WO2023176470A1

WO2023176470A1 - Composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, and camera module

Info

Publication number: WO2023176470A1
Application number: PCT/JP2023/007775
Authority: WO
Inventors: 彰宏原; 季彦松村; 恭平荒山
Original assignee: 富士フイルム株式会社
Priority date: 2022-03-14
Filing date: 2023-03-02
Publication date: 2023-09-21
Also published as: TW202336045A

Abstract

Provided are a composition that exhibits excellent storage stability and that can be used to form a film with excellent light resistance and heat resistance, a film, an optical filter, a solid-state imaging element, an image display device, an infrared sensor, and a camera module. The composition comprises: an infrared absorbing agent containing a compound represented by formula (1); a prescribed antifading agent; and a curable compound.

Description

Compositions, films, optical filters, solid-state imaging devices, image display devices, infrared sensors and camera modules

The present invention relates to a composition containing an infrared absorber. The present invention also relates to a film, an optical filter, a solid-state image sensor, an image display device, an infrared sensor, and a camera module using the composition.

Video cameras, digital still cameras, mobile phones with camera functions, and the like use CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), which are solid-state imaging devices for color images. These solid-state image sensors use silicon photodiodes sensitive to infrared rays in their light receiving portions. For this reason, an infrared cut filter may be provided to correct visibility.

Infrared cut filters are manufactured using a composition containing an infrared absorber. Squarylium compounds and the like are used as infrared absorbers.

Patent Document 1 discloses that a film obtained using a composition containing an infrared absorber containing a squarylium compound and an antioxidant having at least one phosphorus atom in the molecule can be used for an infrared cut filter, etc. Are listed.

JP 2021-039369 Publication

However, squarylium compounds tend to have low light resistance and heat resistance. Therefore, there is room for further improvement in the light resistance and heat resistance of films obtained using compositions containing squarylium compounds.

Further, when the present inventor conducted further studies on compositions using squarylium compounds as infrared absorbers, it was found that there was room for improvement in storage stability.

Therefore, an object of the present invention is to provide a composition that can form a film that has excellent storage stability and excellent light resistance and heat resistance. Further, the present invention provides a film, an optical filter, a solid-state image sensor, an image display device, an infrared sensor, and a camera module.

The present invention provides the following.
<1> Contains an infrared absorber, an anti-fading agent, and a curable compound,
The infrared absorber includes a compound represented by formula (1),
A composition in which the anti-fading agent satisfies the following conditions 1 or 2;
Condition 1: The above anti-fading agent contains at least one selected from the group consisting of phosphorus antioxidants and sulfur antioxidants, a phenolic antioxidant, an amine antioxidant, a quencher, and a singlet oxygen scavenger. at least one selected from the group consisting of agents;
Condition 2: The anti-fading agent contains at least one selected from the group consisting of phenolic antioxidants, amine antioxidants, and singlet oxygen quenchers, and a quencher;
In formula (1), A and B each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle;
Ra and Rb each independently represent a substituent;
m1 represents an integer from 0 to mA, mA represents the maximum integer in which Ra can be replaced by A, m2 represents an integer from 0 to mB, and mB represents the maximum integer in which Rb can be replaced by B. represent;
Ra and A may be combined to form a ring, Rb and B may be combined to form a ring, and when m1 is 2 or more, two Ras out of m1 Ras may be combined to form a ring, and when m2 is 2 or more, two Rb out of m2 Rb may be combined to form a ring;
Y ¹ and Y ² each independently represent an alkyl group, an aryl group, or a group represented by formula (Y-1); provided that at least one of Y ¹ and Y ² contains a fluorine atom;
-L ^Y1 -R ^Y1 ...Formula (Y-1)
In formula (Y-1), L ^Y1 represents -CO-, -CS-, -SO ₂ -, -CONH-, -CSNH- or -COO-, and R ^Y1 represents an alkyl group, an alkenyl group, or an alkynyl group. represents a group, an aryl group or a heteroaryl group.
<2> As described in <1>, wherein at least one of A and B in the above formula (1) is a benzene ring, a thiophene ring, a furan ring, a pyrrole ring, a pyridine ring, an azulene ring, or a fused ring containing these rings. Composition of.
<3> The composition according to <1> or <2>, wherein at least one of A and B in the above formula (1) is a benzene ring or a naphthalene ring.
<4> The compound represented by the above formula (1) has a structure represented by formula (2-1) or formula (2-2), and is described in any one of <1> to <3>composition;
In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1),
Y ³ represents a group represented by the above formula (Y-1),
Rs ¹ represents a substituent, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 5,
Rs ¹¹ and Rs ¹² each independently represent an alkyl group, an aryl group or a heteroaryl group,
Rs ¹¹ and Rs ¹² , Rs ¹¹ and Rs ¹ , and Rs ¹² and Rs ¹ may be bonded to each other to form a ring.
<5> The compound represented by the above formula (1) has a structure represented by formula (2-1a), formula (2-1b), formula (2-1c) or formula (2-1d), The composition according to any one of <1> to <4>;
In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1),
Y ³ represents a group represented by the above formula (Y-1),
Rs ² to Rs ⁴ each independently represent a hydrogen atom or a substituent,
Rs ¹³ and Rs ¹⁴ each independently represent an alkyl group, an aryl group or a heteroaryl group,
A1 to A4 each independently represent a ring containing a nitrogen atom.
<6> The composition according to any one of <1> to <5>, wherein the compound represented by formula (1) is a compound represented by formula (1a);
In the formula, Y ⁴ and Y ⁵ each independently represent a group represented by the above formula (Y-1); provided that at least one of Y ⁴ and Y ⁵ contains a fluorine atom;
Rs ⁵ and Rs ⁶ each independently represent a substituent;
n1a and n1b each independently represent an integer of 0 to 3;
Rs ²¹ to Rs ²⁴ each independently represent an alkyl group, an aryl group, or a heteroaryl group;
Rs ²¹ and Rs ²² , Rs ²³ and Rs ²⁴ , Rs ²¹ and Rs ⁵ , Rs ²² and Rs ⁵ , Rs ²³ and Rs ⁶ , and Rs ²⁴ and Rs ⁶ may be bonded to each other to form a ring.
<7> The composition according to any one of <1> to <6>, wherein the anti-fading agent has a molecular weight of 1170 or less.
<8> The composition according to any one of <1> to <7>, wherein the anti-fading agent satisfies Condition 1 above.
<9> The composition according to any one of <1> to <8>, wherein the curable compound includes a polymerizable compound.
<10> The composition according to <9>, wherein the polymerizable compound includes a compound having an ethylenically unsaturated bond-containing group.
<11> The composition according to any one of <1> to <10>, wherein the infrared absorber contains an infrared absorber other than the compound represented by the formula (1).
<12> A film obtained using the composition according to any one of <1> to <11>.
<13> An optical filter comprising the film according to <12>.
<14> A solid-state imaging device comprising the film according to <12>.
<15> An image display device including the film according to <12>.
<16> An infrared sensor comprising the film according to <12>.
<17> A camera module including the film according to <12>.

According to the present invention, it is possible to provide a composition that can form a film that has excellent storage stability and excellent light resistance and heat resistance. Further, the present invention can provide a film, an optical filter, a solid-state image sensor, an image display device, an infrared sensor, and a camera module.

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

The content of the present invention will be explained in detail below.
In this specification, "~" is used to include the numerical values described before and after it as a lower limit and an upper limit.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents acrylate and/or methacrylate, "(meth)acrylic" represents both acrylic and/or methacrylic, and "(meth)acrylate" represents acrylic and/or methacrylate. ) "Acryloyl" refers to either or both of acryloyl and methacryloyl.
In this specification, the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).
In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, infrared rays refer to light (electromagnetic waves) with a wavelength of 700 to 2,500 nm.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent.
In this specification, the term "process" is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .

<Composition>
The composition of the present invention includes an infrared absorber, an anti-fading agent, and a curable compound,
The infrared absorber includes a compound represented by formula (1),
The above anti-fading agent satisfies Condition 1 or Condition 2 below.
Condition 1: The above anti-fading agent contains at least one selected from the group consisting of phosphorus antioxidants and sulfur antioxidants, a phenolic antioxidant, an amine antioxidant, a quencher, and a singlet oxygen scavenger. and at least one selected from the group consisting of agents.
Condition 2: The anti-fading agent contains at least one selected from the group consisting of phenolic antioxidants, amine antioxidants, and singlet oxygen quenchers, and a quencher.

The composition of the present invention has excellent storage stability. Further, by using the composition of the present invention, a film having excellent light resistance and heat resistance can be formed. Although the detailed reason for obtaining such an effect is unknown, it is presumed to be due to the following reasons.

The compound represented by formula (1) contained in the composition of the present invention has a structure in which at least one of Y ¹ and Y ² contains a fluorine atom, so that it interacts with the anti-fading agent, It is presumed that the anti-fading agent is likely to be present near the compound represented by formula (1).
Therefore, it is presumed that the density of the anti-fading agent around the compound represented by formula (1) can be increased in the composition or in the film.
By containing the anti-fading agent that satisfies Condition 1 or Condition 2 described above, the composition of the present invention can prevent the decomposition of the compound represented by formula (1) by light irradiation or the decomposition of the compound represented by formula (1) by heating. It is presumed that the decomposition of compounds that are exposed to water can be effectively suppressed. For these reasons, it is presumed that by using the composition of the present invention, a film with excellent light resistance and heat resistance could be formed.
Furthermore, it is presumed that the anti-fading agent that satisfies Condition 1 or Condition 2 described above can also suppress the decomposition of the compound represented by formula (1) during storage of the composition. If such decomposition products occur during storage of the composition, the viscosity of the composition tends to increase over time due to reaction or interaction between the decomposition products and the curable compound. On the other hand, since the composition of the present invention can suppress the generation of the above decomposed products during storage, it is presumed that as a result, the increase in viscosity of the composition during storage can be suppressed. For these reasons, it is presumed that the composition of the present invention has excellent storage stability.

In particular, by using an anti-fading agent that satisfies Condition 1 above, the light resistance and heat resistance of the resulting film can be further improved.

Since the compound represented by formula (1) also has excellent visible transparency and infrared shielding properties, the film obtained by using the composition of the present invention is a film that has excellent visible transparency and infrared shielding properties. can also be formed. Therefore, by using the composition of the present invention, a film with excellent spectral properties can be formed.

The composition of the present invention can be used as a composition for optical filters. Types of optical filters include infrared cut filters and infrared transmission filters. Since the compound represented by formula (1) has excellent visible transparency, by using the composition of the present invention, an infrared cut filter having excellent visible transparency can be formed. Furthermore, in the infrared transmission filter, the infrared absorbing agent has the role of limiting transmitted light (infrared rays) to longer wavelengths. Since the compound represented by formula (1) has excellent visible transparency, it is easy to control the spectrum in the visible region to be blocked and the spectrum in the infrared region to be transmitted to an appropriate range.

Each component used in the composition of the present invention will be explained below.

<<Infrared absorber>>
The composition of the invention includes an infrared absorber. The infrared absorber contained in the composition of the present invention includes a compound represented by formula (1). Hereinafter, the compound represented by formula (1) will also be referred to as a specific compound.

(Specific compound (compound represented by formula (1)))

In formula (1), A and B each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle;
Ra and Rb each independently represent a substituent;
m1 represents an integer from 0 to mA, mA represents the maximum integer in which Ra can be replaced by A, m2 represents an integer from 0 to mB, and mB represents the maximum integer in which Rb can be replaced by B. represent;
Ra and A may be combined to form a ring, Rb and B may be combined to form a ring, and when m1 is 2 or more, two Ras out of m1 Ras may be combined to form a ring, and when m2 is 2 or more, two Rb out of m2 Rb may be combined to form a ring;
Y ¹ and Y ² each independently represent an alkyl group, an aryl group, or a group represented by formula (Y-1); provided that at least one of Y ¹ and Y ² contains a fluorine atom;
-L ^Y1 -R ^Y1 ...Formula (Y-1)
In formula (Y-1), L ^Y1 represents -CO-, -CS-, -SO ₂ -, -CONH-, -CSNH- or -COO-, and R ^Y1 represents an alkyl group, an alkenyl group, or an alkynyl group. represents a group, an aryl group or a heteroaryl group.

In formula (1), A and B each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle.
The number of carbon atoms constituting the aromatic hydrocarbon ring is preferably 6 to 48, more preferably 6 to 22, particularly preferably 6 to 12. The aromatic hydrocarbon ring is preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, more preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings, It is more preferably a fused ring of 2 or 3, and particularly preferably a single ring or a fused ring with 2 fused rings.
The aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring. Further, the aromatic heterocycle is preferably a single ring or a condensed ring having 2 to 8 condensed rings, more preferably a monocycle or a condensed ring having 2 to 4 condensed rings, is more preferably a fused ring having 2 or 3 rings, and particularly preferably a single ring or a fused ring having 2 fused rings. Examples of the heteroatom constituting the ring of the aromatic heterocycle include nitrogen atom, oxygen atom, and sulfur atom, with nitrogen atom and sulfur atom being preferred. The number of heteroatoms constituting the ring of the aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.

In formula (1), at least one of A and B (preferably both A and B) is a benzene ring, a thiophene ring, a furan ring, a pyrrole ring, a pyridine ring, an azulene ring, or a fused ring containing these rings. It is preferable. Examples of the above-mentioned condensed rings include a naphthalene ring, a benzothiophene ring, a benzofuran ring, an isobenzofuran ring, a benzimidazole ring, an indole ring, an isoindole ring, a quinoline ring, an isoquinoline ring, a thienopyrrole ring, and a pyrrolothiazole ring. From the viewpoint of visible transparency and infrared shielding properties, at least one of A and B (preferably both A and B) is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

In formula (1), Ra and Rb each independently represent a substituent. Examples of substituents include halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , -CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NHSO ₂ Rt ¹ and -SO ₂ NRt ¹ Rt ² can be mentioned. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Rt ¹ and Rt ² may be combined to form a ring, Rt ¹ and/or Rt ² and A may be combined to form a ring, and Rt ¹ and/or Rt ² and B may be combined to form a ring. They may be combined to form a ring. Note that when Rt ¹ of -COORt ¹ is hydrogen, the hydrogen atom may be dissociated or may be in a salt state. Further, when Rt ¹ of -SO ₂ ORt ¹ is a hydrogen atom, the hydrogen atom may be dissociated or may be in a salt state.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and preferably linear or branched.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched, or cyclic, and preferably linear or branched.
The number of carbon atoms in the alkynyl group is preferably 2 to 40, more preferably 2 to 30, particularly preferably 2 to 25. The alkynyl group may be linear, branched, or cyclic, and preferably linear or branched.
The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
The heteroaryl group is preferably a single ring or a condensed ring having 2 to 8 condensed rings, and more preferably a single ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. Preferably, the heteroaryl group is a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 2 to 30, more preferably 2 to 18, and even more preferably 2 to 12.
The alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups listed below for substituent T.

In formula (1), Ra and A may be combined to form a ring, Rb and B may be combined to form a ring, and when m1 is 2 or more, m1 of Ra Two of the Ra's may be bonded to each other to form a ring, and when m2 is 2 or more, two Rb's of m2 Rb's may be bonded to each other to form a ring. Examples of the linking group when forming the above ring include divalent linking groups selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. It will be done. The alkylene group as a linking group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T.

In formula (1), m1 represents an integer from 0 to mA, mA represents the maximum integer in which Ra can be replaced by A, m2 represents an integer from 0 to mB, and mB represents Rb to be replaced by B. Represents the largest possible integer. For example, if A is a benzene ring, mA is 4. Further, when A is a naphthalene ring, mA is 6. m1 and m2 are each independently preferably an integer of 0 to 4, more preferably an integer of 0 to 3, even more preferably an integer of 1 to 3, particularly preferably 1 or 2, and most preferably 1.

It is preferable that Ra and Rb in formula (1) are each independently -NRt ¹ Rt ² .
Rt ¹ and Rt ² are each independently preferably an alkyl group, an aryl group, or a heteroaryl group, and from the viewpoint of light resistance, an alkyl group or an aryl group is preferable, and an aryl group is preferable. More preferred.
Furthermore, from the viewpoint of light resistance, it is also preferable that Rt ¹ and Rt ² combine to form a ring.
The ring formed by combining Rt ¹ and Rt ² is preferably a 5-membered ring or a 6-membered ring.
When Rt ¹ and Rt ² combine to form a ring, the linking group is selected from the group consisting of -CO-, -O-, -NH-, an alkylene group having 1 to 10 carbon atoms, and combinations thereof. Examples include divalent linking groups, and alkylene groups having 1 to 10 carbon atoms are preferred. The alkylene group as a linking group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T.
Furthermore, from the viewpoint of light resistance, it is preferable that at least one of Rt ¹ and Rt ² and A or B combine to form a ring. The ring formed above is preferably a 5-membered ring or a 6-membered ring. When at least one of Rt ¹ and Rt ² and A or B combine to form a ring, examples of the linking group include -CO-, -O-, -NH-, an alkylene group having 1 to 10 carbon atoms, and Examples include divalent linking groups selected from the group consisting of combinations thereof, and alkylene groups having 1 to 10 carbon atoms are preferred. The alkylene group as a linking group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T.

In formula (1), Y ¹ and Y ² each independently represent an alkyl group, an aryl group, or a group represented by formula (Y-1), and at least one of Y ¹ and Y ² has a fluorine atom. include. In formula (1), Y ¹ and Y ² are each independently preferably a group represented by formula (Y-1).

The number of carbon atoms in the alkyl group represented by Y ¹ and Y ² is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic.
The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
The alkyl group and aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed for the substituent T described below and the groups containing a fluorine atom shown below, and a group containing a fluorine atom is preferable.

The group represented by formula (Y-1) represented by Y ¹ and Y ² will be explained.

L ^Y1 in formula (Y-1) represents -CO-, -CS-, -SO ₂ -, -CONH-, -CSNH- or -COO-, and -CO-, -SO ₂ - or -CONH- is preferable, -CO- or -CONH- is more preferable, and -CONH- is particularly preferable.

R ^Y1 in formula (Y-1) represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
The number of carbon atoms in the alkyl group represented by R ^Y1 is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic.
The alkenyl group represented by R ^Y1 preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched, or cyclic.
The number of carbon atoms in the alkynyl group represented by R ^Y1 is preferably 2 to 20, more preferably 2 to 15, and even more preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic.
The number of carbon atoms in the aryl group represented by R ^Y1 is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
The heteroaryl group represented by R ^Y1 is preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, and more preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. Preferably, the heteroaryl group is a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 2 to 30, more preferably 2 to 18, and even more preferably 2 to 12.
The alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group represented by R ^Y1 may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed for the substituent T described below and the groups containing a fluorine atom shown below, and a group containing a fluorine atom is preferable.

R ^Y1 in formula (Y-1) is preferably an alkyl group or an aryl group, and is an alkyl group having a fluorine atom-containing group as a substituent or an aryl group having a fluorine atom-containing group as a substituent. More preferably, it is an alkyl group having a fluorine atom-containing group as a substituent.

Examples of groups containing a fluorine atom include a fluorine atom, -R ^F1 , -OR ^F1 , -SR ^F1 , -COR ^F1 , -COOR ^F1 , -OCOR ^F1 , -NR ^F1 R ^F2 , -NHCOR ^F1 , -CONR ^F1 R Examples include ^F2 , -NHCONR ^F1 R ^F2 , -NHCOOR ^F1 , -SO ₂ R ^F1 , -SO ₂ OR ^F1 and -NHSO ₂ R ^F1 , with fluorine atoms, -R ^F1 and -COR ^F1 being preferred. R ^F1 represents a hydrocarbon group containing a fluorine atom, and R ^F2 represents a hydrogen atom, a hydrocarbon group, a heteroaryl group, or a hydrocarbon group containing a fluorine atom. Hereinafter, a hydrocarbon group containing a fluorine atom will also be referred to as a fluorine-containing hydrocarbon group.

The hydrocarbon group represented by R ^F2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be a chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, particularly preferably 1 to 5. The alkyl group may be straight chain, branched, or cyclic, but straight chain or branched is preferable, and straight chain is more preferable. The number of carbon atoms in the alkenyl group and the alkynyl group is preferably 2 to 30, more preferably 2 to 20, even more preferably 2 to 10, particularly preferably 2 to 5. The alkenyl group and the alkynyl group may be straight chain, branched, or cyclic, but straight chain or branched is preferable, and straight chain is more preferable. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.

The fluorine-containing hydrocarbon group (hydrocarbon group containing a fluorine atom) represented by R ^F1 and R ^F2 includes a group in which at least a part of the hydrogen atoms of the above hydrocarbon group is substituted with a fluorine atom, and a fluoroalkyl group and a fluoroaryl group, and more preferably a fluoroalkyl group.

The heteroaryl group represented by R ^F2 is preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, and more preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. Preferably, the heteroaryl group is a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 2 to 30, more preferably 2 to 18, and even more preferably 2 to 12.

In addition, in formula (1), the cation exists in a delocalized manner as follows.

The specific compound is preferably a compound having a structure represented by formula (2-1) or formula (2-2), and more preferably a compound having a structure represented by formula (2-1). preferable.
In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1),
Y ³ represents a group represented by the above formula (Y-1),
Rs ¹ represents a substituent, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 5,
Rs ¹¹ and Rs ¹² each independently represent an alkyl group, an aryl group or a heteroaryl group,
Rs ¹¹ and Rs ¹² , Rs ¹¹ and Rs ¹ , and Rs ¹² and Rs ¹ may be bonded to each other to form a ring.

The preferred range of the group represented by formula (Y-1) represented by Y ³ is the same as the above-mentioned range.
Examples of the substituent represented by Rs ¹ include the groups listed below for the substituent T.
Rs ¹¹ and Rs ¹² each independently represent an alkyl group, an aryl group, or a heteroaryl group, preferably an alkyl group or an aryl group, and more preferably an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic. Further, the alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. Further, the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T. The heteroaryl group is preferably a single ring or a condensed ring having 2 to 8 condensed rings, and more preferably a single ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group preferably has a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 2 to 30, more preferably 2 to 18, and even more preferably 2 to 12. The heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T.
n1 represents an integer from 0 to 3, and n2 represents an integer from 0 to 5. n1 is preferably an integer of 0 to 2, more preferably 0. n2 is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, even more preferably an integer of 0 to 2.

In the above formula, Rs ¹¹ and Rs ¹² , Rs ¹¹ and Rs ¹ , and Rs ¹² and Rs ¹ may be bonded to each other to form a ring. The ring formed by bonding these groups to each other is preferably a 5-membered ring or a 6-membered ring. When these groups combine to form a ring, the linking group is 2 selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. Examples include a valent linking group, and an alkylene group having 1 to 10 carbon atoms is preferred. The alkylene group as a linking group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T.

Note that the bonding position with the squaric acid moiety in formula (1) means the bonding position with the following structure in formula (1). The wavy line represents the bonding position with the structure represented by formula (2-1) or formula (2-2).

The specific compound is preferably a compound having a structure represented by formula (2-1a), formula (2-1b), formula (2-1c) or formula (2-1d); ), a compound having a structure represented by formula (2-1c) or formula (2-1d) is more preferable, and a compound having a structure represented by formula (2-1c) or formula (2-1d) is more preferable because it is easier to obtain better infrared shielding properties. Further, it is more preferable that the compound has a structure represented by formula (2-1d).

In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1),
Y ³ represents a group represented by the above formula (Y-1),
Rs ² to Rs ⁴ each independently represent a hydrogen atom or a substituent,
Rs ¹³ and Rs ¹⁴ each independently represent an alkyl group, an aryl group or a heteroaryl group,
A1 to A4 each independently represent a ring containing a nitrogen atom.

Examples of the substituents represented by Rs ² to Rs ⁴ include the groups listed for the substituent T described below.
Details of the alkyl group, aryl group, and heteroaryl group represented by Rs ¹³ and Rs ¹⁴ are the same as those described for Rs ¹¹ and Rs ¹² .

In formula (2-1a), from the viewpoint of light resistance, Rs ¹³ and Rs ¹⁴ are preferably each independently an aryl group.

A1 in formula (2-1b) represents a ring containing a nitrogen atom. The ring represented by A1 is preferably a 5-membered ring or a 6-membered ring. Further, a ring containing only N in the formula as a nitrogen atom is preferable. Specific examples of the structure represented by formula (2-1b) include the structure represented by formula (2-1b1) and the structure represented by formula (2-1b2).

In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1), Y ³ represents the group represented by the above formula (Y-1), and Rs ² to Rs ⁴ are each independently represents a hydrogen atom or a substituent, Rs ¹⁰⁰ represents a substituent, mb1 represents an integer of 0 to 2, and mb2 represents an integer of 0 to 3. When mb1 or mb2 is 2 or more, two Rs ¹⁰⁰ 's may be bonded to each other to form a ring. Examples of the substituent represented by Rs ¹⁰⁰ include the groups listed below for substituent T.

A2 in formula (2-1c) represents a ring containing a nitrogen atom. The ring represented by A2 is preferably a 5-membered ring or a 6-membered ring. Further, a ring containing only N in the formula as a nitrogen atom is preferable. Specific examples of the structure represented by formula (2-1c) include the structure represented by formula (2-1c1) and the structure represented by formula (2-1c2).

In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1), Y ³ represents a group represented by the above formula (Y-1), and Rs ³ and Rs ⁴ are each independently represents a hydrogen atom or a substituent, Rs ¹⁰¹ represents a substituent, mc1 represents an integer of 0 to 2, and mc2 represents an integer of 0 to 3. When mc1 or mc2 is 2 or more, two Rs ¹⁰¹ may be bonded to each other to form a ring. Examples of the substituent represented by Rs ¹⁰¹ include the groups listed below for substituent T.

A3 and A4 in formula (2-1d) each independently represent a ring containing a nitrogen atom. The ring represented by A3 and A4 is preferably a 5-membered ring or a 6-membered ring. Further, a ring containing only N in the formula as a nitrogen atom is preferable. Specific examples of the structure represented by formula (2-1d) include the structure represented by formula (2-1d1) and the structure represented by formula (2-1d2).

In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1), Y ³ represents a group represented by the above formula (Y-1), and Rs ⁴ represents a hydrogen atom or a substituent. , Rs ¹⁰² represents a substituent, md1 represents an integer of 0 to 4, and md2 represents an integer of 0 to 6. When md1 or md2 is 2 or more, two Rs ¹⁰² may be bonded to each other to form a ring. Examples of the substituent represented by Rs ¹⁰² include the groups listed below for substituent T.

It is preferable that the specific compound is a compound represented by formula (1a).

In the formula, Y ⁴ and Y ⁵ each independently represent a group represented by the above formula (Y-1); provided that at least one of Y ⁴ and Y ⁵ contains a fluorine atom;
Rs ⁵ and Rs ⁶ each independently represent a substituent;
n1a and n1b each independently represent an integer of 0 to 3;
Rs ²¹ to Rs ²⁴ each independently represent an alkyl group, an aryl group, or a heteroaryl group;
Rs ²¹ and Rs ²² , Rs ²³ and Rs ²⁴ , Rs ²¹ and Rs ⁵ , Rs ²² and Rs ⁵ , Rs ²³ and Rs ⁶ , and Rs ²⁴ and Rs ⁶ may be bonded to each other to form a ring.

Y ⁴ and Y ⁵ in formula (1a) each independently represent a group represented by the above formula (Y-1).
The details of the group represented by formula (Y-1) represented by Y ⁴ and Y ⁵ are the same as described above, and the preferred ranges are also the same.
It is preferable that Y ⁴ and Y ⁵ in formula (1a) are each a group containing a fluorine atom. Among them, R ^Y1 of formula (Y-1) represented by Y ⁴ and Y ⁵ of formula (1a) is an alkyl group having a fluorine atom-containing group as a substituent, or a group containing a fluorine atom is substituted. It is preferably an aryl group having a fluorine atom-containing group as a substituent, and more preferably an alkyl group having a fluorine atom-containing group as a substituent.

Examples of the substituents represented by Rs ⁵ and Rs ⁶ in formula (1a) include the groups listed below for substituent T.

In formula (1a), n1a and n1b each independently represent an integer of 0 to 3, preferably an integer of 0 to 2.

The alkyl group, aryl group and heteroaryl group represented by Rs ²¹ to Rs ²⁴ in formula (1a) are the same as the ranges explained for Rs ¹¹ and Rs ¹² in formula (2-1) and formula (2-2). .

In formula (1a), Rs ²¹ and Rs ²² , Rs ²³ and Rs ²⁴ , Rs ²¹ and Rs ⁵ , Rs ²² and Rs ⁵ , Rs ²³ and Rs ⁶ , and Rs ²⁴ and Rs ⁶ combine with each other to form a ring. You may. Examples of the linking group when forming the above ring include divalent linking groups selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. It will be done. The alkylene group as a linking group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T.

-Substituent T-
Examples of the substituent T include the following groups. Halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), a heteroaryl group (preferably a heteroaryl group having 1 to 30 carbon atoms), an amino group (preferably a heteroaryl group having 1 to 30 carbon atoms), an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group (preferably a carbon Heteroaryloxy group having 1 to 30 carbon atoms), acyl group (preferably an acyl group having 2 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), heteroaryloxycarbonyl group (preferably heteroaryloxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms) , an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a sulfamoylamino group (preferably a sulfamoyl group having 0 to 30 carbon atoms) sulfamoylamino group), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms) ), a heteroarylthio group (preferably a heteroarylthio group having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), an alkylsulfonylamino group (preferably a carbon number 1 to 30), 30 alkylsulfonylamino groups), arylsulfonyl groups (preferably arylsulfonylamino groups having 6 to 30 carbon atoms), arylsulfonylamino groups (preferably arylsulfonylamino groups having 6 to 30 carbon atoms), heteroarylsulfonyl groups (preferably is a heteroarylsulfonyl group having 1 to 30 carbon atoms), a heteroarylsulfonylamino group (preferably a heteroarylsulfonylamino group having 1 to 30 carbon atoms), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms) , an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), a heteroarylsulfinyl group (preferably a heteroarylsulfinyl group having 1 to 30 carbon atoms), a ureido group (preferably a ureido group having 1 to 30 carbon atoms) ), hydroxy group, nitro group, carboxy group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonamide group, imide group, phosphino group, mercapto group, cyano group, alkylsulfino group, arylsulfino group, arylazo group, heteroarylazo group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, hydrazino group, imino group. These groups may further have a substituent when the group is a substitutable group. Examples of the substituent include the groups described above for the substituent T.

The maximum absorption wavelength of the specific compound is preferably present in a wavelength range of 650 nm or more, more preferably in a wavelength range of 650 to 1500 nm, even more preferably in a wavelength range of 700 to 1200 nm, and even more preferably in a wavelength range of 700 to 1000 nm. It is particularly preferable that it exists in the range of .

Specific examples of the specific compound include, but are not limited to, the compounds described below.

(Other infrared absorbers)
The composition of the present invention can contain an infrared absorber (another infrared absorber) other than the specific compound mentioned above. Furthermore, by containing other infrared absorbers, it is possible to form a film that can block infrared rays in a wider wavelength range. Other infrared absorbers may be dyes or pigments (particles). Other infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyrromethene compounds. , azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like. Examples of pyrrolopyrrole compounds include compounds described in paragraph numbers 0016 to 0058 of JP2009-263614A, compounds described in paragraphs 0037 to 0052 of JP2011-068731A, and compounds described in WO2015/166873A. Examples include compounds described in paragraph numbers 0010 to 0033. Examples of squarylium compounds include compounds described in paragraph numbers 0044 to 0049 of JP-A No. 2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of International Publication No. 2016/181987. Compounds described in JP 2015-176046, compounds Q-1 to Q-10 described in paragraph number 0072 of WO 2016/190162, paragraph number JP 2016-074649 Compounds described in 0196 to 0228, compounds described in paragraph number 0124 of JP 2017-067963, compounds described in International Publication No. 2017/135359, compounds described in JP 2017-114956, International Publication Examples include compounds described in No. 2016/120166. Examples of cyanine compounds include compounds described in paragraph numbers 0044 to 0045 of JP 2009-108267, compounds described in paragraph 0026 to 0030 of JP 2002-194040, and compounds described in JP 2015-172004. Compounds described in JP 2015-172102, compounds described in JP 2008-088426, compounds described in paragraph number 0090 of WO 2016/190162, JP 2017-031394 Examples include the compounds described in . Examples of the croconium compound include compounds described in JP-A No. 2017-082029. Examples of iminium compounds include compounds described in Japanese Patent Publication No. 2008-528706, compounds described in Japanese Patent Application Publication No. 2012-012399, compounds described in Japanese Patent Application Publication No. 2007-092060, and International Publication No. 2018/043564. Examples include the compounds described in paragraph numbers 0048 to 0063 of . Examples of phthalocyanine compounds include compounds described in paragraph number 0093 of JP-A No. 2012-077153, oxytitanium phthalocyanine described in JP-A 2006-343631, and paragraphs 0013 to 0029 of JP-A 2013-195480. , the vanadium phthalocyanine compound described in Patent No. 6081771, and the compound described in International Publication No. 2020/071470. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A No. 2012-077153. Examples of the dithiolene metal complex include compounds described in Japanese Patent No. 5733804. Examples of the metal oxide include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For details on tungsten oxide, paragraph number 0080 of JP-A-2016-006476 can be referred to, the contents of which are incorporated herein. Examples of metal borides include lanthanum boride. Commercially available lanthanum boride products include LaB ₆ -F (manufactured by Nippon Shinkinzoku Co., Ltd.). Moreover, as a metal boride, the compound described in International Publication No. 2017/119394 can also be used. Commercially available indium tin oxide products include F-ITO (manufactured by DOWA Hitech Co., Ltd.).

In addition, as infrared absorbers, squarylium compounds described in JP2017-197437A, squarylium compounds described in JP2017-025311A, squarylium compounds described in International Publication No. 2016/154782, and Japanese Patent No. 5884953 Squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraphs 0090 to 0107 of International Publication No. 2017/213047, Pyrrole ring-containing compounds described in paragraph numbers 0019 to 0075 of JP-A No. 2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078 to 0082 of JP-A No. 2018-040955, paragraphs of JP-A No. 2018-002773 Pyrrole ring-containing compounds described in Nos. 0043 to 0069, squarylium compounds having an aromatic ring at the amide α-position described in paragraph numbers 0024 to 0086 of JP 2018-041047, and amides described in JP 2017-179131. Linked squarylium compounds, compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP 2017-141215, dihydrocarbazole bis-type squarylium compounds described in JP 2017-082029, JP 2017-068120 Asymmetric compounds described in paragraph numbers 0027 to 0114 of the publication, pyrrole ring-containing compounds (carbazole type) described in JP 2017-067963, phthalocyanine compounds described in Patent No. 6251530, etc. are used. You can also do that.

As another infrared absorber, tungsten oxide represented by the following formula described in paragraph number 0025 of European Patent No. 3,628,645 can also be used.
M ¹ _a M ² _b W _c O _d (P(O) _n R _m ) _e
M ¹ and M ² represent ammonium cations or metal cations, a is 0.01 to 0.5, b is 0 to 0.5, c is 1, and d is 2.5 to 3. , e is 0.01 to 0.75, n is 1, 2 or 3, m is 1, 2 or 3, and R represents a hydrocarbon group which may have a substituent. represent.

The content of the infrared absorber is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more based on the total solid content of the composition. , more preferably 3% by mass or more, particularly preferably 5% by mass or more. The upper limit of the content of the infrared absorber is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
The content of the above-mentioned specific compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more based on the total solid content of the composition. It is preferably at least 3% by mass, even more preferably at least 5% by mass. The upper limit of the content of the specific compound mentioned above is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
When the composition of the present invention contains other infrared absorbers, the content of the other infrared absorbers is preferably 1 to 100 parts by mass, and 3 to 60 parts by mass based on 100 parts by mass of the above-mentioned specific compound. It is more preferably 5 to 40 parts by weight, and even more preferably 5 to 40 parts by weight.

<<Anti-browning agent>>
The compositions of the present invention include an antibrowning agent. The anti-browning agent contained in the composition of the present invention satisfies Condition 1 or Condition 2 shown below, and satisfies Condition 1 shown below because it can form a film with better heat resistance. Preferably.

Condition 1: The antifading agent is at least one selected from the group consisting of phosphorus antioxidants and sulfur antioxidants, a phenolic antioxidant, an amine antioxidant, a quencher, and a singlet oxygen scavenger. At least one species selected from the group consisting of:
Condition 2: The anti-fading agent contains at least one selected from the group consisting of phenolic antioxidants, amine antioxidants, and singlet oxygen quenchers, and a quencher.

The browning inhibitor that satisfies the above condition 1 is a phenolic antioxidant, an amine antioxidant, a quencher, and a singlet oxygen scavenger, based on a total of 100 parts by mass of a phosphorus antioxidant and a sulfur antioxidant. It is preferable to contain 10 to 1000 parts by mass in total. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more. When the content is within the above range, the light resistance and heat resistance of the film can be further improved, and the storage stability of the composition can also be improved.

One embodiment of the browning inhibitor that satisfies the above condition 1 includes an embodiment containing 10 to 1000 parts by mass of a phenolic antioxidant based on a total of 100 parts by mass of a phosphorus antioxidant and a sulfur antioxidant. . The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.

Another embodiment of the browning inhibitor that satisfies the above condition 1 is an embodiment in which the amine antioxidant is contained in an amount of 10 to 1000 parts by mass based on a total of 100 parts by mass of the phosphorus antioxidant and the sulfur antioxidant. It will be done. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.

Another embodiment of the browning inhibitor that satisfies the above condition 1 includes an embodiment in which the quencher is contained in an amount of 10 to 1000 parts by mass based on a total of 100 parts by mass of the phosphorus antioxidant and the sulfur antioxidant. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.

Another embodiment of the browning inhibitor that satisfies the above condition 1 is an embodiment in which the singlet oxygen scavenger is contained in an amount of 10 to 1000 parts by mass based on a total of 100 parts by mass of the phosphorus antioxidant and the sulfur antioxidant. It will be done. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.

The browning inhibitor that satisfies the above condition 2 preferably contains a total of 10 to 1000 parts by mass of a phenolic antioxidant, an amine antioxidant, and a singlet oxygen scavenger based on 100 parts by mass of the quencher. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.

One embodiment of the browning inhibitor that satisfies the above condition 2 is an embodiment containing 10 to 1000 parts by mass of a phenolic antioxidant per 100 parts by mass of the quencher. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.

Another embodiment of the browning inhibitor that satisfies the above condition 2 includes an embodiment in which the amine antioxidant is contained in an amount of 10 to 1000 parts by mass based on 100 parts by mass of the quencher. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.

Another embodiment of the browning inhibitor that satisfies the above condition 2 is an embodiment in which the singlet oxygen quencher is contained in an amount of 10 to 1000 parts by mass based on 100 parts by mass of the quencher. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.

The browning inhibitor that satisfies Condition 2 above may further contain at least one selected from the group consisting of phosphorus-based antioxidants and sulfur-based antioxidants. The total content of the phosphorus-based antioxidant and the sulfur-based antioxidant is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and 200 parts by mass based on 100 parts by mass of the quencher. It is more preferable that it is the following. The lower limit can be 10 parts by mass or more, and can be 20 parts by mass or more.

A preferable embodiment of the browning inhibitor used in the present invention is one in which the browning inhibitor contains a phosphorus antioxidant and a phenolic antioxidant. According to the anti-browning agent of this embodiment, a film with better light resistance and heat resistance can be formed. The browning inhibitor of this embodiment preferably contains 10 to 1000 parts by mass of the phenolic antioxidant per 100 parts by mass of the phosphorus antioxidant. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.
The browning inhibitor of this embodiment may further contain at least one selected from the group consisting of amine antioxidants, quenchers, and singlet oxygen scavengers. By including these, the light resistance and heat resistance of the film can be further improved. The content of the amine antioxidant is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and preferably 200 parts by mass or less based on 100 parts by mass of the phosphorus antioxidant. More preferred. The lower limit can be 10 parts by mass or more, and can be 20 parts by mass or more. The content of the quencher is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 200 parts by mass or less, based on 100 parts by mass of the phosphorous antioxidant. The lower limit can be 10 parts by mass or more, and can be 20 parts by mass or more. The content of the singlet oxygen scavenger is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and preferably 200 parts by mass or less based on 100 parts by mass of the phosphorous antioxidant. More preferred. The lower limit can be 10 parts by mass or more, and can be 20 parts by mass or more.

When the browning inhibitor used in the present invention contains a phosphorus antioxidant and a phenolic antioxidant, the content of the phosphorus antioxidant is 0.1 to 20% by mass based on the total solid content of the composition. % is preferable. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
Further, the content of the phosphorus antioxidant is preferably 1 to 1000 parts by mass per 100 parts by mass of the specific compound. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more.

Another preferred embodiment of the browning inhibitor used in the present invention is one in which the browning inhibitor contains a sulfur-based antioxidant and a phenolic antioxidant. According to the anti-browning agent of this aspect, the storage stability of the composition can be further improved. The browning inhibitor of this embodiment preferably contains 10 to 1000 parts by mass of the phenolic antioxidant per 100 parts by mass of the sulfur-based antioxidant. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.
The browning inhibitor of this embodiment may further contain at least one selected from the group consisting of amine antioxidants, quenchers, and singlet oxygen scavengers. By including these, the light resistance and heat resistance of the film can be further improved. The content of the amine antioxidant is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and preferably 200 parts by mass or less based on 100 parts by mass of the phosphorus antioxidant. More preferred. The lower limit can be 10 parts by mass or more, and can be 20 parts by mass or more. The content of the quencher is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 200 parts by mass or less, based on 100 parts by mass of the phosphorous antioxidant. The lower limit can be 10 parts by mass or more, and can be 20 parts by mass or more. The content of the singlet oxygen scavenger is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and preferably 200 parts by mass or less based on 100 parts by mass of the phosphorous antioxidant. More preferred. The lower limit can be 10 parts by mass or more, and can be 20 parts by mass or more.

When the browning inhibitor used in the present invention contains a sulfur-based antioxidant and a phenolic antioxidant, the content of the sulfur-based antioxidant is 0.1 to 20% by mass based on the total solid content of the composition. % is preferable. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
Further, the content of the sulfur-based antioxidant is preferably 1 to 1000 parts by mass per 100 parts by mass of the specific compound. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more.

The molecular weight of the anti-browning agent used in the present invention is preferably 2000 or less, more preferably 1500 or less, and 1170 or less because it can further improve the light resistance and heat resistance of the film. More preferably.

Next, each material used as an anti-fading agent will be explained.

(phosphorus antioxidant)
As the phosphorus antioxidant, a compound represented by formula (b1) and a structure b1-1 obtained by removing one hydrogen atom from at least one of R ^b1 , R ^b2 and R ^b3 of formula (b1) are used. Examples include compounds having two or more in one molecule.

In formula (b1), R ^b1 and R ^b2 each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, and R ^b3 represents an alkyl group or an aryl group. At least two of R ^b1 , R ^b2 and R ^b3 may be linked via a linking group or a single bond.

The number of carbon atoms in the alkyl group represented by R ^b1 to R ^b3 is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups listed above for the substituent T.
The number of carbon atoms in the aryl group represented by R ^b1 to R ^b3 is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups listed above for the substituent T.
The number of carbon atoms in the alkoxy group represented by R ^b1 and R ^b2 is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkoxy group may be linear, branched, or cyclic. The alkoxy group may have a substituent or may be unsubstituted. Examples of the substituent include the groups listed above for the substituent T.
The number of carbon atoms in the aryloxy group represented by R ^b1 and R ^b2 is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include the groups listed above for the substituent T.
Examples of the halogen atom represented by R ^b1 and R ^b2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Regarding phosphorus-based antioxidants, examples of compounds having two or more of the above structures b1-1 in one molecule include compounds having a structure in which a plurality of the above structures b1-1 are bonded to each other via a single bond or a linking group. It will be done.
Examples of the linking group that connects the plurality of structures b1-1 are a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, - Examples include SO ₂ - and a combination of two or more of these groups. R represents a hydrogen atom, an alkyl group or an aryl group.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be cyclic or acyclic. Further, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent T described below. Further, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused rings.
The heterocyclic group may be a single ring or a condensed ring. Examples of the heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom, and the like.

The molecular weight of the phosphorus antioxidant is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1170 or less.

Specific examples of phosphorous antioxidants include compounds b-1 to b-6 described in Examples below. Specific examples of phosphorus antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, and diisooctylphenyl phosphite. , diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol) phosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite , tris(isodecyl) phosphite, tris(tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis(nonylphenyl) phosphite, poly(dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, Trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris[2-tert-butyl- 4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tri(decyl)phosphite, octyldiphenylphosphite, di(decyl)monophenylphosphite, di Mixture of stearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) Ethyl phosphite, tetra(tridecyl)isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1, 1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatridecylphos phyto, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecylphosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite, tris(2- [(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 3,9-bis( 4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphespiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2- Ethyl-1,3-propanediol phosphite, poly4,4'-isopropylidenediphenol C12-15 alcohol phosphite, bis(diisodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis( octadecyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert- butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, etc. It will be done.

(Sulfur-based antioxidant)
As a sulfur-based antioxidant, a compound represented by formula (e1) and a structure e1-1 obtained by removing one hydrogen atom from at least one of R ^e1 and R ^e2 of formula (e1) are used in one molecule. Examples include compounds having two or more.

In formula (e1), R ^e1 and R ^e2 each independently represent an alkyl group, and R ^e1 and R ^e2 may be connected via a linking group or a single bond.

The number of carbon atoms in the alkyl group represented by R ^e1 and R ^e2 is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups listed above for the substituent T. For example, an alkoxy group may be mentioned.

Regarding sulfur-based antioxidants, examples of compounds having two or more of the above structures e1-1 in one molecule include compounds having a structure in which a plurality of the above structures e1-1 are bonded to each other via a single bond or a linking group. It will be done.
The linking group that connects the plurality of structures e1-1 is a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, - Examples include SO ₂ - and a combination of two or more of these groups. R represents a hydrogen atom, an alkyl group or an aryl group.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be cyclic or acyclic. Further, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent T described below. Further, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused rings.
The heterocyclic group may be a single ring or a condensed ring. Examples of the heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom, and the like.

The molecular weight of the sulfur-based antioxidant is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1170 or less.

Specific examples of sulfur-based antioxidants include compounds e-1 to e-4 described in Examples below. Specific examples of sulfur-based antioxidants include tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C12/C14)thiopropionyloxy]5-tert- butylphenyl) sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thio Dipropionate, lauryl/stearyl thiodipropionate, 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), distearyl -Disulfide, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritoltetrakis (3-dodecylthiopropionate), pentaerythritoltetrakis (3-dodecylthiopropionate), - lauryl thiopropionate) and the like.

(phenolic antioxidant)
Examples of the phenolic antioxidant include compounds represented by formulas (a1) to (a3).

In the formula, R ^a1 to R ^a5 each independently represent a hydrogen atom or a substituent, n represents an integer of 1 or more, and when n is 1, L ^a1 represents a hydrogen atom or a substituent, and n is 2 or more, L ^a1 represents an n-valent linking group.
However, at least one of R ^a1 to R ^a4 in formula (a1) is an alkyl group, at least one of R ^a2 to R ^a5 in formula (a2) is an alkyl group, and R in formula (a3) is an alkyl group. At least one of ^a2 to R ^a5 is an alkyl group.

Examples of the substituents represented by R ^a1 to R ^a5 include the groups listed above for the substituent T.

In formulas (a1) and (a2), at least one of R ^a2 and R ^a3 is preferably an alkyl group, more preferably R ^a2 and R ^a3 are each independently an alkyl group, and R ^a2 and R a3 are each independently an alkyl group. It is further preferred that R ^a3 is each independently an alkyl group, and at least one of R ^a2 and R ^a3 is a branched alkyl group. The branched alkyl group mentioned above is preferably a tert-butyl group.

In formula (a3), R ^a3 is preferably an alkyl group, more preferably a branched alkyl group. The branched alkyl group mentioned above is preferably a tert-butyl group.

In formulas (a1) to (a3), when n is 1, L ^a1 represents a hydrogen atom or a substituent. Examples of the substituent represented by L ^a1 include the groups described for the substituent T above.
In formulas (a1) to (a3), when n is 2 or more, L ^a1 represents an n-valent linking group. The n-valent linking group represented by L ^a1 includes a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, -SO ₂ -, and , a combination of two or more of these groups. R represents a hydrogen atom, an alkyl group or an aryl group.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be cyclic or acyclic. Further, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent T described below. Further, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused rings.
The heterocyclic group may be a single ring or a condensed ring. Examples of the heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom, and the like.

In formulas (a1) to (a3), n represents an integer of 1 or more, preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and an integer of 2 to 4. More preferably.

The molecular weight of the phenolic antioxidant is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1170 or less.

Specific examples of phenolic antioxidants include compounds a-1 to a-8 described in Examples described later, compounds described in paragraph number 0054 of International Publication No. 2019/065021, and the like. Commercially available products can also be used as the phenolic antioxidant. Representative examples of commercially available products include ADEKA STAB AO-20, 30, 40, 50, 60, 70, and 80 (manufactured by ADEKA Co., Ltd.).

(Amine antioxidant)
Examples of the amine antioxidant include compounds represented by formulas (c1) to (c5), with compounds represented by formula (c1) being preferred.

In formula (c1), R ^c1 represents a hydrogen atom, an alkyl group, an alkoxy group, or an oxy radical, R ^c2 to R ^c5 each independently represent an alkyl group having 1 to 4 carbon atoms, and n is 1 or more, and when n is 1, L ^c1 represents a hydrogen atom or a substituent, and when n is 2 or more, L ^c1 represents an n-valent linking group. Examples of the substituent represented by L ^c1 include the groups listed above for the substituent T. Examples of the n-valent linking group represented by L ^c1 include the groups described as the n-valent linking group represented by L ^a1 .
R ^c1 in formula (c1) is preferably an alkyl group, an alkoxy group, or an oxy radical, and more preferably an alkyl group or an oxy radical.
In formula (c1), n is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and even more preferably an integer of 1 to 4.

In formula (c2), R ^c11 and R ^c12 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group. The alkyl group, alkenyl group, aryl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group and carbamoyl group may have a substituent. Examples of the substituent include the groups listed above for the substituent T.

In formula (c3), V ^c3 represents a hydrogen atom or a substituent, and R ^c13 to R ^c16 each independently represent a hydrogen atom or a substituent.
In formula (c4), V ^c4 represents a hydrogen atom or a substituent, and R ^c17 to R ^c20 each independently represent a hydrogen atom or a substituent.
In formula (c5), V ^c5 to V ^c8 each independently represent a hydrogen atom or a substituent, V ^c5 and V ^c6 may be combined to form a ring, and V ^c7 and V ^c8 are a bond. may form a ring, and R ^c21 represents a hydrogen atom or a substituent.

Examples of the substituents represented by V ^c4 to V ^c8 include the groups listed above for the substituent T.
Examples of the substituents represented by R ^c13 to R ^c21 include an alkyl group and an aryl group.

The molecular weight of the amine antioxidant is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1170 or less.

Specific examples of amine antioxidants include compounds c-1 to c-7 described in Examples below. Commercially available amine antioxidants can also be used. Commercially available products include ADEKA STAB LA-52, LA-57, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402AF, LA-502XP (ADEKA Co., Ltd.) ), TINUVIN 765, TINUVIN 770 DF, TINUVIN XT 55 FB, TINUVIN 111 FDL, TINUVIN 783 FDL, TINUVIN 791 FB (BAS (manufactured by F).

(quencher)
Examples of the quencher include compounds that have the effect of deactivating the excited state of an infrared absorber such as a specific compound and suppressing oxidation of the specific compound. The quencher includes an electron-donating quencher and an electron-accepting quencher. An electron-donating quencher is one that donates electrons to the lower energy level SOMO of the two SOMOs (single occupied molecular orbitals) of a compound in an excited state, and then receives electrons from the higher energy level SOMO of the compound. This is a compound that has the effect of deactivating a compound in an excited state to a ground state and quenching the light. An electron-accepting quencher is one that receives electrons from the higher energy level SOMO of the two SOMOs (single occupied molecular orbitals) of a compound in an excited state, and then donates electrons to the lower energy level SOMO of the compound. This is a compound that has the effect of deactivating a compound in an excited state to a ground state and quenching the light.

Examples of the quencher include a compound represented by formula (d1), a compound represented by formula (d3), a compound represented by formula (d4), a compound represented by formula (d5), and a compound represented by formula (d6). Compounds represented by formula (d7), compounds represented by formula (d8), and compounds represented by formula (d9), hydroquinones, aminophenols, aminonaphthols, 3-pyrazolidinone saccharin and their precursors, picoliniums, etc.

-Compound represented by formula (d1)-

In formula (d1), R ^d1 represents an alkyl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a trialkylsilyl group,
A represents a nonmetallic atom necessary to complete a 5- or 6-membered ring,
R ^d2 , R ^d3 and R ^d4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkoxy group,
It represents an alkenyl group, an alkenoxy group, an acylamino group, a halogen atom, an alkylthio group, a diacylamino group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, an acyl group, or a sulfonamide group.

Note that the compound represented by formula (d1) also includes a bisspiro compound in which ring A contains a spiro atom. The bisspiro compound, which is a preferred form of the compound represented by formula (d1), includes a compound represented by formula (d1-1). R ^d5 , R ^d6 , R ^d7 , and R ^d8 in formula (d1-1) have the same meanings as R ^d1 , R ^d2 , R ^d3 , and R ^d4 in formula (d1). Furthermore, R ^d9 , R ^d10 , R ^d11 , and R ^d12 in formula (d1-1) are synonymous with R ^d1 , R ^d2 , R ^d3 , and R ^d4 in formula (d1).

-Compound represented by formula (d3)-

In formula (d3), R ^d13 , R ^d14 , and R ^d15 each independently represent an alkyl group, an aryl group, or a heterocyclic group. However, in R ^d13 and R ^d14 , the carbon atom directly bonded to the nitrogen atom is not substituted with an oxo group, thioxo group, or imino group. R ^d16 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

A preferred form of the compound represented by formula (d3) is a compound represented by formula (d3-1).

R ^d17 and R ^d18 in formula (d3-1) each independently represent an alkyl group, an aryl group, or a heterocyclic group. However, in R ^d17 and R ^d18 , the carbon atom directly bonded to the nitrogen atom is not substituted with an oxo group, thioxo group, or imino group.
R ^d19 and R ^d20 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
V ¹ , V ² , V ³ and V ⁴ each represent a hydrogen atom or a substituent.
L ₁ , L ₂ and L ₃ each represent a methine group.
n ₁ represents 0 or 1.

-Compound represented by formula (d4)-

In formula (d4), R ^A1 and R ^A2 each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, or an alkylthio group,
X is a group of nonmetallic atoms that is composed of a carbon atom, an oxygen atom, and/or a nitrogen atom, and together with -C(=O)-C(R ^A1 )=C(R ^A2 )- constitutes a 5- to 6-membered ring. represent.

R ^A1 and R ^A2 in formula (d4) are preferably a hydroxy group, an amino group, an alkylsulfonylamino group or an arylsulfonylamino group, more preferably a hydroxy group or an amino group, and even more preferably a hydroxy group.

X in formula (d4) has at least one -O- bond, -C(R ^A3 )(R ^A4 )-, -C(R ^A5 )=, -C(=O)-, -N( It is preferable to be composed of one or a combination of two or more of R ^a )- and N=. Here, R ^A3 to R ^A5 and R ^a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a hydroxy group, or a carboxy group.

The above-mentioned 5- to 6-membered ring formed via X in formula (d4) includes a cyclopentenone ring (2-cyclopenten-1-one ring; the formed compound becomes reductin acid), a furanone ring [ 2(5H)-furanone ring], dihydropyranone ring [3,4-dihydro-2H-pyran-4-one ring (2,3-dihydro-4H-pyrone ring), 3,6-dihydro-2H-pyran -2-one ring, 3,6-dihydro-2H-pyran-6-one ring (5,6-dihydro-2-pyrone ring)], 3,4-dihydro-2H-pyrone ring, and cyclopene A tenone ring, a furanone ring, and a dihydropyrone ring are preferred, a furanone ring and a dihydropyrone ring are more preferred, and a furanone ring is even more preferred. These rings may be condensed, and the condensed ring may be either a saturated ring or an unsaturated ring.

The compound represented by formula (d4) is preferably a compound represented by formula (d4-1), and more preferably a compound represented by formula (d4-2).

In formula (d4-1), R ^a1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, which may have a substituent.
R ^a1 is preferably an alkyl group which may have a substituent, more preferably -CH(OR ^a3 )CH ₂ OR ^a2 , in which case it becomes a compound represented by formula (d4-2).

R ^a2 and R ^a3 in formula (d4-2) each independently represent a hydrogen atom, an alkyl group, an acyl group, or an alkoxycarbonyl group. R ^a2 and R ^a3 may be combined with each other to form a ring. The ring formed is preferably a 1,3-dioxolane ring. The formed ring may further have a substituent.

In formula (d4-2), one of the preferred combinations of substituents is a compound in which R ^a2 is an acyl group and R ^a3 is a hydrogen atom. The acyl group may be an aliphatic acyl group or an aromatic acyl group. In the case of an aliphatic acyl group, the number of carbon atoms is preferably 2 to 30, more preferably 4 to 24, and even more preferably 8 to 18. In the case of an aromatic acyl group, the number of carbon atoms is preferably 7 to 24, more preferably 7 to 22, and even more preferably 7 to 18. Preferred acyl groups include butanoyl group, hexanoyl group, 2-ethylhexanoyl group, decanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, palmitoyl group, myristrail group, oleoyl group, benzoyl group, 4 Examples include -methylbenzoyl group and 2-methylbenzoyl group.

-Compound represented by formula (d5)-

In formula (d5), R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a carboxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or a heterocyclic group. R ^B3 and R ^B4 each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, or a mercapto group.

The alkyl group represented by R ^B1 and R ^B2 preferably has 1 to 10 carbon atoms. The alkyl group represented by R ^B1 and R ^B2 may be linear, branched, or cyclic. Specific examples of the alkyl group include methyl group, ethyl group, t-butyl group, cyclopropyl group, cyclopentyl group, and cyclohexyl group.
The alkenyl group represented by R ^B1 and R ^B2 preferably has 2 to 10 carbon atoms. The alkyl groups represented by R ^B1 and R ^B2 may be linear or branched. Specific examples of the alkenyl group include a vinyl group and an allyl group, with a vinyl group being preferred.
The alkyl group and alkenyl group may have a substituent. The substituent is preferably at least one selected from a hydroxy group, a carboxy group, and a sulfo group. When the alkenyl group is a vinyl group, it is also preferably a vinyl group substituted with a carboxy group.

The aryl group represented by R ^B1 and R ^B2 preferably has 6 to 12 carbon atoms. The aryl group may have a substituent. The substituent is preferably at least one selected from an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a halogen atom, a nitro group, and a cyano group.
The acyl group represented by R ^B1 and R ^B2 is preferably a formyl group, an acetyl group, an isobutyryl group, or a benzoyl group.
The amino group represented by R ^B1 and R ^B2 includes an amino group, an alkylamino group, an arylamino group, and includes an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a dipropylamino group, and a phenylamino group. or N-methyl-N-phenylamino group.

The alkoxy group represented by R ^B1 and R ^B2 preferably has 1 to 10 carbon atoms. Preferably, the alkoxy group is a methoxy group or an ethoxy group.
The alkoxycarbonyl group represented by R ^B1 and R ^B2 is preferably a methoxycarbonyl group.
In the heterocyclic group represented by R ^B1 and R ^B2 , the ring-constituting heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring structure is preferably a 5-membered ring or a 6-membered ring. This heterocyclic group may be an aromatic heterocyclic group, a saturated heterocyclic group, or may be fused. The heterocycle in the heterocyclic group is preferably a pyridine ring, pyrimidine ring, pyrrole ring, furan ring group, thiophene ring, pyrazole ring, piperidine ring, piperazine ring or morpholine ring.

R ^B1 and R ^B2 are preferably each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The amino group represented by R ^B3 and R ^B4 includes an amino group, an alkylamino group, an arylamino group, and an amino group, an alkylamino group such as an amino group, a methylamino group, an ethylamino group, an n-butylamino group, a hydroxyethylamino group, etc. Groups are preferred.
The acylamino group represented by R ^B3 and R ^B4 is preferably an acetylamino group or a benzoylamino group.
The alkylsulfonylamino group represented by R ^B3 and R ^B4 is preferably a methylsulfonylamino group.
The arylsulfonylamino group represented by R ^B3 and R ^B4 is preferably a benzenesulfonylamino group or a p-toluenesulfonylamino group.
The alkoxycarbonylamino group represented by R ^B3 and R ^B4 is preferably a methoxycarbonylamino group.
It is preferable that R ^B3 and R ^B4 are each independently a hydroxy group, an amino group, an alkylsulfonylamino group, or an arylsulfonylamino group.

-Compounds represented by formulas (d6) to (d8)-
In formula (d6), R ^d21 represents an alkyl group or an aryl group.
In formula (d7), R ^d22 and R ^d23 each independently represent an alkyl group or an aryl group.
In formula (d8), R ^d24 and R ^d25 each independently represent an alkyl group or an aryl group.

-Compound represented by formula (d9)-
In formula (d9), R ^d26 , R ^d27 , R ^d28 , and R ^d29 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an arylthio group, an aryloxy group, a halogen atom, or a cyano group. represents a group, and R ^d26 and R ^d27 or R ^d28 and R ^d29 may be connected to each other to form a ring.

Specific examples of the quencher include compounds d-1 to d-6 described in Examples below, compounds described in paragraph numbers 0194 to 0310 of International Publication No. 2019/066043, and the like.

(Singlet oxygen scavenger)
Examples of the singlet oxygen scavenger include compounds that have the effect of scavenging singlet oxygen. Specific examples of singlet oxygen scavengers include ethylenic compounds such as tetramethylethylene and cyclopentene; amines such as diethylamine, triethylamine, 1,4-diazabicyclooctane (DABCO), and N-ethylimidazole; Fused polycyclic aromatic compounds such as naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene, diphenylanthracene; 1,3-diphenylisobenzofuran, 1,2,3,4-traphenyl-1,3-cyclopentadiene, penta Examples include aromatic compounds such as phenylcyclopentadiene. Also, Harry H. Wasserman, Singlet Oxygen, Chapter 5, Academic Press (1979), Nicholas J. Turro, Modern Molecular Photochemistry, Chapter 14, The Benjamin Cummings Publishing Co. , Inc. (1978) and "High Functional Chemicals for Color Photographic Materials" published by CMC, Chapter 7 (2002), compounds exemplified as singlet oxygen scavengers can also be used.

The content of the browning inhibitor is preferably 0.1 to 30% by mass based on the total solid content of the composition. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
Further, the content of the anti-browning agent is preferably 1 to 1500 parts by weight per 100 parts by weight of the specific compound. The upper limit is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less. The lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more.

<<Curable compound>>
The composition of the invention contains a curable compound. Examples of the curable compound include polymerizable compounds, resins, and the like. The resin may be a non-polymerizable resin (resin that does not have a polymerizable group) or a polymerizable resin (resin that has a polymerizable group). Examples of the polymerizable group include an ethylenically unsaturated bond-containing group, a cyclic ether group, a methylol group, and an alkoxymethyl group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, vinylphenyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, etc. Allyl group, (meth)acryloyl group and (meth)acryloyloxy group are preferred, and (meth)acryloyloxy group is more preferred. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with an epoxy group being preferred.

As the curable compound, it is preferable to use one containing at least a resin. Further, when the composition of the present invention is used as a composition for photolithography, it is preferable to use a resin and a polymerizable monomer (monomer type polymerizable compound) as the curable compound. It is more preferable to use a polymerizable monomer (monomer type polymerizable compound) having an unsaturated bond-containing group.

(Polymerizable compound)
Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group, a compound having a cyclic ether group, a compound having a methylol group, a compound having an alkoxymethyl group, and the like. A compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound. Moreover, a compound having a cyclic ether group can be preferably used as a cationically polymerizable compound.

Examples of resin-type polymerizable compounds include resins containing repeating units having polymerizable groups.

The molecular weight of the monomer-type polymerizable compound (polymerizable monomer) is preferably less than 2,000, more preferably 1,500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more. The weight average molecular weight (Mw) of the resin type polymerizable compound is preferably 2,000 to 2,000,000. The upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit of the weight average molecular weight is preferably 3,000 or more, more preferably 5,000 or more.

The compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, and JP 2013-253224. Described in paragraph numbers 0034 to 0038 of the publication, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662. , the contents of which are incorporated herein.

Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available) Examples of commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa (meth) ) acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.; NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the (meth)acryloyl group of these compounds is ethylene glycol and and/or compounds having a structure in which they are bonded via a propylene glycol residue (eg, SR454, SR499, commercially available from Sartomer). Further, as compounds having an ethylenically unsaturated bond-containing group, diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin Nakamura Chemical Co., Ltd.) (manufactured by Nippon Kayaku Co., Ltd., NK ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Nippon Kayaku Co., Ltd.) Toagosei Co., Ltd.), NK Oligo UA-7200 (Shin Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (Kyoeisha Chemical Co., Ltd.) ) etc. can also be used.

In addition, examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, and isocyanuric acid ethylene oxide. It is also preferable to use trifunctional (meth)acrylate compounds such as modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.

The compound having an ethylenically unsaturated bond-containing group may further have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group. Commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.

As the compound having an ethylenically unsaturated bond-containing group, a compound having a caprolactone structure can also be used. Regarding the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP-A No. 2013-253224 can be referred to, the contents of which are incorporated herein. Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available as a series from Nippon Kayaku Co., Ltd.

As the compound having an ethylenically unsaturated bond-containing group, a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used. Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, and preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. More preferably, it is a 3- to 6-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available products include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. Examples include KAYARAD TPA-330.

As the compound having an ethylenically unsaturated bond-containing group, a polymerizable compound having a fluorene skeleton can also be used. Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).

As the compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound substantially free of environmentally regulated substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Examples of the compound having a cyclic ether group include a compound having an epoxy group, a compound having an oxetanyl group, etc., and a compound having an epoxy group is preferable. Examples of compounds having epoxy groups include compounds having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably 2 or more.

The compound having a cyclic ether group may be a low molecular compound (for example, molecular weight less than 1000) or a macromolecule (for example, molecular weight 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

Examples of compounds having a cyclic ether group include compounds described in paragraph numbers 0034 to 0036 of JP-A No. 2013-011869, compounds described in paragraph numbers 0147 to 0156 of JP-A-2014-043556, and JP-A No. 2014. Compounds described in paragraph numbers 0085 to 0092 of JP-A-089408 and compounds described in JP-A-2017-179172 can also be used.

Commercially available compounds having a cyclic ether group include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX -850 (manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC -7300, ) Daicel), Cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (manufactured by Daicel Corporation), jER1031S, jER157S65, jER152, jER154, jER157S70 (all manufactured by Mitsubishi Chemical Corporation) ), Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.), ADEKA Glycilol ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), Proof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group) containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10, OXE-30 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) Co., Ltd., oxetanyl group-containing monomer).

Examples of compounds having a methylol group (hereinafter also referred to as methylol compounds) include compounds in which a methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
Examples of compounds having an alkoxymethyl group (hereinafter also referred to as alkoxymethyl compounds) include compounds in which an alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethylated Preferred are urea and methylolated urea. Further, compounds described in paragraphs 0134 to 0147 of JP-A No. 2004-295116 and paragraphs 0095 to 0126 of JP-A No. 2014-089408 can also be used.

(resin)
The composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound containing at least a resin. The resin is blended, for example, for dispersing pigments and the like in the composition or for use as a binder. Note that a resin used mainly for dispersing pigments and the like in a composition is also referred to as a dispersant. However, this use of the resin is just one example, and the resin can also be used for purposes other than this use. Note that the resin having a polymerizable group also corresponds to a polymerizable compound.

The weight average molecular weight of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Examples of resins include (meth)acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Examples include polyamide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyurethane resin, and polyurea resin. One type of these resins may be used alone, or two or more types may be used in combination. As the cyclic olefin resin, norbornene resin is preferable from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (eg, ARTON F4520). In addition, the resins include the resin described in the examples of International Publication No. 2016/088645, the resin described in JP 2017-057265, the resin described in JP 2017-032685, and the resin described in JP 2017-032685. The resin described in JP 2017-075248, the resin described in JP 2017-066240, the resin described in JP 2017-167513, the resin described in JP 2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP 2017-206689, resins described in paragraph numbers 0022 to 0071 of JP 2018-010856, and blocks described in JP 2016-222891. Polyisocyanate resin, resin described in JP 2020-122052, resin described in JP 2020-111656, resin described in JP 2020-139021, JP 2017-138503 It is also possible to use a resin containing a constitutional unit having a ring structure in the main chain and a constitutional unit having a biphenyl group in the side chain as described in . Further, as the resin, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, the description in US Patent Application Publication No. 2017/0102610 can be referred to, the contents of which are incorporated herein. In addition, examples of the resin include resins described in paragraphs 0199 to 0233 of JP2020-186373A, alkali-soluble resins described in JP2020-186325A, and Korean Patent Publication No. 10-2020-0078339. A resin represented by Formula 1 can also be used.

It is preferable to use a resin having acid groups as the resin. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. The number of these acid groups may be one, or two or more. A resin having an acid group can also be used as a dispersant. The acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, even more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

As the resin, a resin containing a repeating unit derived from a compound represented by formula (ED1) and/or a compound represented by formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer") is used. It is also preferable to include.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of formula (ED2), the description in JP-A No. 2010-168539 can be referred to.

For specific examples of ether dimers, paragraph number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.

As the resin, it is also preferable to use a resin having a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group.

As the resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by formula (X).
In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0 to 15. The alkylene group represented by R ²¹ and R ²² preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 2 or 3 carbon atoms. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 3.

Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

It is preferable that the resin contains a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. The acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. Moreover, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group that the basic dispersant has is preferably an amino group.

It is also preferable that the resin used as a dispersant is a graft resin. For details of the graft resin, the descriptions in paragraphs 0025 to 0094 of JP-A No. 2012-255128 can be referred to, the contents of which are incorporated herein.

It is also preferable that the resin used as a dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. Preferably, the resin has The basic nitrogen atom is not particularly limited as long as it exhibits basicity. Regarding the polyimine dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.

It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.

The resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in its side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol% of the total repeating units of the resin. More preferably, it is mol%.

In addition, as a dispersant, resins described in JP 2018-087939, block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, Polyethyleneimine having a polyester side chain as described in International Publication No. 2016/104803, block copolymer as described in International Publication No. 2019/125940, block polymer having an acrylamide structural unit as described in JP-A No. 2020-066687 , a block polymer having an acrylamide structural unit described in JP-A No. 2020-066688, etc. can also be used.

Dispersants are also available as commercial products, and specific examples include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Japan Lubrizol, the Efka series manufactured by BASF, and Ajinomoto Fine Techno Co., Ltd. Examples include the Ajisper series manufactured by Manufacturer. Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.

The content of the curable compound is preferably 1 to 95% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 94% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less.

When the composition of the present invention contains a polymerizable compound as a curable compound, the content of the polymerizable compound is preferably 1 to 85% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.

When the composition of the present invention contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.

When the composition of the present invention contains a compound having an ethylenically unsaturated bond-containing group as a curable compound, the content of the compound having an ethylenically unsaturated bond-containing group is 1 to 70% by mass in the total solid content of the composition. % is preferred. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.

When the composition of the present invention contains a resin as a curable compound, the content of the resin is preferably 1 to 85% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 40% by mass or less.

When the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 0.1 to 40% by mass based on the total solid content of the composition. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Further, the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the above-mentioned specific dye. The upper limit is preferably 80 parts by mass or less, more preferably 75 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass or more.

The composition of the present invention may contain only one type of curable compound, or may contain two or more types. When two or more types of curable compounds are included, the total amount thereof is preferably within the above range.

<<Solvent>>
The composition of the present invention preferably contains a solvent. Examples of the solvent include water and organic solvents, with organic solvents being preferred. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For these details, paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxy Butanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as Examples include diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).

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

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

The organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.

It is preferable that the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no peroxide.

The content of the solvent in the composition is preferably 10 to 97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and 70% by mass. It is particularly preferable that it is above. The upper limit is preferably 96% by mass or less, more preferably 95% by mass or less. The composition may contain only one kind of solvent, or may contain two or more kinds. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Photopolymerization initiator>>
When the composition of the present invention contains a polymerizable compound, it is preferable that the composition of the present invention further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet to visible range are preferred. The photopolymerization initiator is preferably a radical photopolymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylbylene compounds. Preferred are imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, α-hydroxyketones The compound is more preferably a compound selected from a compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, as photopolymerization initiators, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A No. 2019-044030, the peroxide-based initiator described in JP-A No. 2019-167313, the photopolymerization initiator described in JP-A No. 2020-055992 The aminoacetophenone initiator having an oxazolidine group as described, the oxime photopolymerization initiator described in JP 2013-190459, the polymer described in JP 2020-172619, the WO 2020/152120 Examples include compounds represented by Formula 1, the contents of which are incorporated herein.

Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc. can be mentioned.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 1. 173, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure. 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF) (manufactured by). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.

Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000 - Compounds described in Publication No. 066385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No. 2017 /051680, compounds described in JP 2017-198865, compounds described in paragraph numbers 0025 to 0038 of WO 2017/164127, WO 2013/167515, WO 2017 /169819, and the compounds described in paragraph numbers 0029 to 0044 of JP-A-2019-168654. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by Tronley), and Adeka Optomer N-1919. ((stock) ) Photopolymerization initiator 2) manufactured by ADEKA and described in JP-A-2012-014052. Further, as the oxime compound, it is also preferable to use a compound without coloring property or a compound with high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Co., Ltd.).

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compounds described in JP-A No. 2014-137466, the compounds described in Japanese Patent No. 6636081, and the compounds described in Korean Patent Publication No. 10-2016-0109444. It will be done.

As the photopolymerization initiator, it is also possible to use an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

As a photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of oxime compounds having a fluorine atom include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is in the form of a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

As a photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As a photopolymerization initiator, it is also possible to use an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055.

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

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. In addition, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photopolymerization initiator, a difunctional, trifunctional or more functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. Furthermore, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in solvents and the like improves, making it difficult to precipitate over time, thereby improving the stability of the composition over time. Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Application Publication No. 2016-532675. Dimers of oxime compounds described in paragraph numbers 0407 to 0412, paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound ( G), Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester initiator described in paragraph number 0007 of Japanese Patent Application Publication No. 2017-523465, paragraph of Japanese Patent Application Publication No. 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP2017-151342A, oxime described in Japanese Patent No. 6469669 Examples include ester-based initiators.

The content of the photopolymerization initiator is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight, and even more preferably 1 to 30% by weight based on the total solid content of the composition. The composition may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Curing agent>>
When the composition of the present invention contains a compound having a cyclic ether group, it is preferable that the composition further contains a curing agent. Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polyhydric carboxylic acids, and thiol compounds. Specific examples of the curing agent include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), and the like. As the curing agent, compounds described in paragraph numbers 0072 to 0078 of JP-A No. 2016-075720 and compounds described in JP-A No. 2017-036379 can also be used. The content of the curing agent is preferably 0.01 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and 0.1 to 6.0 parts by weight per 100 parts by weight of the compound having a cyclic ether group. is even more preferable.

<<Acid generator>>
The composition of the present invention may contain an acid generator. The acid generator is preferably a compound that generates an acid upon irradiation with light (photoacid generator). Examples of acid generators include onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, imidosulfonates, oxime sulfonates, diazodisulfones, disulfones, and ortho-nitrobenzylsulfonates, which decompose to generate acids when exposed to light. Examples include sulfonate compounds such as. Types, specific compounds, and preferred examples of the acid generator include compounds described in paragraphs 0066 to 0122 of JP-A No. 2008-013646.

Commercially available acid generators include the WPAG series manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. and the CPI series (CPI-100P, etc.) manufactured by San-Apro Co., Ltd.

The content of the acid generator is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight, and even more preferably 1 to 30% by weight based on the total solid content of the composition. The composition may contain only one kind of acid generator, or may contain two or more kinds. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Chromatic colorant>>
The compositions of the invention can contain chromatic colorants. In the present invention, a chromatic colorant means a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant having absorption in a wavelength range of 400 nm or more and less than 650 nm.

Chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. The chromatic colorant may be a pigment or a dye. A pigment and a dye may be used together. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or an organic-inorganic pigment partially substituted with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.

The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the composition is good. In the present invention, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles. Moreover, the primary particles of pigment refer to independent particles without agglomeration.

The chromatic colorant preferably contains a pigment. The content of pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. It is particularly preferable. Examples of pigments include those shown below.

Color Index (C.I.) 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, 215, 228, 231, 232 (methine type), 233 (quinoline type), 234 ( (aminoketone type), 235 (aminoketone type), 236 (aminoketone type), etc. (yellow pigments),
C. I. 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. (Above, orange pigment)
C. I. 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, 269, 270, 272, 279, 291, 294 (xanthene type, Organo Ultramarine, Bluish Red), 295 (monoazo type), 296 (diazo type), 297 (aminoketone type), etc. (red pigments),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine type), 65 (phthalocyanine type), 66 (phthalocyanine type), etc. (green pigments),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane type), 61 (xanthene type), etc. (purple pigments),
C. I. Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,29,60,64,66,79,80,87 (monoazo type), 88 (methine type), etc. (the above are blue pigments).

In addition, as a green pigment, halogenated zinc phthalocyanine pigments have an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average of 2 to 5 chlorine atoms. You can also use Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green pigment, a compound described in Chinese Patent Application No. 106909027, a phthalocyanine compound having a phosphoric acid ester as a ligand described in International Publication No. 2012/102395, a phthalocyanine compound described in JP-A No. 2019-008014, A phthalocyanine compound, a phthalocyanine compound described in JP 2018-180023, a compound described in JP 2019-038958, a core-shell type dye described in JP 2020-076995, etc. can also be used.

Additionally, an aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.

In addition, as yellow pigments, compounds described in JP-A No. 2017-201003, compounds described in JP-A No. 2017-197719, and compounds described in paragraph numbers 0011-0062 and 0137-0276 of JP-A No. 2017-171912 are used. Compounds, compounds described in paragraph numbers 0010 to 0062, 0138 to 0295 of JP 2017-171913, compounds described in paragraph numbers 0011 to 0062, 0139 to 0190 of JP 2017-171914, JP 2017- Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A No. 171915, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A No. 2013-054339, and paragraph numbers 0013 to 0058 of JP-A-2014-026228. The quinophthalone compound described in JP 2018-062644, the quinophthalone compound described in JP 2018-203798, the quinophthalone compound described in JP 2018-062578, and Japanese Patent No. 6432076. Quinophthalone compounds described in the publication, quinophthalone compounds described in JP2018-155881, quinophthalone compounds described in JP2018-111757, quinophthalone compounds described in JP2018-040835, JP2017- Quinophthalone compounds described in JP 2016-145282, quinophthalone compounds described in JP 2014-085565, quinophthalone compounds described in JP 2014-021139, JP 2014-021139; Quinophthalone compounds described in JP2013-209614, quinophthalone compounds described in JP2013-209435, quinophthalone compounds described in JP2013-181015, quinophthalone compounds described in JP2013-061622, Quinophthalone compounds described in JP2013-032486A, quinophthalone compounds described in JP2012-226110A, quinophthalone compounds described in JP2008-074987A, quinophthalone compounds described in JP2008-081565A Compounds, quinophthalone compounds described in JP 2008-074986, quinophthalone compounds described in JP 2008-074985, quinophthalone compounds described in JP 2008-050420, quinophthalone compounds described in JP 2008-031281 Quinophthalone compounds described in Japanese Patent Publication No. 48-032765, Quinophthalone compounds described in Japanese Patent Application Publication No. 2019-008014, Quinophthalone compounds described in Japanese Patent No. 6607427, Korean Published Patent No. 10-2014-0034963 Compounds described in Japanese Patent Publication No. 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Japanese Patent No. 6607427, compounds described in Japanese Patent Application Publication No. 2020-033525 Compounds described in JP2020-033524A, compounds described in JP2020-033523A, compounds described in JP2020-033522A, compounds described in JP2020-033521A Compounds described in International Publication No. 2020/045200, compounds described in International Publication No. 2020/045199, and compounds described in International Publication No. 2020/045197 can also be used. Furthermore, polymerized versions of these compounds are also preferably used from the viewpoint of improving color value.

As a red pigment, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP 2017-201384, a diketopyrrolopyrrole compound described in paragraph numbers 0016 to 0022 of Patent No. 6248838, Diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, naphthol azo compounds described in JP2012-229344A, Patent No. 6516119 Red pigment described in the publication, red pigment described in Patent No. 6525101, brominated diketopyrrolopyrrole compound described in paragraph number 0229 of JP 2020-090632, Korean Published Patent No. 10-2019-0140741 Anthraquinone compounds described in the publication, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, perylene compounds described in JP 2020-079396, etc. can also be used. Further, as a red pigment, a compound having a structure in which an aromatic ring group into which a group to which an oxygen atom, sulfur atom, or nitrogen atom is bonded is bonded to a diketopyrrolopyrrole skeleton may also be used. can.

Regarding the diffraction angles that various pigments preferably have, the descriptions in Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, and Japanese Patent Application Laid-open No. 2020-026503 can be referred to. Incorporated herein. In addition, as a pyrrolopyrrole pigment, the crystallite size in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes (±1±1±1) of the crystal lattice planes is 140 Å or less. It is also preferable to use one. Furthermore, it is also preferable to set the physical properties of the pyrrolopyrrole pigment as described in paragraphs 0028 to 0073 of JP-A-2020-097744.

Dyes can also be used as chromatic colorants. There are no particular restrictions on the dye, and any known dye can be used. For example, pyrazole azo dyes, anilinoazo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, and phenothiazines. Examples include pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyrromethene dyes, and the like.

Pigment multimers can also be used as chromatic colorants. The dye multimer is preferably a dye that is dissolved in a solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent. The dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may be the same dye structure or may be different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, WO 2016/031442, etc. Compounds can also be used.

In addition, chromatic colorants include thiazole compounds described in JP-A No. 2012-158649, azo compounds described in JP-A No. 2011-184493, azo compounds described in JP-A No. 2011-145540, and azo compounds described in JP-A No. 2011-145540. Triarylmethane dye polymer described in Patent No. 10-2020-0028160, xanthene compound described in JP 2020-117638, phthalocyanine compound described in WO 2020/174991, JP 2020-160279 The isoindoline compounds or salts thereof described in the above publication can be used.

When the composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention. When the composition of the present invention contains two or more chromatic colorants, the total amount thereof is preferably within the above range. When the composition of the present invention contains two or more chromatic colorants, the total amount thereof is preferably within the above range.

When the composition of the present invention is used for an infrared cut filter, it is preferable that the composition of the present invention does not substantially contain a chromatic colorant. In addition, when the composition of the present invention does not substantially contain a chromatic colorant, the content of the chromatic colorant in the total solid content of the composition of the present invention is 0.5% by mass or less. This means that it is preferably 0.1% by mass or less, and more preferably does not contain a chromatic colorant.

<<Color material that transmits infrared rays and blocks visible light>>
The composition of the present invention can also contain a coloring material that transmits infrared rays and blocks visible light (hereinafter also referred to as a coloring material that blocks visible light). A composition containing a coloring material that blocks visible light is preferably used as a composition for forming an infrared transmission filter.

The coloring material that blocks visible light is preferably a coloring material that absorbs light in the wavelength range from violet to red. Further, the coloring material that blocks visible light is preferably a coloring material that blocks light in a wavelength range of 450 to 650 nm. Further, the coloring material that blocks visible light is preferably a coloring material that transmits light with a wavelength of 900 to 1500 nm. The coloring material that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
(A): Contains two or more types of chromatic colorants, and black color is formed by a combination of two or more types of chromatic colorants.
(B): Contains an organic black colorant.

Examples of the chromatic colorant include those mentioned above. Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. Examples of bisbenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, and Japanese Patent Application Publication No. 2012-515234, and for example, as "Irgaphor Black" manufactured by BASF. available. Examples of perylene compounds include compounds described in paragraph numbers 0016 to 0020 of JP-A No. 2017-226821, C.I. I. Pigment Black 31, 32, etc. Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichiseika Kaisha, Ltd., for example.

When a black color is formed by a combination of two or more chromatic colorants, examples of the combination of chromatic colorants include the following embodiments (1) to (8).
(1) Embodiment containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant.
(2) Embodiment containing a yellow colorant, a blue colorant, and a red colorant.
(3) Embodiment containing a yellow colorant, a purple colorant, and a red colorant.
(4) Embodiment containing a yellow colorant and a purple colorant.
(5) An embodiment containing a green colorant, a blue colorant, a purple colorant, and a red colorant.
(6) Embodiment containing a purple colorant and an orange colorant.
(7) Embodiment containing a green colorant, a purple colorant, and a red colorant.
(8) Embodiment containing a green colorant and a red colorant.

When the composition of the present invention contains a colorant that blocks visible light, the content of the colorant that blocks visible light is preferably 1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more.

When the composition of the present invention is used for an infrared cut filter, it is preferable that the composition of the present invention does not substantially contain a coloring material that blocks visible light. Note that the case where the composition of the present invention does not substantially contain a colorant that blocks visible light means that the content of the colorant that blocks visible light in the total solid content of the composition of the present invention is 0. This means 5% by mass or less, preferably 0.1% by mass or less, and more preferably no coloring material that blocks visible light.

<<Pigment derivative>>
The composition of the invention may further contain a pigment derivative. Pigment derivatives are used as dispersion aids. Examples of pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.

The pigment skeletons constituting the pigment derivatives include squarylium pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, benzisoindole pigment skeleton, and thiazine indigo pigment skeleton. , azo dye skeleton, quinophthalone dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, dioxazine dye skeleton, perylene dye skeleton, perinone dye skeleton, benzimidazolone dye skeleton, benzothiazole dye skeleton, benzimidazole dye skeleton and benzoxazole dye skeleton Examples include squarylium dye skeleton, pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, phthalocyanine dye skeleton, quinacridone dye skeleton and benzimidazolone dye skeleton, and squarylium dye skeleton and pyrrolopyrrole dye skeleton are more preferable.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imide acid group, and salts thereof. Atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ^{+ ,} etc.), alkaline earth metal ions (Ca ²⁺ , Mg ^{2+ ,} etc.), ammonium ions, imidazolium ions, pyridinium ions, Examples include phosphonium ions. As the carboxylic acid amide group, a group represented by -NHCOR ^A1 is preferable. As the sulfonamide group, a group represented by -NHSO ₂ R ^A2 is preferable. The imide acid group is preferably a group represented by -SO ₂ NHSO ₂ R ^A3 , -CONHSO ₂ R ^A4 , -CONHCOR ^A5 or -SO ₂ NHCOR ^A6 , and -SO ₂ NHSO ₂ R ^A3 is more preferred. R ^A1 to R ^A6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R ^A1 to R ^A6 may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.

Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

Specific examples of pigment derivatives include JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP 03-153780, JP 03-045662, JP 04-285669, JP 06-145546, JP 06-212088, JP 06-240158, JP 06-240158, Examples include compounds described in JP-A No. 10-030063, JP-A-10-195326, paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, and paragraph numbers 0063 to 0094 of International Publication No. 2012/102399.

The content of the pigment derivative is preferably 1 to 50 parts by weight based on 100 parts by weight of the pigment. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

<<Surfactant>>
Preferably, the composition of the invention contains a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The surfactant is preferably a silicone surfactant or a fluorine surfactant. Examples of the surfactant include the surfactants described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779, the contents of which are incorporated herein.

Examples of fluorine-based surfactants include surfactants described in paragraph numbers 0060 to 0064 of JP 2014-041318 (corresponding paragraph numbers 0060 to 0064 of WO 2014/017669), and the like; Examples include the surfactants described in paragraph numbers 0117 to 0132 of Publication No. 132503 and the surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560 , F-561, F-563, F-565, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R -41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo Corporation) 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by 3M Co., Ltd.), AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Ftergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 71 0FS, FTX-218 (all of which are manufactured by NEOS Co., Ltd.), and the like.

In addition, as fluorine-based surfactants, there are also acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing a fluorine atom is cut off and the fluorine atom volatizes. It can be used suitably. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), An example is DS-21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant. Examples of such fluorine-based surfactants include the fluorine-based surfactants described in JP-A No. 2016-216602, the content of which is incorporated herein.

A block polymer can also be used as the fluorosurfactant. As a fluorine-based surfactant, a (meth) having a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraph numbers 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion of repeating units is mol%.

Furthermore, a fluoropolymer having an ethylenically unsaturated bond-containing group in its side chain can also be used as the fluorinated surfactant. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, Examples include RS-72-K. Further, as the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

Furthermore, it is also preferable from the viewpoint of environmental regulations to use the surfactant described in International Publication No. 2020/084854 as a substitute for a surfactant having a perfluoroalkyl group having 6 or more carbon atoms.

It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.
In formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, and X ^a+ represents an a-valent metal ion, a primary ammonium ion, or Represents a secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH ₄ ⁺ .

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, 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 (BASF Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.) (manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) Examples include.

Examples of the cationic surfactant include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidemethylpyridium chloride, and the like.

Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl Examples include sodium sulfate salt.

Examples of silicone surfactants include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4440, TSF-4300 , TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie Co., Ltd.), and the like.

Moreover, a compound having the following structure can also be used as the silicone surfactant.

The content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and even more preferably 0.001 to 0.2% by mass based on the total solid content of the composition. . The composition may contain only one kind of surfactant, or may contain two or more kinds of surfactants. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Polymerization inhibitor>>
The composition of the present invention may contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), with p-methoxyphenol being preferred. The content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the composition. The composition may contain only one kind of polymerization inhibitor, or may contain two or more kinds of polymerization inhibitors. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Silane coupling agent>>
The composition of the present invention may contain a silane coupling agent. In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Furthermore, the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups. (meth)acryloyl group and epoxy group are preferred. Examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A No. 2009-288703, and compounds described in paragraph numbers 0056 to 0066 of JP-A No. 2009-242604, the contents of which are incorporated herein by reference. Incorporated into the specification. The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass based on the total solid content of the composition. The composition may contain only one type of silane coupling agent, or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Ultraviolet absorber>>
The composition of the present invention can contain a UV absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, dibenzoyl compounds, and the like. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraphs 0052 to 0072 of JP2012-208374A, and paragraphs 0317 to 0317 of JP2013-068814A. 0334, paragraph numbers 0061 to 0080 of JP 2016-162946, paragraph numbers 0052 and 0074 of International Publication No. 2021/131355, and paragraph numbers 0022 to 0024 of International Publication No. 2021/132247. , the contents of which are incorporated herein. Commercially available UV absorbers include the Tinuvin series and Uvinul series manufactured by BASF. Furthermore, examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Yushi (Kagaku Kogyo Nippo, February 1, 2016). Further, as the ultraviolet absorber, compounds described in paragraph numbers 0049 to 0059 of Patent No. 6268967 and paragraph numbers 0059 to 0076 of International Publication No. 2016/181987 can also be used. The content of the ultraviolet absorber is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass based on the total solid content of the composition. The composition may contain only one type of ultraviolet absorber, or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range.

＜＜Other ingredients＞＞
The composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, etc.). agent, peeling accelerator, fragrance, surface tension regulator, chain transfer agent, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described, for example, in paragraphs 0183 and after of JP-A-2012-003225 (corresponding paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812), and in paragraphs of JP-A-2008-250074. The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated into the present specification.

<Storage container>
The container for storing the composition of the present invention is not particularly limited, and any known container can be used. In addition, in order to prevent impurities from entering raw materials and compositions, we use multi-layer bottles with an inner wall made of 6 types of 6 layers of resin, and bottles with 7 layers of 6 types of resin as storage containers. It is also preferable to use Examples of such a container include the container described in JP-A No. 2015-123351. Furthermore, the inner wall of the container is preferably made of glass, stainless steel, or the like for the purpose of preventing metal elution from the inner wall of the container, increasing stability of the composition over time, and suppressing deterioration of components.

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the components described above. When preparing a composition, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, or if necessary, two or more solutions or dispersions containing each component may be prepared in advance. The composition may be prepared by mixing these at the time of use (at the time of application).

The preparation of the composition may include a process of dispersing the pigment. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In addition, when pulverizing pigments in a sand mill (bead mill), it is preferable to use small-diameter beads or increase the filling rate of the beads, thereby increasing the pulverizing efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the pulverization treatment. In addition, the process and dispersion machine for dispersing pigments are described in ``Complete Works of Dispersion Technology, Published by Information Technology Corporation, July 15, 2005'' and ``Dispersion technology centered on suspension (solid/liquid dispersion system) and industrial The process and dispersion machine described in Paragraph No. 0022 of JP 2015-157893 A, "Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used. Further, in the process of dispersing the pigment, the pigment may be subjected to a finer treatment in a salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example. Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Moreover, an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads. The composition may contain 1 to 10,000 ppm of the beads.

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

The pore diameter of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used. .

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

When using filters, different filters (for example, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed two or more times. Further, filters having different pore diameters within the above-mentioned range may be combined. Alternatively, only the dispersion liquid may be filtered with the first filter, and then filtered with the second filter after other components are mixed.

<Membrane>
Next, the membrane of the present invention will be explained. The membrane of the present invention is obtained from the composition of the present invention described above. The film of the present invention can be preferably used as an optical filter. Applications of the optical filter are not particularly limited, but include infrared cut filters, infrared transmission filters, and the like. Examples of the infrared cut filter include an infrared cut filter on the light receiving side of the solid-state image sensor (for example, an infrared cut filter for a wafer level lens, etc.), and an infrared cut filter on the back side of the solid-state image sensor (opposite side to the light receiving side). , infrared cut filters for environmental light sensors (for example, illuminance sensors that detect the illumination and color tone of the environment in which the information terminal device is placed and adjust the color tone of the display, and color correction sensors that adjust the color tone). It will be done. In particular, it can be preferably used as an infrared cut filter on the light receiving side of a solid-state image sensor. Examples of the infrared transmission filter include a filter that can block visible light and selectively transmit infrared rays having a specific wavelength or more.

The film of the present invention may have a pattern or may be a film without a pattern (flat film). Further, the membrane of the present invention may be used by being laminated on a support, or the membrane of the present invention may be used by being peeled off from the support. Examples of the support include semiconductor base materials such as silicon substrates and transparent base materials.

A charge coupled device (CCD), complementary metal oxide semiconductor (CMOS), transparent conductive film, etc. may be formed on the semiconductor substrate used as the support. Further, a black matrix may be formed on the semiconductor substrate to isolate each pixel. Further, an undercoat layer may be provided on the semiconductor substrate, if necessary, for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface.

The transparent substrate used as the support is not particularly limited as long as it is made of a material that can transmit at least visible light. Examples include base materials made of materials such as glass and resin. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymers, acrylic resins such as norbornene resins, polyacrylates, and polymethyl methacrylates, urethane resins, and vinyl chloride resins. , fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, and the like. Examples of the glass include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and glass containing copper. Examples of glass containing copper include phosphate glass containing copper, fluorophosphate glass containing copper, and the like. A commercially available glass containing copper can also be used. Examples of commercially available glass containing copper include NF-50 (manufactured by AGC Techno Glass Co., Ltd.).

The thickness of the film of the present invention can be adjusted as appropriate depending on the purpose. The thickness of the film can be 200 μm or less, 150 μm or less, 120 μm or less, 20 μm or less, 10 μm or less, and 5 μm or less. You can also do it. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more.

When the film of the present invention is used as an infrared cut filter, it is preferable that the film of the present invention has a maximum absorption wavelength in a wavelength range of 650 to 1500 nm (preferably a wavelength of 660 to 1200 nm, more preferably a wavelength of 660 to 1000 nm). . Further, the average transmittance of light with a wavelength of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, even more preferably 80% or more, and especially 85% or more. preferable. Further, the transmittance over the entire wavelength range of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more. Further, the film of the present invention preferably has a transmittance of 15% or less at at least one point in the wavelength range of 650 to 1500 nm (preferably wavelength 660 to 1200 nm, more preferably wavelength 660 to 1000 nm), and preferably 10% or less. The content is more preferably 5% or less, and even more preferably 5% or less. Further, in the film of the present invention, when the absorbance at the maximum absorption wavelength is 1, the average absorbance in the wavelength range of 420 to 550 nm is preferably 0.30 or less, more preferably 0.20 or less, It is more preferably 0.15 or less, particularly preferably 0.10 or less.

When the film of the present invention is used as an infrared transmission filter, the film of the present invention preferably has, for example, any one of the following spectral properties (i1) to (i3).
(i1): The maximum value of transmittance in the wavelength range of 400 to 850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in a wavelength range of 400 to 850 nm and transmit light with a wavelength exceeding 950 nm.
(i2): The maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1050 nm.
(i3): The maximum value of transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1200 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength exceeding 1150 nm.

The film of the present invention can also be used in combination with a color filter containing a chromatic colorant. A color filter can be manufactured using a coloring composition containing a chromatic colorant. When the film of the present invention is used as an infrared cut filter and is used in combination with a color filter, the color filter is preferably disposed on the optical path of the film of the present invention. For example, it is preferable to laminate the film of the present invention and a color filter to form a laminate. In the laminate, the film of the present invention and the color filter may or may not be adjacent to each other in the thickness direction. 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 support different from the support on which the color filter is formed, and the film of the present invention may be formed on a support different from the support on which the color filter is formed. Other members (for example, microlenses, flattening layers, etc.) constituting the solid-state imaging device may be interposed between the film and the color filter.

The film of the present invention can be used in various devices such as solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), infrared sensors, and image display devices.

<Membrane manufacturing method>
The membrane of the present invention can be manufactured through a step of applying the composition of the present invention.

Examples of the support include those mentioned above. As a method for applying the composition, a known method can be used. For example, drop casting method; slit coating method; spray method; roll coating method; spin coating method; casting coating method; slit and spin method; Various methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include printing method; transfer method using a mold etc.; nanoimprint method. The application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115). 133 pages), and methods described in JP-A No. 2003-262716, JP-A No. 2003-185831, JP-A No. 2003-261827, JP-A No. 2012-126830, JP-A No. 2006-169325, etc. Can be mentioned.

The composition layer formed by applying the composition may be dried (prebaked). When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or 80°C or higher. The prebake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed using a hot plate, oven, or the like.

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

(When forming a pattern using photolithography)
The pattern forming method using the photolithography method includes a step of exposing a composition layer formed by applying the composition of the present invention to light in a pattern (exposure step), and developing and removing the unexposed portions of the composition layer. It is preferable to include a step of forming a pattern (developing step). If necessary, a step of baking the developed pattern (post-bake step) may be provided. Each step will be explained below.

In the exposure step, the composition layer is exposed in a pattern. For example, the composition layer can be exposed in a pattern by exposing the composition layer to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.

Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used.

Furthermore, during exposure, light may be exposed by continuous irradiation, or exposure may be performed by irradiation in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be performed in an oxygen-free environment (in the absence of oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %). Further, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m ² to 100000W/m ² (for example, 5000W/m ² , 15000W/m ² , or 35000W/m ² ). I can do it. The oxygen concentration and the exposure illuminance may be appropriately combined. For example, the illumination intensity may be 10,000 W/m ² at an oxygen concentration of 10% by volume, or 20,000 W/m ² at an oxygen concentration of 35% by volume.

Next, the unexposed portions of the composition layer after exposure are removed by development to form a pattern. The composition layer in the unexposed area can be removed by development using a developer. As a result, the unexposed portions of the composition layer in the exposure step are eluted into the developer, and only the photocured portions remain on the support. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) prepared by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, etc. Examples include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. As for the alkali agent, compounds with a large molecular weight are preferable from the environmental and safety viewpoints. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. As the surfactant, nonionic surfactants are preferred. For convenience in transportation and storage, the developing solution may be manufactured as a concentrated solution and then diluted to a required concentration before use. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, rinsing is preferably performed by supplying a rinsing liquid to the developed composition layer while rotating the support on which the developed composition layer is formed. It is also preferable to move the nozzle that discharges the rinsing liquid from the center of the support to the periphery of the support. At this time, when moving the nozzle from the center of the support to the peripheral edge, the nozzle may be moved while gradually decreasing its moving speed. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. The same effect can also be obtained by gradually reducing the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.

After development, it is preferable to perform additional exposure treatment or heat treatment (post-bake) after drying. Additional exposure processing and post-bake are post-development curing processing to complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions. . When performing additional exposure processing, the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

(When forming a pattern using dry etching method)
Pattern formation by the dry etching method involves applying the above composition onto a support and curing the composition layer to form a cured product layer, and then forming a patterned photoresist layer on this cured product layer. This can be carried out by forming a patterned photoresist layer as a mask, and dry etching the cured material layer using an etching gas. In forming the photoresist layer, it is preferable to perform a prebaking process. Regarding pattern formation by the dry etching method, the descriptions in paragraphs 0010 to 0067 of JP-A No. 2013-064993 can be referred to, and the contents thereof are incorporated into the present specification.

<Optical filter>
The optical filter of the present invention has the film of the present invention described above. Types of optical filters include infrared cut filters and infrared transmission filters.

In addition to the film of the invention described above, the optical filter of the invention may further include a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, and the like. Examples of the ultraviolet absorbing layer include the absorbing layers described in paragraph numbers 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060. Examples of the dielectric multilayer film include the dielectric multilayer films described in paragraph numbers 0255 to 0259 of JP-A No. 2014-041318. As the layer containing copper, a glass substrate made of glass containing copper (copper-containing glass substrate) or a layer containing a copper complex (copper complex-containing layer) can also be used. Examples of the copper-containing glass substrate include phosphate glass containing copper, fluorophosphate glass containing copper, and the like. Commercially available copper-containing glasses include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (all manufactured by Schott Co., Ltd.), and CD5000 (manufactured by HOYA Co., Ltd.).

<Solid-state image sensor>
The solid-state imaging device of the present invention includes the film of the present invention described above. The structure of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor. For example, the following configurations may be mentioned.

A plurality of photodiodes constituting the light-receiving area of the solid-state image sensor and a transfer electrode made of polysilicon are formed on the support body, and a transfer electrode made of tungsten or the like with only the light-receiving part of the photodiode opened above the photodiode and the transfer electrode. A device protective film formed of silicon nitride or the like is formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light-receiving part. The structure has a film of Furthermore, a configuration in which a light focusing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the film of the present invention (on the side closer to the support), or a structure in which light is focused on the film of the present invention A configuration having a means or the like may be used. Further, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls. In this case, the partition wall preferably has a lower refractive index than each pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Laid-open Nos. 2012-227478 and 2014-179577.

<Image display device>
The image display device of the present invention includes the film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For definitions and details of image display devices, see, for example, "Electronic Display Devices (written by Akio Sasaki, published by Industrial Research Institute Co., Ltd., 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo Tosho Co., Ltd., published in 1989). Publication)” etc. Further, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)". There is no particular restriction on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology." The image display device may include a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, see Japanese Patent Application Laid-open No. 2003-045676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development - High brightness, high precision, long life, collection of know-how", Technical Information Association, It is described in pages 326-328, 2008, etc. The spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430 to 485 nm), green region (530 to 580 nm), and yellow region (580 to 620 nm). In addition to these emission peaks, it is more preferable to have a maximum emission peak in the red region (650 to 700 nm).

<Infrared sensor>
The infrared sensor of the present invention includes the film of the present invention described above. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. EMBODIMENT OF THE INVENTION Hereinafter, one embodiment of the infrared sensor of this invention is described using drawings.

In FIG. 1, numeral 110 is a solid-state image sensor. An infrared cut filter 111 and an infrared transmission filter 114 are arranged on the imaging area of the solid-state image sensor 110. Furthermore, a color filter 112 is arranged on the infrared cut filter 111. A microlens 115 is arranged on the incident light hv side of the color filter 112 and the infrared transmission filter 114. A flattening layer 116 is formed to cover the microlens 115.

The infrared cut filter 111 can be formed using the composition of the present invention. The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and there is no particular limitation, and a conventionally known color filter for forming pixels can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the descriptions in paragraph numbers 0214 to 0263 of JP-A No. 2014-043556 can be referred to, and the contents thereof are incorporated herein. The characteristics of the infrared transmission filter 114 are selected depending on the emission wavelength of the infrared LED used. The infrared transmission filter 114 can be formed using the composition of the present invention.

In the infrared sensor shown in FIG. 1, an infrared cut filter other than the infrared cut filter 111 (another infrared cut filter) may be further disposed on the flattening layer 116. Other infrared cut filters include those having a layer containing copper and/or a dielectric multilayer film. Details of these are mentioned above. Moreover, a dual band pass filter may be used as another infrared cut filter.

<Camera module>
The camera module of the present invention includes the membrane of the present invention described above. Preferably, the camera module further includes a lens and a circuit that processes images obtained from the solid-state image sensor. The solid-state image sensor used in the camera module may be the solid-state image sensor according to the present disclosure described above, or may be a known solid-state image sensor. Further, as the lens used in the camera module and the circuit that processes the image obtained from the solid-state image sensor, known ones can be used. As an example of the camera module, camera modules described in JP-A No. 2016-006476 and JP-A No. 2014-197190 can be referred to, and the contents thereof are incorporated into this specification.

The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. In the structural formula shown below, Me represents a methyl group, Et represents an ethyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group.

<Manufacture of composition>
The materials listed in the table below were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 μm to produce each composition.

Details of the materials indicated by abbreviations in the table are as follows.

(Infrared absorber)
SQ-1 to SQ-17: Compounds SQ-1 to SQ-17 listed as specific examples of the compound represented by formula (1) (specific compound)
SQ-c1, dyes A to T: compounds with the following structure

(Anti-fading agent)
a-1 to a-8: Compounds with the following structure (phenolic antioxidants)

b-1 to b-6: Compounds with the following structure (phosphorus antioxidants)

c-1 to c-7: Compounds with the following structure (amine antioxidants)

d-1 to d-6: Compounds with the following structure (quencher)

e-1 to e-4 Compounds with the following structure (sulfur-based antioxidants)

f-1: Tetramethylethylene (singlet oxygen scavenger)
f-2: 1,3-diphenylisobenzofuran (singlet oxygen scavenger)
f-3: N-ethylimidazole (singlet oxygen scavenger)

(resin)
Resin 1: Resin with the following structure (the numbers appended to the main chain are the molar ratio of repeating units, weight average molecular weight 17,000, degree of dispersion 2.3)
Resin 2: Resin with the following structure (the numbers added to the main chain are the molar ratio of repeating units, weight average molecular weight 9700, dispersity 1.8)
Resin 3: Resin with the following structure (the numbers added to the main chain are the molar ratio of repeating units, weight average molecular weight 10100, dispersity 1.7)
Resin 4: Resin with the following structure (the numbers appended to the main chain are the molar ratio of repeating units, weight average molecular weight 25,000, dispersity 2.2)
Resin 5: Resin with the following structure (the numbers appended to the main chain are the molar ratio of repeating units, weight average molecular weight 13000, degree of dispersion 2.0)
Resin 6: Resin with the following structure (the numbers appended to the main chain are the molar ratio of repeating units, weight average molecular weight 10,000, degree of dispersion 2.0)
Resin 7: Resin with the following structure (the numbers appended to the main chain are the molar ratio of repeating units, weight average molecular weight 8000, dispersity 1.8)
Resin 8: Resin with the following structure (the numbers appended to the main chain are the molar ratio of repeating units, weight average molecular weight 10500, dispersity 2.4)
Resin 9: ARTON F4520 (manufactured by JSR Corporation, cyclic polyolefin resin)

(UV absorber)
Ultraviolet absorber 1: UV-503 (Daito Chemical Co., Ltd.)
Ultraviolet absorber 2: UVinul3050 (manufactured by BASF, compound with the following structure)
Ultraviolet absorber 3: Compound with the following structure (maximum absorption wavelength in dichloromethane: 394 nm)
Ultraviolet absorber 4: Tinuvin477 (manufactured by BASF, hydroxyphenyltriazine-based ultraviolet absorber)
Ultraviolet absorber 5: Tinuvin326 (manufactured by BASF, compound with the following structure)
Ultraviolet absorber 6: Compound (2)-22 (compound with the following structure) described in International Publication No. 2021/131355
Ultraviolet absorber 7: Compound (1)-46 described in International Publication No. 2021/131355 (compound with the following structure)
Ultraviolet absorber 8: Compound A-1 (compound with the following structure) described in International Publication No. 2021/132247
Ultraviolet absorber 9: NeoHeliopan357 (manufactured by Symrise, compound with the following structure)
Ultraviolet absorber 10: Compound with the following structure

(surfactant)
Surfactant 1: FTX-218D (manufactured by Neos, fluorine-based surfactant)
Surfactant 2: Compound with the following structure (weight average molecular weight 14,000, the numerical value of % indicating the proportion of repeating units is mol%)
Surfactant 3: Megafac F-554 (manufactured by DIC Corporation, fluorine-based surfactant)

(Photopolymerization initiator)
Photoinitiator 1: IRGACURE-OXE01 (manufactured by BASF) [2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione]
Photopolymerization initiator 2: Compound No. 2 described in International Publication No. 2017/169819. 1 (compound with the following structure)
Photopolymerization initiator 3: Compound No. 3 described in International Publication No. 2017/169819. 10 (compound with the following structure)
Photopolymerization initiator 4: Compound No. described in JP-A No. 2019-168654. 5 (compound with the following structure)
Photopolymerization initiator 5: Compound No. described in JP-A No. 2019-168654. 73 (compound with the following structure)

(acid generator)
Acid generator 1: CPI-100P (manufactured by San-Apro Co., Ltd.)

(Polymerizable compound)
Polymerizable compound 1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
Polymerizable compound 2: Aronix M-510 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer)

(Polymerization inhibitor)
Polymerization inhibitor 1: p-methoxyphenol

(solvent)
Solvent 1: Propylene glycol monomethyl ether acetate Solvent 2: Cyclopentanone

<Evaluation of infrared shielding properties, visible transparency, light resistance, and heat resistance>
For the compositions of Examples 1 to 86 and Comparative Examples 1 to 4, films were produced according to the following film production method 1. For the compositions of Examples 501 to 580 and Comparative Examples 501 to 504, films were produced according to the following film production method 2.

Film production method 1: Each composition was coated on a glass substrate (Corning Co., Ltd. 1737) using a spin coater so that the film thickness after drying was 1.0 μm, and coated using a 100°C hot plate. A heat treatment (prebaking) was performed for 120 seconds. Next, the entire surface was exposed using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) at an exposure dose of 500 mJ/cm ² . Furthermore, heat treatment (post-bake) was performed for 300 seconds using a 200° C. hot plate to obtain a film.

Film production method 2: Each composition was applied onto a glass substrate (Corning Co., Ltd. 1737) using a spin coater so that the film thickness after drying was 1.0 μm, and then coated using a hot plate at 100°C. Then, heating (prebaking) was performed at 100° C. for 10 minutes. Next, a curing treatment was performed by heating at 200° C. for 8 minutes to obtain a film.

-Evaluation of infrared shielding properties-
The average transmittance of the obtained film in the wavelength range exceeding 700 nm and the maximum absorption wavelength ±10 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), and the average transmittance was measured according to the following criteria. The infrared shielding properties were evaluated.
A: Average transmittance ≦5% in the wavelength range exceeding 700 nm and within the maximum absorption wavelength ±10 nm.
B: Average transmittance in the range of maximum absorption wavelength ± 10 nm in the wavelength range exceeding 5% < wavelength 700 nm ≦ 10%
C: Average transmittance in the range of maximum absorption wavelength ± 10 nm in the wavelength range exceeding 10% < wavelength 700 nm

-Evaluation of visible transparency-
The average transmittance of the obtained film at a wavelength of 420 to 550 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), and the visible transparency was evaluated according to the following criteria.
A: Average transmittance in the wavelength range of 420 to 550 nm ≧95%
B: 90%≦average transmittance in the wavelength range of 420 to 550 nm<95%
C: Average transmittance in the wavelength range of 420 to 550 nm <90%

-Evaluation of light resistance-
The obtained film was subjected to a light resistance test by irradiating it with 50,000 lux light for 20 hours through an ultraviolet cut filter using a Xe lamp. The ΔEab value of the color difference of the film before and after the property test was measured, and the light resistance was evaluated based on the following criteria. The smaller the ΔEab value, the better the light resistance.
A: ΔEab value<2.5
B: 2.5≦ΔEab value<5
C: 5≦ΔEab value<10
D: 10≦ΔEab value

-Evaluation of heat resistance-
The obtained film was stored in a thermostat at 150°C for 6 months to perform a heat resistance test, and the color difference of the film before and after the heat resistance test was measured using a color meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The ΔEab value was measured, and the heat resistance was evaluated based on the following criteria. The smaller the ΔEab value, the better the heat resistance.
A: ΔEab value<2.5
B: 2.5≦ΔEab value<5
C: 5≦ΔEab value<7.5
D: 7.5≦ΔEab value<10
E: 10≦ΔEab value

<Evaluation of storage stability>
The viscosity of the composition immediately after production (referred to as initial viscosity A) was measured. After the composition whose viscosity was measured was stored in a constant temperature bath at 45° C. for 72 hours, the viscosity (referred to as viscosity B after storage) was measured again. In addition, the viscosity was measured by adjusting the temperature of the composition to 23°C. Then, the viscosity increase rate was calculated from the following formula, and the storage stability was evaluated based on the following criteria. The lower the thickening rate, the better the storage stability.
Thickening rate (%) = [(viscosity B after storage/initial viscosity A) -1] x 100.
A: The viscosity increase rate is 5% or less B: The viscosity increase rate is more than 5% and 10% or less C: The viscosity increase rate is more than 10% and 20% or less D: The viscosity increase rate is more than 20% and less than 30% E: The thickening rate is more than 30%

As shown in the table above, the examples had better evaluations of storage stability, light resistance, and heat resistance than the comparative examples.

110: solid-state image sensor, 111: infrared cut filter, 112: color filter, 114: infrared transmission filter, 115: microlens, 116: flattening layer

Claims

Contains an infrared absorber, an anti-fading agent, and a curable compound,
The infrared absorber includes a compound represented by formula (1),
A composition in which the anti-fading agent satisfies the following conditions 1 or 2;
Condition 1: The anti-fading agent is at least one selected from the group consisting of a phosphorus antioxidant and a sulfur antioxidant, a phenolic antioxidant, an amine antioxidant, a quencher, and a singlet oxygen scavenger. at least one selected from the group consisting of agents;
Condition 2: The anti-fading agent contains at least one selected from the group consisting of phenolic antioxidants, amine antioxidants, and singlet oxygen quenchers, and a quencher;
In formula (1), A and B each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle;
Ra and Rb each independently represent a substituent;
m1 represents an integer from 0 to mA, mA represents the maximum integer in which Ra can be replaced by A, m2 represents an integer from 0 to mB, and mB represents the maximum integer in which Rb can be replaced by B. represent;
Ra and A may be combined to form a ring, Rb and B may be combined to form a ring, and when m1 is 2 or more, two Ras out of m1 Ras may be combined to form a ring, and when m2 is 2 or more, two Rb out of m2 Rb may be combined to form a ring;
Y 1 and Y 2 each independently represent an alkyl group, an aryl group, or a group represented by formula (Y-1); provided that at least one of Y 1 and Y 2 contains a fluorine atom;
-L Y1 -R Y1 ...Formula (Y-1)
In formula (Y-1), L Y1 represents -CO-, -CS-, -SO 2 -, -CONH-, -CSNH- or -COO-, and R Y1 represents an alkyl group, an alkenyl group, or an alkynyl group. represents a group, an aryl group or a heteroaryl group.
The composition according to claim 1, wherein at least one of A and B in the formula (1) is a benzene ring, a thiophene ring, a furan ring, a pyrrole ring, a pyridine ring, an azulene ring, or a fused ring containing these rings. .
The composition according to claim 1 or 2, wherein at least one of A and B in the formula (1) is a benzene ring or a naphthalene ring.
The composition according to any one of claims 1 to 3, wherein the compound represented by formula (1) has a structure represented by formula (2-1) or formula (2-2);
In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1),
Y 3 represents a group represented by the above formula (Y-1),
Rs 1 represents a substituent, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 5,
Rs 11 and Rs 12 each independently represent an alkyl group, an aryl group or a heteroaryl group,
Rs 11 and Rs 12 , Rs 11 and Rs 1 , and Rs 12 and Rs 1 may be bonded to each other to form a ring.
Claim 1, wherein the compound represented by formula (1) has a structure represented by formula (2-1a), formula (2-1b), formula (2-1c), or formula (2-1d). The composition according to any one of -4;
In the formula, the wavy line represents the bonding position with the squaric acid moiety in formula (1),
Y 3 represents a group represented by the above formula (Y-1),
Rs 2 to Rs 4 each independently represent a hydrogen atom or a substituent,
Rs 13 and Rs 14 each independently represent an alkyl group, an aryl group or a heteroaryl group,
A1 to A4 each independently represent a ring containing a nitrogen atom.
The composition according to any one of claims 1 to 5, wherein the compound represented by formula (1) is a compound represented by formula (1a);
In the formula, Y 4 and Y 5 each independently represent a group represented by the above formula (Y-1); provided that at least one of Y 4 and Y 5 contains a fluorine atom;
Rs 5 and Rs 6 each independently represent a substituent;
n1a and n1b each independently represent an integer of 0 to 3;
Rs 21 to Rs 24 each independently represent an alkyl group, an aryl group, or a heteroaryl group;
Rs 21 and Rs 22 , Rs 23 and Rs 24 , Rs 21 and Rs 5 , Rs 22 and Rs 5 , Rs 23 and Rs 6 , and Rs 24 and Rs 6 may be bonded to each other to form a ring.
The composition according to any one of claims 1 to 6, wherein the anti-fading agent has a molecular weight of 1170 or less.
The composition according to any one of claims 1 to 7, wherein the anti-fading agent satisfies the condition 1.
The composition according to any one of claims 1 to 8, wherein the curable compound includes a polymerizable compound.
The composition according to claim 9, wherein the polymerizable compound includes a compound having an ethylenically unsaturated bond-containing group.
The composition according to any one of claims 1 to 10, wherein the infrared absorber contains an infrared absorber other than the compound represented by the formula (1).
A film obtained using the composition according to any one of claims 1 to 11.
An optical filter comprising the film according to claim 12.
A solid-state imaging device comprising the film according to claim 12.
An image display device comprising the film according to claim 12.
An infrared sensor comprising the film according to claim 12.
A camera module comprising the membrane according to claim 12.