patterned by the dry etching method, and the second layer is patterned by the photolithography method later.

The pattern forming method by the photolithography method includes a process of forming a composition layer on a support by using each composition, a process of exposing the composition layer into a pattern, and a process of forming a pattern by removing unexposed parts by development. . According to requirements, a process for baking the composition layer (pre-baking process) and a process for baking the developed pattern (post-baking) can be set. In addition, the pattern forming method by the dry etching method includes a process of forming a composition layer on a support by using each composition and hardening to form a hardened layer, a process of forming a photoresist layer on the hardened layer, and exposing The process of developing and patterning the photoresist layer to obtain the photoresist pattern and the process of forming the pattern by dry etching the hardened layer with the photoresist pattern as an etching mask are preferred. Hereinafter, each process will be described.

<<< Process of Forming a Composition Layer >> In the process of forming a composition layer, each composition is used to form a composition layer on a support.

As the support, for example, a substrate for a solid-state imaging element in which a solid-state imaging element (light-receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicone substrate) can be used. The pattern may be formed on the solid-state imaging element formation surface side (front surface) of the solid-state imaging element substrate, or may be formed on the solid-state imaging element non-formation surface side (back surface). An undercoat layer may be provided on the support as needed to improve adhesion to the upper layer, prevent substance diffusion, or planarize the surface of the substrate.

As a method of applying the composition to the support, a known method can be used. For example, a drip method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method; a cast coating method; a slit and rotation method; For example, the method described in Japanese Patent Application Laid-Open No. 2009-145395); inkjet method (for example, on-demand method, piezoelectric method, thermal method), nozzle ejection, and other discharge systems such as flexographic printing, screen printing, gravure printing, Various printing methods, such as reverse printing, metal mask printing, transfer methods using molds, etc., nanoimprinting, etc. The application method by inkjet is not particularly limited. For example, it can be shown in "Expanding and Using Inkjet-Unlimited Possibilities Appeared in Patent-Issued in February 2005, Sumitbe Techon Research Co., Ltd." The method described in the published patent publication (especially pages 115 to 133), in Japanese Patent Application Laid-Open No. 2003-262716, Japanese Patent Application No. 2003-185831, Japanese Patent Application No. 2003-261827, and Japanese Patent Application No. 2012 -126830, Japanese Patent Application Laid-Open No. 2006-169325, and the like.

The composition layer formed on the support can be dried (pre-baked). When a pattern is formed by a low temperature process, pre-baking may not be performed. When pre-baking, the pre-baking temperature is preferably below 150 ° C, more preferably below 120 ° C, and even more preferably below 110 ° C. The lower limit can be set to, for example, 50 ° C or higher, and can also be set to 80 ° C or higher. By performing pre-baking at a pre-baking temperature of 150 ° C. or lower, for example, when a photoelectric conversion film of an image sensor is formed of an organic material, these characteristics can be more effectively maintained. The pre-baking time is preferably from 10 seconds to 300 seconds, more preferably from 40 to 250 seconds, and even more preferably from 80 to 220 seconds. Drying can be performed by a hot plate, an oven, or the like.

(When pattern formation is performed by photolithography) << Exposure Process >> Next, the composition layer is exposed to a pattern (exposure process). For example, pattern exposure can be performed by exposing the composition layer with a mask having a predetermined mask pattern using an exposure device such as a stepper. This makes it possible to harden the exposed portion. As the radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferred, and i-rays are more preferred. Irradiation amount (exposure amount) is, for example 0.03 ~ 2.5J / cm ² is preferred, 0.05 ~ 1.0J / cm ² is more preferably, 0.08 ~ 0.5J / cm ² is optimal. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed in the atmosphere, it can be performed in a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, and substantially free of oxygen). The exposure can also be performed under a high-oxygen environment (for example, 22% by volume, 30% by volume, and 50% by volume) in an oxygen concentration greater than 21% by volume. In addition, the exposure illuminance can be appropriately set, and can usually be selected from a range of 1000 W / m ² to 100,000 W / m ² (for example, 5000 W / m ² , 15000 W / m ² , and 35000 W / m ² ). Oxygen concentration may be appropriately combined exposure illuminance condition, for example, can be set as follows, i.e. an oxygen concentration of 10 vol% when the illuminance is 10000W / m ^2, an oxygen concentration of 35% by volume when the illuminance is 20000W / m ² and the like.

<< Developing Process >> Next, the unexposed portions are removed by development to form a pattern. The development and removal of the unexposed portion can be performed using a developing solution. Thereby, the composition layer of the unexposed part in an exposure process is melt | dissolved by a developing solution, and only a photohardened part remains on a support body. As the developing solution, an alkali developing solution that does not cause damage to the solid-state imaging element or circuit of the substrate is preferred. The temperature of the developing solution is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of the residue, the following process can be repeatedly performed, that is, the developing solution is thrown off every 60 seconds, and then a new developing solution is supplied.

Examples of the alkaline agent used in the developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, diethyleneglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, and hydrogen. Tetraethylammonium oxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperazine Organic compounds such as pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, metasilicic acid Inorganic basic compounds such as sodium. The developing solution is preferably an alkaline aqueous solution in which these alkaline agents are diluted with pure water. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. A surfactant may be used in the developing solution. Examples of the surfactant include the surfactants described with the composition described above, and nonionic surfactants are preferred. In addition, when a developing solution including such an alkaline aqueous solution is used, it is preferable to wash (rinse) with pure water after development.

After development and after drying, heat treatment (post-baking) can be performed. Post-baking is a heat treatment after development for completely curing the film. When performing the post-baking, the post-baking temperature is preferably, for example, 100 to 240 ° C. From the viewpoint of film hardening, 200 to 230 ° C is more preferable. In addition, when an organic electroluminescence (organic EL) element is used as a light source, or when a photoelectric conversion film of an image sensor is constituted by an organic material, the post-baking temperature is preferably 150 ° C or lower, 120 ° C. Below is more preferred, below 100 ° C is even more preferred, and below 90 ° C is particularly preferred. The lower limit can be set to, for example, 50 ° C or higher. As for the post-baking, the developed film can be performed continuously or intermittently using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater so that the conditions described above can be achieved. When a pattern is formed by a low-temperature process, post-baking may not be performed.

(When patterning is performed by a dry etching method) Patterning by a dry etching method can be performed by hardening a composition layer formed on a support to form a hardened layer, and then patterning the photoresist The layer was used as a mask to pattern the obtained cured layer using an etching gas. In the formation of the photoresist layer, a pre-baking treatment is preferably performed. In particular, as a process for forming the photoresist layer, it is preferable to perform a heat treatment after exposure and a heat treatment (post-baking treatment) after development. Regarding pattern formation by the dry etching method, the descriptions in paragraphs 0010 to 0067 of Japanese Patent Application Laid-Open No. 2013-064993 can be referred to, and the contents are incorporated into this specification.

<Solid-state imaging element> The solid-state imaging element of the present invention includes the film of the present invention described above. The structure of the solid-state imaging element of the present invention is not particularly limited as long as it has a structure of the film of the present invention and functions as a solid-state imaging element. For example, the following structures are listed.

It has a structure in which a plurality of photodiodes, polycrystalline silicon, and the like are provided on a support, and the light-receiving portion openings of only the photodiode are provided on the photodiode and the transfer electrode. A light-shielding film including tungsten is provided on the light-shielding film with a device protection film including silicon nitride and the like formed so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion, and the device protection film has the film of the present invention. . Furthermore, it is possible to have a structure that has a light condensing mechanism (for example, a micro lens, etc. below) on the device protective film and on the underside (close to the support side) of the film of the present invention, and that has light condensing on the film of the present invention. Organizational structure. In addition, the color filter may have a structure in which a hardened film forming each color pixel is embedded by partitioning a space partitioned into a grid shape, for example. In this case, it is preferable that the partition has a low refractive index for each color pixel. Examples of the imaging device having such a structure include the devices described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577.

<Image display device> The film of the present invention can also be used in an image display device such as a liquid crystal display device or an organic electroluminescence element (organic EL) display device. For example, it can be used for the purpose of shielding infrared light included in a backlight of an image display device (for example, a white light emitting diode (white LED)), the purpose of preventing malfunction of peripheral devices, and the like in addition to each colored pixel. The purpose of infrared pixels is to use the film of the present invention.

The definition or details of the image display device are described in, for example, "electronic display device (by Sasaki Akio, Kogyo Chosakai Publishing Co., Ltd., 1990)", "display device (by Ibuki Sosun, Sangyo Tosho Publishing Co. ., Ltd. issued in the 1st year of Heisei) ". The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Compiled by Ryuu Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the liquid crystal display device can be applied to various types of liquid crystal display devices described in the "next-generation liquid crystal display technology" described above.

The image display device may include a white organic EL element. As the white organic EL element, a tandem structure is preferable. Regarding the tandem structure of organic EL devices, it is described in Japanese Patent Application Laid-Open No. 2003-45676, Mikami nominal supervision, "Front line of organic EL technology development-high brightness / high precision / long life / technology set-", technical information Association, pages 326-328, 2008, etc. The spectrum of the white light emitted by the organic EL element has the maximum emission peak in the blue region (430nm-485nm), the green region (530nm-580nm), and the yellow region (580nm-620nm). In addition to these emission peaks, those with the maximum emission peak in the red region (650nm-700nm) are more preferred.

<Infrared sensor> The infrared sensor of the present invention includes the film of the present invention described above. The structure of the infrared sensor of the present invention is not particularly limited as long as it has a structure of the film of the present invention and a structure that functions as an infrared sensor.

Hereinafter, an embodiment of the infrared sensor of the present invention will be described using drawings. In FIG. 1, the infrared sensor has an imaging area including a near-infrared cut-off filter 111 and an infrared transmission filter 114 on the solid-state imaging device 110. A color filter 112 is laminated on the near-infrared cut-off filter 111. Microlenses 115 are arranged on the color light filter 112 and the incident light hν side of the infrared transmission filter 114. A planarization layer 116 is formed so as to cover the microlenses 115.

The near-infrared cut-off filter 111 transmits light in the visible region (for example, light with a wavelength of 400 to 650 nm) and shields light in the near-infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm, and more It is preferably a filter with a wavelength of 900 to 1000 nm. The spectral characteristics of the near-infrared cut-off filter 111 can be selected according to the emission wavelength of the infrared light emitting diode (infrared LED) used.

The color filter 112 is a color filter in which a pixel that transmits and absorbs light of a specific wavelength in a visible light region is formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which pixels of red (R), green (G), and blue (B) are formed can be used. For example, it is possible to refer to the descriptions in paragraphs 0214 to 0263 of Japanese Patent Application Laid-Open No. 2014-043556 and incorporate the contents into this specification.

The infrared transmission filter 114 can select its characteristics according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, the maximum value of the light transmittance of the infrared transmission filter 114 in the thickness direction of the film in the range of 400 to 650 nm is preferably 30% or less, and 20% or less More preferably, 10% or less is further preferable, and 0.1% or less is particularly preferable. It is preferable that the entire area of the transmittance in the range of the wavelength of 400 to 650 nm satisfies the above conditions. The maximum value in the range of 400 to 650 nm is usually 0.1% or more.

The minimum value of the light transmittance of the infrared transmission filter 114 in the thickness direction of the film at a wavelength of 800 nm or more (preferably 800 to 1300 nm) is preferably 70% or more, more preferably 80% or more, and 90% The above is further preferred. It is preferable that a part of the transmittance in a range of a wavelength of 800 nm or more satisfies the above conditions, and it is preferable that the wavelengths corresponding to the emission wavelength of the infrared LED satisfy the above conditions. The minimum value of the light transmittance in the wavelength range of 900 to 1300 nm is usually 99.9% or less.

The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, even more preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit value is preferably 0.1 μm. As long as the film thickness is within the above range, it can be a film that satisfies the above-mentioned spectral characteristics. A method for measuring the spectral characteristics and film thickness of the infrared transmission filter 114 is shown below. About the film thickness, the board | substrate with a film after drying was measured with the stylus-type surface shape measuring device (DEKTAK150 by ULVAC, Inc.). The spectral characteristics of the film were measured by using a UV-Vis near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) in a wavelength range of 300 to 1300 nm.

The infrared transmission filter 114 having the above-mentioned spectral characteristics can use a composition including a color material that blocks visible light. The details of the color material that blocks visible light are the same as those described with the composition of the present invention described above.

For example, when the emission wavelength of the infrared LED is 940 nm, the maximum value of the light transmittance of the infrared transmission filter 114 in the thickness direction of the film is 20% or less in the range of the wavelength of 450 to 650 nm, which is in the thickness direction of the film. The transmittance of light at a wavelength of 835 nm is 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film in a range of wavelengths of 1000 to 1300 nm is preferably 70% or more.

The infrared transmission filter 114 having the above-mentioned spectral characteristics can be manufactured using a composition containing a color material that blocks visible light and a compound having a maximum absorption in a wavelength range of 750 to 950 nm. The details of the color material that blocks visible light are the same as those described with the composition of the present invention described above. Examples of the compound having the maximum absorption in the wavelength range of 750 to 950 nm include the compound (1) and the like described with the composition of the present invention described above. Moreover, it can also be formed using the composition of this invention containing the color material which blocks visible light.

<Compound> Next, the compound of this invention is demonstrated. The compound of the present invention is a compound represented by the formula (1) (compound (1)) described with the composition of the present invention, and the preferred range is also the same as the above range. The compound of the present invention can be preferably used as an infrared absorber. It can also be used as a pigment derivative. The compound of the present invention can be preferably used, for example, in the formation of a near-infrared cut filter that shields light having a wavelength of 700 to 1000 nm. It can also be used as a light-to-heat conversion material in near-infrared cut-off filters such as plasma display panels or solid-state imaging devices, optical filters such as heat-ray shielding films, write-once optical discs (CD-R), and flash-melt fixing materials . It can also be used as information display materials in anti-counterfeit inks and invisible barcode inks. [Example]

The following examples illustrate the invention in further detail. The materials, usage amounts, proportions, processing contents, and processing order shown in the following examples are within a range not departing from the spirit of the present invention, and can be appropriately changed. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards.

<Synthesis example> (Synthesis example of compound D-14) The compound D-14 was synthesized according to the following scheme. Using 4- (1-methylheptyloxy) benzonitrile as a raw material, compound D-14-a was synthesized according to the method described in the specification of US Pat. No. 5,969,154. 50 parts by mass of compound D-14-a and 52.4 parts by mass of 2- (2- (6,7-dichloro-quinoxaline)) acetonitrile were stirred in 1,000 parts by mass of toluene, and then 127 parts by mass was dropped. Phosphorous oxychloride, heated in circulation for 3.5 hours. After the completion of the reaction, the internal temperature was cooled to 25 ° C., and the internal temperature was maintained at 30 ° C. or lower, and 1,000 parts by mass of methanol was dropped over 60 minutes. After the dropping was completed, the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were filtered off and washed with 500 parts by mass of methanol. 500 parts by mass of methanol was added to the obtained crystals, and the mixture was heated in a circulating flow for 30 minutes, cooled to 30 ° C, and the crystals were filtered off. The obtained crystal was air-dried at 40 ° C for 12 hours to obtain 56.6 parts by mass of compound D-14-b. 51 parts by mass of 2-aminoethyl diphenylborate was stirred in 500 parts by mass of 1,2-dichlorobenzene, the set temperature of the reaction apparatus was set to 40 ° C, and it was dropped over 10 minutes. 72.2 parts by mass of titanium tetrachloride was stirred for 30 minutes. Furthermore, 25 parts by mass of compound D-14-b was added thereto, and the set temperature was raised to 130 ° C. to heat-circulate for 90 minutes. After cooling until the internal temperature became 30 ° C., the internal temperature was maintained at 30 ° C. or lower, and 1,000 parts by mass of methanol was dropped on the circulating solution. After stirring for 30 minutes, the crystals were filtered off and washed with 500 parts by mass of methanol. 250 parts by mass of methanol was added to the obtained crystals, and the mixture was heated in a loop for 30 minutes, and cooled to 30 ° C. to remove the crystals by filtration. The obtained crystal was blow-dried at 40 ° C for 12 hours to obtain 25 parts by mass of compound D-14-c. 24 parts by mass of the compound D-14-c was stirred in 700 parts by mass of tetrahydrofuran, and 89.2 parts by mass of triethylamine 89.2 parts by mass and 25.2 parts by mass of benzamidine chloride were dropped in this order. The set temperature of the reaction apparatus was raised to 75 ° C. and heated in a loop for 1 hour. Cooling was performed until the internal temperature became 30 ° C, and 400 parts by mass of methanol was dropped on the solution after maintaining the internal temperature at 30 ° C and circulating. The mixture was stirred for 30 minutes after dropping, and the crystals were filtered off and washed with 500 parts by mass of methanol. 500 parts by mass of methanol was added to the obtained crystals, and the mixture was heated in a loop for 1 hour, and cooled to 30 ° C. to remove the crystals by filtration. The obtained crystal was air-dried at 40 ° C for 12 hours to obtain 20 parts by mass of compound D-14.

Nuclear magnetic resonance analysis ( ¹ H-NMR (CDCl ₃ )) of compound D-14: δ: 9.05 (s, 2H), 8.32 to 8.29 (m, 6H), 7.81 (s, 2H), 7.75 to 7.68 (m, 2H), 7.59 to 7.55 (m, 4H), 7.38 to 7.36 (m, 10H), 7.26 to 7.19 (m, 10H), 6.96 (d, 4H), 6.35 (d, 4H) by MALDI-MS (Matrix Assisted Laser Desorption / Ionization-Mass Spectrometry (Mass Assisted Laser Desorption / Ionization-Mass Spectrometry). The peak of molecular weight 1294.2 was observed to confirm that it was Compound D-14. As a result of measurement with chloroform, the maximum absorption wavelength (λmax) of Compound D-14 was 883 nm. In this synthesis example, the obtained compound D-14 was added with a cleaning process using an adjusted concentration HCl solution, thereby significantly reducing impurities (especially impurity metal ions, metal salts, etc.). [Chemical Formula 38]

(Synthesis Example of Compound D-44) Compound D-44 was synthesized according to the following scheme. 65 parts by mass of trimellitic anhydride was dissolved in 450 parts by mass of DMF (dimethylformamide), and under ice cooling, 70.8 parts by mass of tridecylamine (Tokyo Chemical Industry Co., Ltd.) was dropped until the internal temperature became 30 ° C or lower. , Ltd., branched chain isomer mixture). After the reaction solution was stirred at 20 to 30 ° C. for 20 minutes, the set temperature of the reaction apparatus was raised to 155 ° C. and the heat was circulated for 3 hours. After the reaction solution was cooled to 30 ° C, 300 mL of ethyl acetate was added, and then 300 mL of 1 mol / L hydrochloric acid water under ice-cooling was dropped while maintaining the internal temperature at 30 ° C or lower. After the dripped solution was stirred at 20 to 30 ° C. for 30 minutes, a liquid separation operation was performed to discard the aqueous layer. To the organic layer, 300 mL of 1 mol / L hydrochloric acid water was added and stirred at 20 to 30 ° C. for 30 minutes. A liquid separation operation was performed, and the aqueous layer was discarded. Magnesium sulfate was added to the organic layer and stirred at 20 to 30 ° C for 10 minutes. This organic layer was filtered off, and the filtrate was concentrated under reduced pressure at 60 ° C to obtain 114 parts by mass of compound D-44-E. Nuclear magnetic resonance analysis of compound D-44-E ( ¹ H-NMR (400 MHz, CDCl ₃ )): δ 0.56-1.80 (m, 25H), 3.63-3.80 (m, 2H), 7.89-8.00 (m, 1H) , 8.43-8.51 (m, 1H), 8.54 (s, 1H), 11.7 (br s, 1H)

20 parts by mass of compound D-44-E was dissolved in 80 parts by mass of tetrahydrofuran (THF), and under ice cooling, 10.2 parts by mass of ethylenedichloride and 0.09 parts by mass of DMF were dropped until the internal temperature became 30 ° C. The reaction solution was stirred at 40 ° C for 60 minutes, and then concentrated under reduced pressure at 40 ° C to obtain 21.0 parts by mass of compound D-44-F.

Using compound D-44-G and compound D-44-F, compound D-44 was synthesized in the same manner as in the synthesis of compound D-14. Nuclear magnetic resonance analysis of compound D-44 ( ¹ H-NMR (400 MHz, CDCl ₃ )): δ 0.57-1.89 (m, 50H), 2.07-2.22 (s, 6H), 3.54-3.86 (m, 4H), 6.23 -6.38 (m, 2H), 6.54-6.79 (m, 4H), 6.87-7.41 (m, 28H), 7.93-8.05 (m, 2H), 8.43-8.54 (m, 2H), 8.58 (s, 2H)

[Chemical Formula 39]

(Synthesis examples of compounds D-43, D-45 to D-84) Synthesis was performed in the same manner as in the synthesis examples of compounds D-14 and D-44. In addition, a compound D-63-E used as an intermediate of D-63 and D-64 was synthesized as follows.

(Synthesis of Compound D-63-E) 60 parts by mass of trimellitic anhydride was dissolved in 420 parts by mass of DMF, and 42.7 parts by mass of 3-diethylaminopropylamine was dropped under ice cooling while maintaining the internal temperature at 30 ° C or lower. After the reaction solution was stirred at 20 to 30 ° C. for 20 minutes, the set temperature of the reaction apparatus was raised to 155 ° C. and the heat was circulated for 3 hours. This reaction solution was cooled to 30 ° C, 420 mL of ethyl acetate was added, and the mixture was stirred at 20 to 30 ° C for 20 minutes. This reaction solution was filtered off and spray-washed with 420 mL of ethyl acetate to obtain 90 parts by mass of compound D-44-E. Nuclear magnetic resonance analysis of compound D-63-E ( ¹ H-NMR (400 MHz, CDCl ₃ )): δ 1.22 (t, 6H), 1.98-2.12 (m, 2H), 3.11-3.25 (m, 6H), 3.71 (T, 2H), 7.77-7.82 (m, 1H), 8.10 (s, 1H), 8.13-8.18 (m, 1H) [Chemical Formula 40]

<Test Example 1> The compound shown in the following table was dissolved in a measurement solvent (concentration 2.5 × 10 ^-6 mol / L) described in the following table to measure an absorption spectrum (optical path length 10 mm). The maximum absorption wavelength of each compound, the absorbance A _max of the maximum absorption wavelength, and the absorbance A ₄₅₀ at a wavelength of 450 nm were obtained from the absorption spectrum of each compound. The absorbance ratio (absorbance A ₄₅₀ / absorbance A _max ) which is the value of the maximum absorption wavelength and absorbance A ₄₅₀ of the compound divided by the absorbance A _max is shown in the following table.

[Table 2]

[table 3]

Compounds D-1, D-2, D-3, D-6, D-8, D-9, D-12, D-13, D-14, D-15, D-17, D-19, D -20, D-22, D-23, D-34, D-37, D-40, D-43 to D-84: compounds having the structure shown in the specific examples of the compound (1) described above. Compound E-1: A compound having the following structure. In the structural formula, Ph is phenyl. [Chemical Formula 41]

As shown in the above table, the compounds of the Examples had an absorbance ratio of 0.015 or less and excellent transparency. In contrast, the compound of the comparative example had an absorbance ratio of more than 0.015, and the transparency was inferior to that of the compound of the example.

<Test Example 2> After the components shown in the following table were mixed and stirred at the ratio shown in the following table, the mixture was filtered through a nylon filter (manufactured by NIHON PALL LTD.) Having a pore diameter of 0.45 μm to prepare a composition. Thing.

[Table 4]

[table 5]

In addition, in Examples 2-46 to 2-50, near-infrared absorbing compounds (D-100 to D-104) other than the compound (1) were prepared. Compounds D-34 to D-50, D-52, D-55, D-57 to D-61, D-65 to D-83: Those having the structure shown in the specific examples of the compound (1) described above Compound. Compounds D-100 to D-104: Compounds having the following structures. [Chemical Formula 42] Polymerizable compound: a mixture of the following compounds (a mixture in which the molar ratio of the left compound to the right compound is 7: 3) [Chemical Formula 43] Photopolymerization initiator: IRGACURE-OXE01 (manufactured by BASF) Surfactant: MAGAFAC RS-72-K (manufactured by DIC Corporation, propylene glycol monomethyl ether acetate 30% by mass solution) Polymerization inhibitor: p-hydroxyphenol organic solvent : Cyclohexanone

(Production of film) Each of the obtained compositions was spin-coated on a glass substrate so that the film thickness after film formation became 1.0 μm, and an i-ray step exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) was used at 1000 mJ. / cm ² for full exposure. Next, the glass substrate was heated at 220 ° C. for 5 minutes using a hot plate to produce a film. With respect to the glass substrate used for manufacturing the film, the transmittance was measured in the range of a wavelength of 400 to 1300 nm by using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). These films are excellent in visible transparency and infrared shielding properties.

An infrared transmission filter capable of selectively transmitting a predetermined infrared ray can be manufactured by further preparing a color material that blocks visible light from the above composition.

<Test Example 3> (Preparation of color material solutions 1 to 29) The compound (1) described in the following table, the pigment derivative described in the following table, the resin described in the following table, 150 mass Parts of propylene glycol monomethyl ether acetate (PGMEA) and 230 parts by mass of zirconia beads having a diameter of 0.3 mm were mixed, and a paint shaker was used for 5 hours to disperse the zirconia beads by filtering and The color material solutions 1 to 29 were prepared by separation. The compounding amount of the compound (1), the pigment derivative, and the resin is as described in the table. In the color material solutions 16, 18, and 28, the compound D-63 was used as a pigment derivative. In the color material solutions 19 and 29, the compound D-64 was used as a pigment derivative.

[TABLE 6]

Compounds D-1, D-3, D-8, D-12, D-14, D-15, D-19, D-20, D-30, D-33, D-36, D-39, D -45, D-51, D-53, D-54, D-56, D-62, D-63, D-64, D-80, D-84: Specific examples of the compound (1) described above Compounds of the structure shown in.

Pigment derivative 1: A compound having the following structure. In the structural formula, Ph is phenyl. [Chemical Formula 44]

Resin 1: A resin having the following structure (acid value = 105 mgKOH / g, weight average molecular weight = 8000). The value attached to the main chain represents the mass ratio of the repeating unit, and the value attached to the side chain represents the number of repeating units. [Chemical Formula 45]

Resin 2: A resin having the following structure (acid value = 32.3 mgKOH / g, amine value = 45.0 mgKOH / g, weight average molecular weight = 22900). The value attached to the main chain represents the mass ratio of the repeating unit, and the value attached to the side chain represents the number of repeating units. [Chemical Formula 46]

Resin 3: A resin having the following structure (acid value = 99.1 mgKOH / g, weight average molecular weight = 38000). The value attached to the main chain represents the mass ratio of the repeating unit, and the value attached to the side chain represents the number of repeating units. [Chemical Formula 47]

(Preparation of composition) A composition was prepared by mixing the following components.・ Color material solution obtained in the above: 55 parts by mass ・ Resin (manufactured by ACRYBASE FF-426, NIPPON SHOKUBAI CO., LTD.): 7.0 parts by mass ・ Polymerizable compound (ARONIX M-305, pentaerythritol triacrylate and pentaerythritol) Mixture of four acrylates, containing 55 to 63% by mass of pentaerythritol triacrylate, manufactured by TOAGOSEI CO., LTD .: 4.5 parts by mass · Photopolymerization initiator (IRGACURE-OXE02, manufactured by BASF): 0.8 parts by mass · Polymerization inhibitor (p-hydroxyphenol): 0.001 part by mass · surfactant (the following mixture (Mw = 14000). In the following formula, the percentage representing the proportion of the repeating unit is mass%.): 0.03 part by mass [Chemical Formula 48 ] ・ Ultraviolet absorber (manufactured by UV-503, DAITO CHEMICAL CO., LTD.): 1.3 parts by mass ・ PGMEA: 31 parts by mass

(Manufacturing of film) Each composition was spin-coated on a glass substrate so that the film thickness after film formation became 1.0 μm, and an i-ray step exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) was used at 1000 mJ / cm ^{2 Make} a full exposure. Next, a film was produced by heating at 220 ° C for 5 minutes using a hot plate. With respect to the glass substrate used for manufacturing the film, the transmittance was measured in the range of a wavelength of 400 to 1300 nm by using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). These films are excellent in visible transparency and infrared shielding properties.

An infrared transmission filter capable of selectively transmitting a predetermined infrared ray can be manufactured by further preparing a color material that blocks visible light from the above composition.

110‧‧‧ solid-state imaging element
111‧‧‧Near infrared cut-off filter
112‧‧‧Color Filter
114‧‧‧ infrared transmission filter
115‧‧‧ micro lens
116‧‧‧ flattening layer
hν‧‧‧ incident light

FIG. 1 is a schematic diagram showing an embodiment of an infrared sensor.

110‧‧‧ solid-state imaging element

111‧‧‧Near infrared cut-off filter

112‧‧‧Color Filter

114‧‧‧ infrared transmission filter

115‧‧‧ micro lens

116‧‧‧ flattening layer

hν‧‧‧ incident light

Claims (17)

A composition containing a compound represented by the following formula (1), a resin, and a solvent, In formula (1), R ¹ and R ² each independently represent a halogen atom, a cyano group, a nitro group, a fluoroalkyl group, -OCOR ¹¹ , -SOR ¹² or -SO ₂ R ¹³ , and R ¹¹ to R ¹³ are each independently Ground represents a hydrocarbon group or a heteroaryl group, n represents an integer of 1 to 3, R ³ to R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring, R ⁷ to R ¹⁰ each independently represent a hydrogen atom or a substituent, X ¹ and X ² each independently represent a hydrogen atom or -BR ^21a R ^22a , R ^21a and R ^22a each independently represent a substituent, and R ^21a and R ^22a They may be bonded to each other to form a ring. The composition according to item 1 of the scope of patent application, wherein R ⁷ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group. The composition according to item 1 of the scope of patent application, wherein at least one of R ⁷ to R ¹⁰ represents a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group. The composition according to item 1 of the scope of patent application, wherein R ⁷ and R ⁹ each independently represent a halogen atom, a hydrocarbon group, an alkoxy group, or a cyano group, and R ⁸ and R ^{10 each} represent a hydrogen atom. The composition according to any one of claims 1 to 4, in which the compound represented by the aforementioned formula (1) has a maximum absorption wavelength in a range of 700 to 1000 nm, and is an absorbance A at a wavelength of 450 nm. The value A ₄₅₀ / A _max of ₄₅₀ divided by the absorbance A _max of the aforementioned maximum absorption wavelength is 0.015 or less. The composition according to any one of claims 1 to 4 of the scope of patent application, further comprising a colorant. The composition according to any one of claims 1 to 4 of the scope of patent application, further comprising a color material that transmits infrared rays and blocks visible light. The composition according to any one of claims 1 to 4 of the scope of patent application, further comprising a radical polymerizable compound and a photopolymerization initiator. A film comprising the composition according to any one of claims 1 to 8 of the scope of patent application. An optical filter having the film described in item 9 of the scope of patent application. The optical filter according to item 10 of the scope of patent application, wherein the aforementioned optical filter is a near-infrared cut-off filter or an infrared transmission filter. The optical filter according to item 10 or 11 of the scope of patent application, comprising: a pixel of the film according to item 9 of the scope of patent application; and a pixel selected from red, green, blue, magenta, yellow, cyan, At least one of black and colorless pixels. A laminated body having the film as described in item 9 of the scope of patent application, and a color filter including a colorant. A solid-state imaging element having the film described in item 9 of the scope of patent application. An image display device having the film described in item 9 of the scope of patent application. An infrared sensor having a film as described in item 9 of the scope of patent application. A compound represented by the following formula (1), In formula (1), R ¹ and R ² each independently represent a halogen atom, a cyano group, a nitro group, a fluoroalkyl group, -OCOR ¹¹ , -SOR ¹² or -SO ₂ R ¹³ , and R ¹¹ to R ¹³ are each independently Ground represents a hydrocarbon group or a heteroaryl group, n represents an integer of 1 to 3, R ³ to R ⁶ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to form a ring, R ⁷ to R ¹⁰ each independently represent a hydrogen atom or a substituent, X ¹ and X ² each independently represent a hydrogen atom or -BR ^21a R ^22a , R ^21a and R ^22a each independently represent a substituent, and R ^21a and R ^22a They may be bonded to each other to form a ring.