Composition for optical sensors, optical sensors, and solid-state imaging devices and camera modules using the optical filters.

Abstract

To provide a composition for optical sensors that can form an optical filter for optical sensors having excellent properties relating to visible light-transmissive window range, infrared ray-shielding range, heat resistance, chemical resistance, coating defect reduction after low-temperature storage, and coating defect reduction after long-term low-temperature storage.SOLUTION: A composition for optical sensors contains a copolymer (P) of an unsaturated mixture containing (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and (a2) at least one selected from the group consisting of an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound, and a dye [Q] composed of at least one polymethine compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for optical sensors and an optical sensor. [Background technology]

[0002] Video cameras, digital cameras, and mobile phones with camera functions are equipped with solid-state image sensors, which are optical sensors. Specifically, known solid-state image sensors include CCD (Charge-Coupled Device) image sensors and CMOS (Complementary MOS) image sensors. The sensitivity of the photodiodes in these solid-state image sensors extends from the visible light region to the infrared region. Therefore, solid-state image sensors are equipped with filters to block infrared light. These optical filters (infrared blocking filters) allow the sensitivity of the solid-state image sensor to be adjusted to approximate human visual sensitivity. Similarly, other optical sensors may also be equipped with filters to block infrared light.

[0003] The optical filter described above contains dyes or pigments as infrared shielding agents. These infrared shielding agents are required to have the property of absorbing infrared rays while sufficiently transmitting visible light. As one such infrared shielding agent, the use of phthalocyanine compounds has been investigated, particularly as a good shielding agent for near-infrared rays (see Japanese Patent Publication No. 2008-201952). Furthermore, a pattern-forming composition containing a squarylium compound along with an acrylic polymer is disclosed for the purpose of improving the suppression of developing residue, the shape of the pattern, and the heat resistance (Japanese Patent No. 6903143). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-201952 [Patent Document 2] Patent No. 6903143 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, with the increasing demand for high-performance optical characteristics in recent years, it has become difficult to obtain sufficient characteristics, and further improvements are desired. In addition, with the diversification of applications for optical sensors, there is a need for optical filters that can withstand harsher environments. On the other hand, from the perspective of production process margins, there is also a desire for infrared shielding films that have few defects such as foreign matter even after being left to cure for a period of time after coating in the production process. Considering the above circumstances, there has been a need for optical sensor compositions that can balance optical characteristics with heat resistance and storage stability.

[0006] The present invention has been made based on the above circumstances, and its object is to provide an optical sensor composition that can form an optical filter for an optical sensor having good properties with respect to the visible light transmission window range, infrared shielding range, heat resistance, chemical resistance, suppression of coating defects after low-temperature storage, and suppression of coating defects after long-term low-temperature storage. [Means for solving the problem]

[0007] The invention made to solve the above problems is a copolymer (P) of an unsaturated mixture containing (a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and (a2) at least one selected from the group consisting of oxiranyl group-containing unsaturated compounds and oxetanyl group-containing unsaturated compounds, and The optical sensor composition contains at least one polymethine-based compound dye [Q]. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an optical sensor composition that can form an optical filter for an optical sensor having good properties with respect to the visible light transmission window range, infrared shielding range, heat resistance, chemical resistance, suppression of coating defects after low-temperature storage, and suppression of coating defects after long-term low-temperature storage. [Modes for carrying out the invention]

[0009] The following describes in detail an optical sensor composition according to one embodiment of the present invention. <Composition for optical sensors> The optical sensor composition of the present invention comprises (a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and (a2) a copolymer (P) of an unsaturated mixture containing at least one selected from the group consisting of oxiranyl group-containing unsaturated compounds and oxetanyl group-containing unsaturated compounds, and It contains a dye [Q] comprising at least one polymethine compound.

[0010] (Pigment [Q]) (Polymethine compounds) The polymethine-based compounds used in the present invention are polymethine dyes other than squarylium-based compounds, crokonium-based compounds, and cyanine-based compounds, and are not particularly limited as long as they do not impair the effects of the present invention. For example, the compounds described in Japanese Patent Application Publication No. 2019-164269 can be used, and they can be synthesized by generally known methods.

[0011] • Polymethine compounds (iii) As the aforementioned polymethine-based compound, a compound represented by the following formula (III) is preferred, in that it allows for easy acquisition of optical filters that exhibit the aforementioned effects more effectively.

[0012] Cn + An - (III) [In formula (III), Cn + is a monovalent cation represented by the following formula (IV) or formula (VI), and An -is a monovalent anion.

[0013] [Chemical formula]

[0014] In formula (IV) and formula (VI), unit A is any one of the following formulas (A-I) to (A-III), unit B is any one of the following formulas (B-I) to (B-III), Z A ~Z C and Y A ~Y I are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, an amide group, an imide group, a cyano group, a silyl group, -Q 1 , -N=N-Q 1 , -S-Q 2 , -SSQ 2 , or, -SO2Q 3 and Z A ~Z C and Y A ~Y I among them, two adjacent ones may be bonded to each other to form a ring, some groups in unit A may be bonded to Y A or Y F to form a cyclic hydrocarbon group having 5 or 6 carbon atoms, and some groups in unit B may be bonded to Y E or Y I to form a cyclic hydrocarbon group having 5 or​​​​​​​​​​​​​​​​​​​​​~L h It is one of the following, Q 3 is a hydroxyl group or L below a ~L h It is either R i The following L a ~L h It is one of the following:

[0015] [ka]

[0016] In equations (AI) to (A-III), -* represents Y in equation (IV) above. A or Y F This demonstrates that it forms a single bond with the carbon atom to which it is bonded. In equations (BI) to (B-III), =** represents Y in equation (IV) above. E or Y I This shows that it forms a double bond with the carbon it is bonded to. In formulas (AI)~(B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR 8 -and, R 1 ~R 6 Each of these independently consists of a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, and -NR. g R h Base, -SR i Base, -SO2R i Base, -OSO2R i group, -C(O)R i Base or the following L a ~L h It is one of the following: Adjacent R 1 ~R 6These groups may bond to each other to form a 4-7 membered alicyclic group containing at least one C6-C14 aromatic hydrocarbon group, a nitrogen atom, an oxygen atom, or a sulfur atom, or a C3-C14 heteroaromatic group containing at least one nitrogen atom, an oxygen atom, or a sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may also have a hydroxyl group, a C1-C9 aliphatic hydrocarbon group, or a halogen atom, and the alicyclic group may also have =O. R 8 These are independently hydrogen atoms, halogen atoms, and -C(O)R i Based on the following L a ~L h It is one of the following: R i These are independent of the following L a ~L h It is one of the following: (L a ): Aliphatic hydrocarbon groups with 1 to 15 carbon atoms (L b ): Halogen-substituted alkyl groups with 1 to 15 carbon atoms (L c ): A cycloaliphatic hydrocarbon group having 3 to 14 carbon atoms, which may have a substituent K. (L d ): A C6-C14 aromatic hydrocarbon group which may have a substituent K (L e ): A heterocyclic group having 3 to 14 carbon atoms, which may have a substituent K. (L f ):-OR (R is a hydrocarbon group having 1 to 12 carbon atoms, which may have substituent L) (L g ): Acyl group having 1 to 9 carbon atoms, which may have substituent L. (L h ): A carbon-1 to carbon-9 alkoxycarbonyl group which may have a substituent L. The substituent K is L a ~L b At least one more selected substituent L is L a ~L f It is at least one of the more selected species.

[0017] Note that the above-NR 8- is a group represented by the following formula (a), and the -NR g R h group is a group represented by the following formula (b), and the -SR i group is a group represented by the following formula (c), and the -SO2R i group is a group represented by the following formula (d), and the -OSO2R i group is a group represented by the following formula (e), and the -C(O)R i group is a group represented by the following formula (f).

[0018] Also, the -SSQ 2 is a group represented by -S-S-Q 2 and the -SO2Q 3 is a group obtained by replacing R i with Q 3 in the group represented by the following formula (d).

[0019] [Chemical formula]

[0020] When the unit A is the formula (A-I) and the unit B is the formula (B-I), Cn + is represented by the following formula (IV-1) or the following formula (VI-1). That is, the single bond (-) of "*-" in the formulas (A-I) to (A-III) corresponds to the single bond between the carbon atom to which Y A in the following formula (IV) or Y F in the following formula (VI) is bonded and the unit A, and the double bond (=) of "**=" in the formulas (B-I) to (B-III) corresponds to the double bond between the carbon atom to which Y E in the following formula (IV) or Y I in the following formula (VI) is bonded and the unit B.

[0021] [Chemical formula]

[0022] The Y B and YD , Y G and Y H is each independently, more preferably, a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, Y B and Y D a 4- to 6-membered alicyclic hydrocarbon group formed by bonding with each other (the alicyclic hydrocarbon group may have a substituent R selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a hydroxyl group, a halogen atom, and =O).) 9 .

[0023] Incidentally, Y B and Y D When it is a 4- to 6-membered alicyclic hydrocarbon group formed by bonding with each other, Formula (IV) can each preferably be represented by the following Formulas (IV-A) to (IV-C), and Y G and Y H When it is a 4- to 6-membered alicyclic hydrocarbon group formed by bonding with each other, Formula (VI) can each preferably be represented by the following Formulas (VI-A) to (VI-B).

[0024]

Chemical formula

[0025]

Chemical formula

[0026]

Chemical formula

[0027]

Chemical formula

[0028]

Chemical formula

[0029] Substituent R9 Preferred members include hydrogen atoms, hydroxyl groups, =O, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, and cyclohexyl groups, with hydrogen atoms, hydroxyl groups, =O, methyl groups, ethyl groups, and tert-butyl groups being more preferred.

[0030] The aforementioned Y A , Y C , Y E , and Z A ~Z C Each of these is independently preferably a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, or -NR g R h Group, amide group, imide group, cyano group, silyl group, -Q 1 -N=NQ 1 , -SQ 2 -SSQ 2 , -SO2Q 3 , or the aforementioned Y A , Y C , Y E , and Z A ~Z C Two adjacent carbon atoms may bond to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms: a 5 to 6-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom, or sulfur atom; or a heteroaromatic group having 3 to 14 carbon atoms which contains at least one nitrogen atom, oxygen atom, or sulfur atom; and these alicyclic groups, aromatic hydrocarbon groups, and heteroaromatic groups may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

[0031] Said L a Preferably, the group is a methyl group (Me), an ethyl group (Et), an n-propyl group, an isopropyl group (i-Pr), an n-butyl group, a sec-butyl group, a tert-butyl group (tert-Bu), a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, or a dodecyl group, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.

[0032] Said La This may be an alkenyl group such as a vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, or hexenyl group; or an alkynyl group such as an ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, or hexynyl group.

[0033] Said L b Examples of halogen-substituted alkyl groups having 1 to 15 carbon atoms include groups in which at least one hydrogen atom of an alkyl group having 1 to 15 carbon atoms is substituted with a halogen atom, and are preferably trichloromethyl, trifluoromethyl, 1,1-dichloroethyl, pentachloroethyl, pentafluoroethyl, heptachloropropyl, and heptafluoropropyl groups.

[0034] Said L c Examples of alicyclic hydrocarbon groups having 3 to 14 carbon atoms that may have a substituent K include cycloalkyl groups such as cyclopropyl, cyclopropylmethyl, methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic alicyclic groups such as norbornane and adamantyl.

[0035] Said L d The C6-C14 aromatic hydrocarbon group which may have substituent K is preferably a phenyl group, a tolyl group, a xylyl group, a mesityl group (trimethylphenyl group), a cumenyl group, a bis(trifluoromethyl)phenyl group, a 1-naphthyl group, a 2-naphthyl group, anthracenyl group, a phenanthryl group, or a benzyl group (CH2Ph).

[0036] Said L e The heterocyclic group having 3 to 14 carbon atoms that may have a substituent K is preferably furan, thiophene, pyrrole, indole, indoline, indorenine, benzofuran, benzothiophene, morpholine, or pyridine.

[0037] Said L f The -OR in this formula is preferably a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, methoxymethyl group, methoxyethyl group, pentyloxy group, hexyloxy group, octyloxy group, phenoxy group (OPh), 4-methylphenoxy group, or cyclohexyloxy group.

[0038] Said L g The acyl group having 1 to 9 carbon atoms that may have substituent L is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, or a trifluoromethylcarbonyl group.

[0039] Said L h The C1-C9 alkoxycarbonyl group which may have substituent L is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group.

[0040] The aforementioned X is preferably an oxygen atom, a sulfur atom, or -NR 8 - is particularly preferably an oxygen atom.

[0041] In equations (IV) and (VI), the left and right units A and B may be identical or different, but it is preferable that they be identical because it is easier to combine them.

[0042] In this case, the combinations in which units A and B are identical are equation (AI) and equation (BI), equation (A-II) and equation (B-II), and equation (A-III) and equation (B-III).

[0043] The aforementioned R 1 ~R 6Each of these groups is independently, preferably, a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a 1,1-dimethylbutyl group, a cyclopropyl group, a cyclopropylmethyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,4,6-trimethylphenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a hydroxyl group, an amino group, a dimethylamino group (NMe2), a diethylamino group (NEt2), a dibutylamino group (N(n-Bu)2), a cyano group, a nitro group, an acetylamino group, a propionylamino group, or an N-methyl group. The group is a tylacetylamino group, a trifluoromethylamino group, a pentafluoroethanolamino group, a tert-butanoylamino group, a cyclohexinoylamino group, an n-butylsulfonyl group, a benzyl group, a diphenylmethyl group, a trifluoromethyl group, a difluoromethyl group, or a methoxy group; more preferably, it is a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, an amino group, a benzyl group, a diphenylmethyl group, a trifluoromethyl group, a difluoromethyl group, or a methoxy group.

[0044] The aforementioned R 1 ~R 6 At least one of them has high near-infrared cutting performance and high visible light transmission performance at absorption maximums around wavelengths of 700-750 nm or 720-900 nm, and a compound with excellent optical properties and sufficient resistance to heat and light can be easily obtained, and the above L a , L c or L d It is preferable that this is the case. Furthermore, if unit A is formula (A-III) and unit B is formula (B-III), then "R 1 ~R 6 At least one of L a , L c or L d "is" means "R 1 , R 2 , R 4 , R5 At least one of L a , L c or L d It means "to be".

[0045] The aforementioned R 8 Preferably, the group is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a benzyl group, an n-pentyl group, an n-hexyl group, or a tert-butyl group; more preferably, it is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a benzyl group.

[0046] The aforementioned An - The anion is not particularly limited as long as it is monovalent, but preferably chloride ions, bromide ions, iodide ions, and PF4. - Examples include perchlorate anion, tristrifluoromethanesulfonylmethide anion, tetrafluoroborate anion, hexafluorophosphate anion, bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonic acid anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion, and more preferably bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonic acid anion, tristrifluoromethanesulfonylmethide anion, The tetrakis(pentafluorophenyl)borate anion and the tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion are preferred, and more preferably, the bis(trifluoromethanesulfonyl)imide anion, tristrifluoromethanesulfonylmethide anion, tetrakis(pentafluorophenyl)borate anion, and tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion are preferred, particularly the tetrakis(pentafluorophenyl)borate anion, as these allow for easy acquisition of compounds with superior heat resistance.

[0047] Specific examples of compounds (III) having a monovalent cation represented by formula (IV) include the following compounds (III-1) to (III-3).

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] Specific examples of compounds (III) having a monovalent cation represented by formula (VI) include the following compounds (III-4) to (III-6).

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] In this invention, the above-mentioned polymethine compound is included as an essential component as the dye [Q]. The composition contains 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more, of the total dye [Q]. By including a predetermined amount of the polymethine compound in this way, an optical sensor composition with excellent properties such as long-term low-temperature storage, heat resistance, and chemical resistance can be obtained. The dye [Q] may further contain a squarylium compound.

[0056] (Squallium compounds) The squarylium-based compound used in the present invention is preferably a compound represented by the following formula (I) or a compound represented by the following formula (II) (hereinafter also referred to as "compound (I)" and "compound (II)," respectively). ·Compound (I)

[0057] [ka]

[0058] In formula (I), R a , R b And Y satisfies either condition (i) or (ii) below.

[0059] (i) Multiple R a These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L 1 or -NR e R f Group (R e and R f Each is an independent hydrogen atom, -L a , -L b , -L c , -L d or -L e It represents. ) represents, Multiple R b These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L 1 or -NR g R h Group (R g and R h Each is an independent hydrogen atom, -L a , -L b , -L c , -L d , -L e , -SO2R i base or -C(O)R i Group (Ri is, -L a , -L b , -L c , -L d or -L e This represents R bonded to the same N atom. g and R h Multiple R's inside i (These may be joined together to form a ring.) Multiple Ys are independently -NR j R k Group (R j and R k Each is an independent hydrogen atom, -L a , -L b , -L c , -L d or -L e It represents. ) represents, L 1 teeth, (L a ) an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have substituent L. (L b ) A halogen-substituted alkyl group with 1 to 20 carbon atoms, which may have substituent L. (L c ) A cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms, which may have substituent L. (L d ) A C6-C20 aromatic hydrocarbon group which may have substituent L, (L e ) A heterocyclic group having 3 to 20 carbon atoms, which may have substituent L. (L f ) A carbon-1 to carbon-20 alkoxy group which may have a substituent L, (L g ) A carbon-1 to carbon-20 acyl group which may have substituent L, or (L h ) A C1-C20 alkoxycarbonyl group which may have a substituent L The substituent L is at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a heterocyclic group having 3 to 20 carbon atoms.a ~L h The L may further have at least one atom or group selected from the group consisting of halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and amino groups. a ~L h Preferably, the total number of carbon atoms, including substituents, is 50 or less, more preferably 40 or less, and particularly preferably 30 or less. If the number of carbon atoms is greater than this range, it may become difficult to synthesize the dye, and the absorption intensity per unit mass tends to decrease.

[0060] (ii) Two R on one benzene ring a At least one of these is bonded to Y on the same benzene ring to form a heterocycle with 5 or 6 constituent atoms, which contains at least one nitrogen atom, and the heterocycle may have substituents. R b and R that does not participate in the formation of the heterocycle a Each of these independently corresponds to R of condition (i) above. b and R a It is synonymous with [the above].

[0061] • Compound (II) [ka]

[0062] In equation (II), there are multiple R c These are hydrogen atoms, -L a , -L b , -L c , -L d or -L e This represents, Multiple R d These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L 1 or -NR e R f The base is represented, and adjacent R d They may be linked together to form a ring which may have substituents. X is O, S, Se, NR c or CR d R d This represents, L a ~L e , L 1 , R e and R f L is defined in equation (I) above. a ~L e , L 1 , R e and R f It is synonymous with [the above].

[0063] R in equation (II) above c Preferably, the group is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a tolfluoromethyl group, or a pentafluoroethyl group; more preferably, it is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0064] R in equation (II) above d Preferably, the group is a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, or 4-aminocyclohexyl group, and more preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, trifluoromethyl group, or pentafluoroethyl group.

[0065] The aforementioned X is preferably O, S, Se, N-Me, N-Et, CH2, C-Me2, C-Et2, and more preferably S, C-Me2, C-Et2.

[0066] In equation (II) above, adjacent R dThese rings may be linked together to form a ring. Examples of such rings include a benzoindorenine ring, an α-naphthoimidazole ring, a β-naphthoimidazole ring, an α-naphthoxazole ring, a β-naphthoxazole ring, an α-naphthothiazole ring, a β-naphthothiadazole ring, an α-naphthoserenazole ring, and a β-naphthoserenazole ring.

[0067] Compounds (I) and (II) may adopt resonance structures as described in International Patent Publication WO2013 / 054864. Specific examples of compound (I) and compound (II) include the following compounds (ID-1) to (ID-4).

[0068] [ka]

[0069] (Other organic pigments) The composition may contain other known organic dyes in addition to polymethine compounds and squarylium compounds. Examples of other organic dyes include phthalocyanine compounds, diiminium compounds, cyanine compounds, naphthalocyanine compounds, quaterylene compounds, aminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, crokonium compounds, hexaphylline compounds, etc. (excluding those containing copper atoms).

[0070] (Copolymer (P)) The copolymer (P) used in the present invention is a copolymer of (a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "compound (a1)") and (a2) at least one selected from the group consisting of oxiranyl group-containing unsaturated compounds and oxetanyl group-containing unsaturated compounds (hereinafter sometimes referred to as "compound (a2)"). Such copolymers can be produced by radical copolymerization of an unsaturated mixture containing compounds (a1) and (a2) in a solvent in the presence of a polymerization initiator.

[0071] Compound (a1) is a radically polymerizable unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, and examples include monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids, mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polycyclic compounds having carboxyl groups and their anhydrides.

[0072] Specific examples of these include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Examples of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; Examples of dicarboxylic acid anhydrides include the anhydrides of the compounds exemplified above as dicarboxylic acids; Examples of mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids include mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; Examples of mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends include ω-carboxypolycaprolactone mono(meth)acrylate; Examples of polycyclic compounds having a carboxyl group and their anhydrides include 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

[0073] Of these, monocarboxylic acids and dicarboxylic acid anhydrides are preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferred because they enhance copolymerization reactivity, heat resistance, and chemical resistance of the film, and are readily available. These compounds (a1) can be used individually or in combination of two or more.

[0074] Compound (a2) is an unsaturated compound having an oxiranil group and / or an unsaturated compound having an oxetanyl group. Examples of unsaturated compounds having an oxiranil group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, and p-vinylbenzylglycidyl ether. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 3,4-epoxycyclohexyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate are preferred for their copolymerization reactivity and for improving the heat resistance and chemical resistance of the resulting film.

[0075] Examples of unsaturated compounds having an oxetanyl group include 3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2,2-difluorooxetane, 3-(acryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3- Acrylic acid esters such as (2-acryloyloxyethyl)oxetane, 3-(2-acryloyloxyethyl)-2-ethyloxetane, 3-(2-acryloyloxyethyl)-3-ethyloxetane, 3-(2-acryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-acryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-acryloyloxyethyl)-2-phenyloxetane, 3-(2-acryloyloxyethyl)-2,2-difluorooxetane, 3-(2-acryloyloxyethyl)-2,2,4-trifluorooxetane, and 3-(2-acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane. 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-methacryloyloxyethyl)oxetane Examples of methacrylic acid esters such as tan, 3-(2-methacryloyloxyethyl)-2-ethyloxetane, 3-(2-methacryloyloxyethyl)-3-ethyloxetane, 3-(2-methacryloyloxyethyl)-2-tolylololomethyloxetane, 3-(2-methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloyloxyethyl)-2-phenyloxetane, 3-(2-methacryloyloxyethyl)-2,2-difluorooxetane, 3-(2-methacryloyloxyethyl)-2,2,4-trifluorooxetane, and 3-(2-methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane can be listed.

[0076] Of these, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, and 3-(methacryloyloxymethyl)-3-ethyloxetane are preferred from the viewpoint of copolymerization reactivity.

[0077] These compounds (a2) can be used individually or in combination.

[0078] The copolymer (P) has a mass ratio (a2) / (a1) of repeating units derived from compound (a1) to repeating units derived from compound (a2) of 1 or more, preferably 1.1 or more, and more preferably 1.2 or more. This ratio provides high low-temperature storage stability, allows for long-term storage, and yields a composition with excellent heat resistance, chemical resistance, and other properties. It is preferable that the constituent unit (a2) derived from (a2) is present in an amount of 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more, relative to the total constituent units of the copolymer. Within this range, a composition can be obtained that has high low-temperature storage stability, can be stored for a long period of time, and has excellent heat resistance, chemical resistance, etc.

[0079] The copolymer (P) used in the present invention is a copolymer of the above compounds (a1) and (a2). Furthermore, it may be a copolymer of these with other unsaturated compounds (hereinafter sometimes referred to as "compound (a3)"). Such compounds (a3) ​​are not particularly limited as long as they are unsaturated compounds with radical polymerizability, but examples include alkyl methacrylates, cyclic alkyl methacrylates, alkyl acrylates, cyclic alkyl acrylates, aryl methacrylates, aryl acrylates, unsaturated dicarboxylic acid diesters, methacrylate esters having hydroxyl groups, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, or a (poly)alkylene glycol skeleton, unsaturated compounds having phenolic hydroxyl groups, and other unsaturated compounds.

[0080] Specific examples of these include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, etc.; and cyclic methacrylates such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 2,6 Decane-8-yl methacrylate (hereinafter referred to as "dicyclopentanyl methacrylate"), tricyclo[5.2.1.0 2,6 ] Decane-8-yloxyethyl methacrylate, isobolonyl methacrylate, adamantane-1-yl methacrylate, etc.; as alkyl acrylates, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, etc.; as cyclic acrylates, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 2,6 Decane-8-yl acrylate (hereinafter referred to as "dicyclopentanyl acrylate"), tricyclo[5.2.1.0 2,6 Decane-8-yloxyethyl acrylate, isoboronyl acrylate, adamantane-1-yl acrylate, etc.; aryl acrylates, for example, phenyl acrylate, benzyl acrylate, etc.; aryl methacrylates, for example, phenyl methacrylate, benzyl methacrylate, etc.; unsaturated dicarboxylic acid diesters, for example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; methacrylic acid esters having a hydroxyl group, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, etc.; Examples of bicyclounsaturated compounds include: bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1] Hept-2-ene, 5,6-di(hydroxymethyl)bicyclo [2.2.1] Hept-2-ene, 5,6-di(2-hydroxyethyl)bicyclo [2.2.1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] Hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] Hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] Hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] Hept-2-ene anhydride (Hymic acid anhydride), 5-t-butoxycarbonylbicyclo [2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] Hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo [2.2.1] Hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo [2.2.1] Hept-2-ene, etc. Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-(4-hydroxyphenyl)maleimide, N-(4-hydroxybenzyl)maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide, etc. Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc.; examples of conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.; examples of unsaturated compounds containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth)acrylate, 2-methacryloyloxypropionic acid tetrahydrofurfuryl ester, 3-(meth)acryloyloxytetrahydrofuran-2-one, etc.; examples of unsaturated compounds containing a furan skeleton include 2-methyl-5-(3-furyl)-1-penten-3-one, furfuryl (meth)acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)- Examples include 2-methyl-1-hexen-3-one, 6-furan-2-yl-hexy-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furyl)-6-methyl-1-hepten-3-one; and unsaturated compounds containing a tetrahydropyran skeleton, such as (tetrahydropyran-2-yl)methyl methacrylate and 2,6-dimethyl-8-(tetrahydropyran-2-yl) Examples include oxy)-octo-1-en-3-one, tetrahydropyran-2-yl methacrylate, 1-(tetrahydropyran-2-oxy)-butyl-3-en-2-one; and unsaturated compounds containing a pyran skeleton, such as 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyrone, 4-(1,5-dioxa-6-oxo-7-octenyl)-6-methyl-2-pyrone; Examples of unsaturated compounds having a (poly)alkylene glycol skeleton include polyethylene glycol (n=2~10) mono(meth)acrylate and polypropylene glycol (n=2~10) mono(meth)acrylate; Examples of unsaturated compounds having phenolic hydroxyl groups include 4-hydroxybenzyl(meth)acrylate, 4-hydroxyphenyl(meth)acrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-(4-hydroxybenzyl)(meth)acrylamide, N-(3,5-dimethyl-4-hydroxybenzyl)(meth)acrylamide, and N-(4-hydroxyphenyl)(meth)acrylamide; Other unsaturated compounds include, for example, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

[0081] Of these, alkyl methacrylates, cyclic alkyl methacrylates, cyclic alkyl acrylates, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, pyran skeletons, unsaturated compounds having (poly)alkylene glycol skeletons, and unsaturated compounds having phenolic hydroxyl groups are preferably used. In particular, the inclusion of an unsaturated compound having an alicyclic structure is preferred from the viewpoint of heat resistance. Examples of unsaturated compounds having an alicyclic structure include cyclic alkyl methacrylates and cyclic alkyl acrylates.

[0082] These compounds (a3) ​​can be used individually or in combination of two or more.

[0083] The copolymer (P) used in the present invention contains repeating units derived from compound (a1) in an amount of preferably 5 to 40% by mass, and particularly preferably 5 to 25% by mass, based on the total amount of repeating units derived from compounds (a1), (a2), and (a3). This range tends to enhance the heat resistance and chemical resistance of the film.

[0084] Furthermore, the copolymer (P) used in the present invention contains repeating units derived from compound (a2) in an amount of preferably 10 to 80% by mass, and particularly preferably 20 to 60% by mass, based on the total amount of repeating units derived from compounds (a1), (a2), and (a3). This range tends to enhance the heat resistance and chemical resistance of the film.

[0085] Furthermore, in the present invention, when an unsaturated compound having an alicyclic structure is used as compound (a3) ​​in the copolymer (P), the repeating units derived therefrom may be preferably 10 to 80% by mass, and particularly preferably 20 to 60% by mass, based on the total of the repeating units derived from compounds (a1), (a2), and (a3), in order to further enhance the heat resistance of the film.

[0086] The polystyrene-based mass-average molecular weight (hereinafter referred to as "Mw") of the copolymer (P) used in the present invention is preferably 2 × 10⁻⁶. 3 ~1 × 10 5 , comfortable 5×10 3 ~5×10 4 Furthermore, the molecular weight distribution (hereinafter referred to as "Mw / Mn") is preferably 5.0 or less, and more preferably 3.0 or less.

[0087] Copolymer (P) can be synthesized, for example, by polymerizing compound (a1), compound (a2), and compound (a3) ​​in a suitable solvent in the presence of a radical polymerization initiator.

[0088] Examples of solvents used in the production of copolymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, and esters.

[0089] Specific examples of these include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol; and ethers such as tetrahydrofuran. Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Examples of propylene glycol alkyl ether propionates include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Examples of aromatic hydrocarbons include toluene and xylene; Examples of ketones include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; As esters, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-Propyl methoxypropionate, 2-butyl methoxypropionate, 2-methyl ethoxypropionate, 2-ethyl ethoxypropionate, 2-propyl ethoxypropionate, 2-butyl ethoxypropionate, 2-methyl ethoxypropionate, 2-ethyl ethoxypropionate, 2-propyl ethoxypropionate, 2-butyl ethoxypropionate, 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-propyl methoxypropionate, 3-methoxypropionic acid Examples of esters include butyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

[0090] Of these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferred, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate, and methyl 3-methoxypropionate are preferred.

[0091] Polymerization initiators known as radical polymerization initiators can be used in the production of copolymers (P). Examples include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, and 1,1'-bis-(t-butylperoxy)cyclohexane; and hydrogen peroxide. When using peroxides as radical polymerization initiators, they may also be used together with a reducing agent to act as redox initiators.

[0092] In the production of copolymers (P), molecular weight modifiers can be used to adjust the molecular weight. Specific examples include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and thioglycolic acid; xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; and terpinolene and α-methylstyrene dimer.

[0093] The lower limit of the copolymer (P) content in the total solids of the composition is preferably 60% by mass, more preferably 70% by mass, and even more preferably 80% by mass. By setting the copolymer (P) content within the above range, the heat resistance and other properties can be improved while fully exhibiting the visible light transmittance and infrared shielding properties of the resulting optical filter. In addition, polymers other than copolymer (P) may be used in combination with the composition, as long as they do not impair the physical properties.

[0094] ([C] Other infrared shielding agents) The composition may further contain [C] and other infrared shielding agents. The other infrared shielding agents are infrared shielding agents other than the aforementioned squarylium, polymethine, and other organic dyes, and are preferably metal oxides, copper compounds, or combinations thereof. The [C] and other infrared shielding agents are preferably compounds having a maximum absorption wavelength in the range of 800 nm to 2000 nm. The [C] and other infrared shielding agents may be used individually or in combination of two or more.

[0095] [C] Other examples of metal oxides used as infrared shielding agents include tungsten oxide compounds, quartz (SiO2), magnetite (Fe3O4), alumina (Al2O3), titania (TiO2), zirconia (ZrO2), and spinel (MgAl2O4).

[0096] [C] Other infrared shielding agents include metal oxides, and more preferably tungsten oxide compounds. Tungsten oxide compounds are infrared shielding agents that have high absorption (i.e., high shielding against infrared rays) for infrared rays (especially infrared rays with wavelengths of about 800 nm to 1200 nm) and low absorption for visible light.

[0097] The tungsten oxide compound is more preferably a tungsten oxide compound represented by the following formula (3).

[0098] A x WO y...(3) In equation (3), A is a metallic element. 0.001 ≤ x ≤ 1.1. 2.2 ≤ y ≤ 3.0.

[0099] Examples of metal elements represented by A in formula (3) above include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, etc. The metal element represented by A may be one or more types.

[0100] As for A above, alkali metals are preferred, Rb and Cs are more preferred, and Cs is even more preferred. In other words, the metal oxide is more preferably tungsten cesium oxide.

[0101] When x in formula (3) above is 0.001 or greater, infrared rays can be sufficiently shielded. The lower limit of x is preferably 0.01, and more preferably 0.1. On the other hand, when x is 1.1 or less, the formation of an impurity phase in the tungsten oxide-based compound can be more reliably avoided. The upper limit of x is preferably 1, and more preferably 0.5.

[0102] By setting y in equation (3) above to 2.2 or higher, the chemical stability of the material can be further improved. The lower limit of y is preferably 2.5. On the other hand, by setting y to 3.0 or lower, infrared rays can be sufficiently shielded.

[0103] A specific example of a tungsten oxide compound represented by the above formula (3) is Cs 0.33 WO3, Rb 0.33 WO3, K 0.33 WO3, Ba 0.33 Examples include WO3, etc. 0.33 WO3 and Rb 0.33 WO3 is preferred, Cs 0.33 WO3 is even more preferable.

[0104] [C] As other copper compounds used as infrared shielding agents, copper complexes are preferred. Preferred copper complexes are those of copper and a compound (ligand) having a coordination site for copper. Examples of coordination sites for copper include coordination sites that coordinate with anions and coordination atoms that coordinate with lone pairs of electrons. Copper complexes may have two or more ligands. If there are two or more ligands, each ligand may be the same or different. Examples of copper complexes include 4-coordinate, 5-coordinate, and 6-coordinate complexes, with 4-coordinate and 5-coordinate complexes being more preferred, and 5-coordinate complexes being even more preferred.

[0105] Copper complexes can be obtained, for example, by mixing or reacting a copper component (copper or a copper-containing compound) with a compound (ligand) that has a coordinating site for copper. The compound (ligand) having a coordinating site for copper may be a low-molecular-weight compound or a polymer. Both can also be used in combination.

[0106] The copper component is preferably a compound containing divalent copper. Only one type of copper component may be used, or two or more types may be used. Examples of copper components include copper oxide and copper salts. Examples of copper salts include copper carboxylates (e.g., copper acetate, copper ethylacetoacetate, copper formate, copper benzoate, copper stearate, copper naphthenate, copper citrate, copper 2-ethylhexanoate, etc.), copper sulfonates (e.g., copper methanesulfonate, etc.), copper phosphate, copper phosphate esters, copper phosphonates, copper phosphonate esters, copper phosphinate, copper amide, copper sulfonamide, copper imide, copper acylsulfonimide, copper bissulfonimide, copper methide, copper alkoxy, copper phenoxy, copper hydroxide, and carbonic acid. Copper, copper sulfate, copper nitrate, copper perchlorate, copper fluoride, copper chloride, and copper bromide are preferred; copper carboxylate, copper sulfonate, copper sulfonamide, copper imide, copper acylsulfonimide, copper bissulfonimide, copper alkoxy, copper phenoxy, copper hydroxide, copper carbonate, copper fluoride, copper chloride, copper sulfate, and copper nitrate are more preferred; copper carboxylate, copper acylsulfonimide, copper phenoxy, copper chloride, copper sulfate, and copper nitrate are even more preferred; and copper carboxylate, copper acylsulfonimide, copper chloride, and copper sulfate are particularly preferred.

[0107] [C]Other infrared shielding agents are preferably fine particles. The upper limit of the average particle size (D50) of [C]other infrared shielding agents is preferably 500 nm, more preferably 200 nm, even more preferably 50 nm, and even more preferably 30 nm. By keeping the average particle size below the above upper limit, visible light transmittance can be further increased. On the other hand, for reasons such as ease of handling during manufacturing, the average particle size of [C]other infrared shielding agents is usually 1 nm or more, and may be 10 nm or more.

[0108] [C] Other infrared shielding agents can be synthesized by known methods, but are also available commercially. When the metal oxide is, for example, a tungsten oxide compound, the tungsten oxide compound can be obtained, for example, by heat-treating a tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. Tungsten oxide compounds are also available as dispersions of tungsten fine particles, such as Sumitomo Metal Mining's "YMF-02".

[0109] The lower limit of the total infrared shielding agent content in the composition is preferably 0.1% by mass, more preferably 0.5% by mass, even more preferably 1% by mass, and still more preferably 2% by mass. On the other hand, the upper limit of this content is preferably 50% by mass, more preferably 40% by mass, even more preferably 30% by mass, and still more preferably 20% by mass. Here, the total infrared shielding agent includes the dye [Q], other organic dyes, [C], and other infrared shielding agents. By setting the infrared shielding agent content within the above range, the visible light transmittance and infrared shielding properties of the resulting optical filter are improved.

[0110] ([D] Dispersant) The composition may further contain a [D] dispersant. The [D] dispersant enhances the uniform dispersibility of [C] other infrared shielding agents (especially metal oxides), resulting in better visible light transmittance and infrared shielding properties of the resulting optical filter.

[0111] [D]Examples of dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, polyethylene glycol diester-based dispersants, sorbitan fatty acid ester-based dispersants, polyester-based dispersants, and (meth)acrylic-based dispersants. Among these, (meth)acrylic-based dispersants are preferred. [D]The dispersant is preferably a block copolymer.

[0112] ([E] Polymerizable compound) The composition may further contain an [E]polymerizable compound. When the composition contains an [E]polymerizable compound, it can exhibit good curability and good heat resistance of the resulting optical filter. An [E]polymerizable compound is a compound having two or more polymerizable groups. Examples of polymerizable groups include ethylenically unsaturated groups, oxyranyl groups, oxetanyl groups, and N-alkoxymethylamino groups. Preferred [E]polymerizable compounds are compounds having two or more (meth)acryloyl groups, two or more oxyranyl groups, and two or more N-alkoxymethylamino groups, and more preferably compounds having two or more (meth)acryloyl groups and two or more oxyranyl groups. One or more [E]polymerizable compounds can be used.

[0113] Examples of compounds having two or more (meth)acryloyl groups include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxyethanol full orange (meth)acrylate, bisphenoxyethanol full orange (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl) phosphate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0114] Examples of compounds having two or more oxiranil groups include aliphatic epoxy compounds. These are available as commercially produced products. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, Examples include EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (all manufactured by Nagase ChemteX Co., Ltd.), Celoxide 2021P, 2081, 3000, EHPE3150, Epolid GT401, Cellvinace B0134, B0177 (manufactured by Daicel Corporation), and others. [E] The polymerizable compound content is preferably 20% by mass or more and 120% by mass or less, based on 100% by mass of the total amount of copolymer (P) component.

[0115] ([F] polymerization initiator) The composition may contain a [F] polymerization initiator. Examples of [F] polymerization initiators include photopolymerization initiators and thermal polymerization initiators, but photopolymerization initiators are preferred. This allows the composition to be given photosensitivity (radiation sensitivity). A photopolymerization initiator is a compound that generates active species capable of initiating polymerization of [E] polymerizable compounds, etc., upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. One or more [F] polymerization initiators can be used.

[0116] ([G] Acid Generator) The composition may contain an [G] acid generator. The [G] acid generator is a compound that generates acid upon irradiation with radiation. By containing the [G] acid generator, the composition can exhibit positive-type radiation sensitivity to, for example, alkaline developers. The [G] acid generator is not particularly limited as long as it is a compound that generates acid (e.g., carboxylic acid, sulfonic acid, etc.) upon irradiation with radiation. Examples of [G] acid generators include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, quinone diazide compounds, etc. Of these, quinone diazide compounds are preferred.

[0117] (Additives) In addition to the components described above, the composition may also contain various additives as needed.

[0118] Examples of additives include surfactants, adhesion promoters, antioxidants, UV absorbers, anti-flocculation agents, residue improvers, developability improvers, and reaction modifiers.

[0119] Examples of surfactants include fluorine surfactants and silicone surfactants.

[0120] Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

[0121] Examples of antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0122] Any conventionally known UV absorber capable of exhibiting UV absorption can be used. Among such UV absorbers, it is preferable to use a benzotriazole-based or hydroxyphenyltriazine-based UV absorber from the viewpoint of obtaining UV absorption capacity (UV blocking capacity). Furthermore, in order to broaden the UV absorption range, two or more UV absorbers with different maximum absorption wavelengths can be used in combination. Specific examples of UV absorbers include, for example, the compounds described in paragraphs

[0258] to

[0259] of Japanese Patent Application Publication No. 2012-18395 and the compounds described in paragraphs

[0055] to

[0105] of Japanese Patent Application Publication No. 2007-72163. In addition, commercially available products such as Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, and Tinuvin 1577 (all manufactured by BASF) can be used.

[0123] Examples of anti-coagulants include sodium polyacrylate.

[0124] Examples of residue improving agents include malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol.

[0125] Examples of developing agents include mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, ω-carboxypolycaprolactone mono(meth)acrylate, etc.

[0126] Examples of reaction modifiers include polyfunctional thiols.

[0127] (solvent) The composition (I) is usually prepared as a liquid composition containing a solvent (dispersion medium). Any solvent can be appropriately selected and used, as long as it disperses or dissolves other components, does not react with these components, and has appropriate volatility.

[0128] Examples of such solvents include, for example... (Poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. Alkyl lactate esters such as methyl lactate and ethyl lactate, (Cyclo)alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, and cyclohexanol, Keto alcohols such as diacetone alcohol, (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran, Ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone and other linear ketones, and cyclopentanone and cyclohexanone and other cyclic ketones. Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate, Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and methyl-3-methoxybutylpropionate, Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, and other esters, Aromatic hydrocarbons such as toluene and xylene, Examples include amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0129] The solvent content in the composition is not particularly limited. The lower limit of the solid content concentration (total concentration of each component excluding the solvent) in the composition is preferably 5% by mass, and more preferably 10% by mass. On the other hand, the upper limit of this solid content concentration is preferably 50% by mass, and more preferably 40% by mass. By setting the solid content concentration within the above range, dispersibility, stability, and coatability are improved.

[0130] (Preparation method) The method for preparing the composition is not particularly limited and can be prepared by mixing the components. The composition can be filtered as needed to remove aggregates.

[0131] <Infrared shielding film> An infrared shielding film for optical filters can be formed from the composition of the present invention. This infrared shielding film has good properties in terms of visible light transmission window range, infrared shielding range, heat resistance, and chemical resistance.

[0132] The infrared shielding film can be formed, for example, by the following method. First, the composition is applied to a support, and then pre-baking is performed to evaporate the solvent and form a coating film. After that, post-baking is performed to obtain the infrared shielding film. If development is performed, after the coating film is formed, the coating film is exposed to light, and then developed using a developer to dissolve and remove the unexposed parts of the coating film. After that, post-baking is performed to obtain an infrared shielding film patterned into a predetermined shape.

[0133] The support to which the composition is applied includes the transparent substrate, microlens, color filter, etc. The application can be carried out using various methods such as spray coating, roll coating, rotary coating (spin coating), slit die coating (slit coating), or bar coating.

[0134] The heating and drying conditions in the above pre-bake process are, for example, 70°C to 110°C and for 1 to 10 minutes.

[0135] When developing a coating, the radiation light source used for exposure of the coating can include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, as well as laser light sources such as argon ion lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers. Ultraviolet LEDs can also be used as the exposure light source. The wavelength of the radiation is preferably in the range of 190 nm to 450 nm. The radiation exposure dose is generally 10 J / m². 2 More than 50,000J / m 2 It is approximately as follows.

[0136] The developer used is typically an alkaline developer. Preferred alkaline developers include aqueous solutions of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene. Appropriate amounts of water-soluble organic solvents such as methanol and ethanol, or surfactants, can also be added to the alkaline developer. After development, the image is usually washed with water.

[0137] Applicable development methods include shower development, spray development, dip development, and paddle development. Development conditions are approximately 5 to 300 seconds at room temperature.

[0138] The typical post-bake conditions are between 180°C and 280°C, and for between 1 minute and 60 minutes.

[0139] The lower limit of the average thickness of the infrared shielding film formed in this manner is usually 0.5 μm, with 1 μm being preferred. On the other hand, the upper limit of this average thickness is usually 20 μm, with 10 μm being preferred. Having the average thickness of the infrared shielding film within the above range results in a better balance between visible light transmittance and infrared shielding properties.

[0140] <Optical filters> An infrared shielding film formed from a composition according to one embodiment of the present invention can be used in an optical filter. An optical filter having the above infrared shielding film has few defects such as foreign matter and has good characteristics regarding visible light transmittance and infrared shielding. This optical filter can be used as an optical filter for optical sensors such as solid-state image sensors.

[0141] The optical filter may consist solely of the infrared shielding film, or it may consist of the infrared shielding film and other components. For example, the optical filter may be a laminate having the infrared shielding film and other layers.

[0142] It is preferable that the infrared shielding film is incorporated as a component into an optical sensor such as a solid-state image sensor. In this case, the infrared shielding film functions as an optical filter (infrared cut filter) on its own. It is preferable that the infrared shielding film is incorporated into the optical sensor, as this allows for obtaining a large process margin. When the infrared shielding film is incorporated into a solid-state image sensor, it can be placed, for example, on the outer surface of the microlenses of the solid-state image sensor, between the microlenses and the color filter, or between the color filter and the photodiode. It is preferable that the infrared shielding film is laminated between the microlenses and the color filter or between the color filter and the photodiode.

[0143] As the optical filter, it may be one in which the infrared shielding film is laminated on the surface of a transparent substrate. As the transparent substrate, glass, transparent resin, etc. are adopted. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. As the optical filter, in order to shield light in a wider near-infrared region to infrared region, a dielectric multilayer film may be provided on the infrared shielding film or on the transparent substrate. Examples of the dielectric multilayer film include a laminate in which a high refractive index material layer and a low refractive index material layer are alternately laminated. Also, instead of providing a dielectric multilayer film directly above the infrared shielding film laminate, another transparent substrate having a dielectric multilayer film may be separately disposed in the element. Such an optical filter is also suitably used as an infrared cut filter in a solid-state imaging device, etc.

[0144] Optical sensors such as solid-state imaging devices equipped with the above optical filter are useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, portable information terminals, personal computers, video games, medical devices, etc.

[0145] <Optical sensor> The above optical filter is used in optical sensors such as solid-state imaging devices. Since the above optical filter has few defects such as foreign matters and has good characteristics regarding visible light transmittance and infrared shielding property, optical sensors such as solid-state imaging devices having the optical filter have high sensitivity, color reproducibility, etc. and are excellent in practicality.

[0146] The following describes a solid-state image sensor as an example of an optical sensor. Generally, this solid-state image sensor has a structure in which layers of multiple photodiodes, color filters, and microlenses are stacked in this order. Planarization layers may also be provided between these layers. In this solid-state image sensor, light is incident from the microlens side. The incident light passes through the microlenses and color filters and reaches the photodiodes. The color filters, for example, are configured so that only light within a specific wavelength range is transmitted in each of the R (red), G (green), and B (blue) filters.

[0147] In the solid-state image sensor, the optical filter (infrared shielding film) can be provided on the outer surface of the microlens, between the microlens and the color filter, or between the color filter and the layer on which the plurality of photodiodes are arranged. Preferably, the optical filter is laminated between the microlens and the color filter or between the color filter and the photodiodes. In addition, another layer (such as a planarization layer) may be provided between the optical filter and the microlens, color filter, photodiodes, etc.

[0148] Specific examples of such solid-state image sensors include CCDs and CMOS sensors used in camera modules. These solid-state image sensors are useful in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, personal digital assistants (PDAs), personal computers, video games, medical equipment, and the like. [Examples]

[0149] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0150] The abbreviations for the compounds are as follows. In the following, the compound represented by formula (X) may simply be referred to as "compound (X)".

[0151] M1: Methacrylic acid M2: Acrylic acid M3: Mono[2-(meth)acryloyloxyethyl] succinate M4: Glycidyl methacrylate M5: 3,4-epoxycyclohexyl methacrylate M6:3-(methacryloyloxymethyl)-2-methyloxetane M7: Styrene M8: Tricyclomethacrylate [ 5.2.1.0 2,6 ] Decan-8-il M9: Methyl methacrylate M10: Benzyl methacrylate M11: Cyclohexyl methacrylate M12: 1-adamantyl methacrylate Squallium 1: Compound represented by the above formula (ID-1) Squallium-2: A compound represented by the above formula (ID-2). Squallium-3: Compound represented by the above formula (ID-4) Polymethine 1: Compound represented by the above formula (III-6) Polymethine 2: Compound represented by the above formula (III-2) Polymethine 3: Compound represented by the above formula (III-3) Polymerizable compound 1: Celoxide 2021P, manufactured by Daicel Corporation. Other organic dyes 1: Daito Chemix 1371F (manufactured by Daito Chemix Co., Ltd.) Other organic pigments 2: Compounds represented by the following formula (color-2)

[0152] [ka]

[0153] UV absorber 1: Compound represented by the following formula (UVA-1)

[0154] [ka]

[0155] Ultraviolet absorber 2: A compound represented by the following formula (UVA-2)

[0156] [Chemical formula]

[0157] Surfactant 1: KF-643 (silicone type) manufactured by Shin-Etsu Chemical Co., Ltd. Surfactant 2: Megafac F-474 (fluorine type) manufactured by DIC Corporation Adhesion promoter 1: γ-Glycidoxypropyltrimethoxysilane Adhesion promoter 2: 3-Aminopropyltriethoxysilane Antioxidant 1: Irganox1010 manufactured by BASF Solvent 1: Cyclopentanone

[0158] (Synthesis example 1) In a flask equipped with a condenser and a stirrer, when the mass of the unsaturated mixture was 100% by mass, 7% by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200% by mass of diethylene glycol ethyl methyl ether were charged in advance. Then, an unsaturated mixture containing 20% by mass of methacrylic acid, 30% by mass of glycidyl methacrylate, and 50% by mass of methyl methacrylate, a total of 100% by mass, was added, and after nitrogen substitution, gentle stirring was started. The temperature of the solution was raised to 70 °C, and this temperature was maintained for 4 hours to terminate the polymerization. Thereafter, the reaction product solution was dropped into a large amount of methanol to coagulate the reaction product. After washing this coagulum with water, it was redissolved in tetrahydrofuran and coagulated again with a large amount of methanol. After performing this redissolution-coagulation operation a total of 3 times, the obtained coagulum was vacuum dried at 60 °C for 48 hours to obtain the target [Polymer 1].

[0159] In Synthesis Example 1, [Polymer 2] to [Polymer 8] were obtained in the same manner as in Synthesis Example 1, except that the types and amounts of the monomer components were used as shown in Table 1.

[0160] [Table 1]

[0161] [Example 1] When polymer 1 is considered to be 100% by mass, 0.7% by mass of squarylium 1, 1.5% by mass of polymethine 1, 0.7% by mass of ultraviolet absorber 1, 1.8% by mass of adhesion promoter 1, 1.1% by mass of antioxidant 1, and 354% by mass of cyclopentanone as a solvent were weighed into a container and mixed with a stirrer. The composition of Example 1 was obtained by pressure filtration of this mixture using a 0.5 μm PTFE filter under a constant pressure of 0.05 MPa.

[0162] [Examples 2-6, Comparative Examples 1-9] The compositions of Examples 2-6 and Comparative Examples 1-9 were obtained in the same manner as in Example 1, except that the types and blending ratios (mass%) of polymers, dyes, various additives, and solvents were as shown in Table 1. [evaluation] The following evaluations were performed using each of the obtained compositions. The evaluation results are shown in Table 1.

[0163] Each composition was applied to a glass substrate by spin coating to a predetermined thickness. The coating was then heated at 100°C for 120 seconds, followed by heating at 200°C for 300 seconds to create an infrared shielding film with an average thickness of 10 μm on the glass substrate. The film thickness was measured using a stylus-type step meter ("Alpha Step IQ" by Yamato Scientific Co., Ltd.). Next, the transmittance of the infrared shielding film fabricated on the glass substrate in each wavelength range was measured relative to the glass substrate using a spectrophotometer ("V-7300" by JASCO Corporation). The obtained spectra were evaluated according to the following criteria.

[0164] (Visible light transmission window range) We determined the range in the 400-700nm range where the transmittance is continuously 70% or higher. If the range with continuous transmittance of 70% or higher extends to 180nm or longer, it is estimated to have high sensitivity and therefore high practicality when used as an infrared shielding film. Furthermore, the visible light transmission window range was evaluated according to the following criteria. ○:180nm or more △: 170nm or more and less than 180nm ×: Less than 170nm

[0165] (Infrared shielding range) We determined the range in the 600-1200nm range where the transmittance is continuously 20% or less. If the range where the transmittance is continuously 20% or less is 70nm or longer, it is estimated that the film will have high noise shielding capabilities when used as an infrared shielding film, making it highly practical. Furthermore, the above infrared shielding range was evaluated according to the following criteria. ○:70nm or more ×: 40nm or more and less than 70nm ××: Less than 40nm

[0166] (Heat resistance) The infrared shielding film fabricated on the glass substrate described above was heated at 220°C for 30 minutes using a hot plate. The transmittance in each wavelength range before and after heating was measured relative to the glass substrate using a spectrophotometer (JASCO's "V-7300"). At this time, the absorbance at the wavelength in the 600-1200nm range where the transmittance of the fabricated infrared shielding film was lowest was (A1), and the absorbance at the same wavelength after heating at 220°C was (A2). The heat resistance at 220°C was evaluated using the following criteria, with absorbance retention rate = 100 × (A2) / (A1). If the retention rate is 50% or higher, it is estimated that the film can maintain high heat resistance when used as an infrared shielding film, and is highly practical. Furthermore, the above retention rate was evaluated using the following criteria. ◎: 80% or more ○: 50% or more but less than 80% △: 30% or more but less than 50% ×: Less than 30%

[0167] (chemical resistance) The infrared shielding film fabricated on the glass substrate described above was immersed in N-methyl-2-pyrrolidone in a petri dish for 10 minutes at room temperature. The transmittance in each wavelength range before and after immersion was measured relative to the glass substrate using a spectrophotometer (JASCO Corporation's "V-7300"). At this time, the absorbance at the wavelength in the 600-1200 nm range where the transmittance of the fabricated infrared shielding film was lowest was (A1), and the absorbance at the same wavelength after immersion in N-methyl-2-pyrrolidone was (A2). The absorbance retention rate was set to 100 × (A2) / (A1), and the chemical resistance was evaluated according to the following criteria. If the retention rate is 50% or higher, it is estimated that the film can maintain high chemical resistance when used as an infrared shielding film, and is highly practical. Furthermore, the above retention rate was evaluated according to the following criteria. ○: 50% or more △: 30% or more but less than 50% ×: Less than 30%

[0168] (Coating defects after low-temperature storage) An infrared-absorbing composition, left to stand at -15°C for one week, was coated onto a silicon substrate using a spinner to form a coating with a thickness of 1 μm. The defect density of the coating was measured using a defect / foreign matter inspection device (KLA-Tencor's "KLA 2351"). A smaller defect density indicates higher foreign matter removal efficiency, i.e., that foreign matter has been sufficiently removed. Based on the above defect density, the foreign matter removal efficiency was evaluated according to the following criteria. ○: 10 / cm 2 below △: 10 / cm 2 Super 50 / cm 2 below ×: 50 / cm 2 super

[0169] (Coating defects after long-term low-temperature storage) An infrared-absorbing composition, left to stand at -15°C for two months, was coated onto a silicon substrate using a spinner to form a coating with a thickness of 1 μm. The defect density of the coating was measured using a defect / foreign matter inspection device (KLA-Tencor's "KLA 2351"). A smaller defect density indicates higher foreign matter removal efficiency, i.e., that foreign matter has been sufficiently removed. Based on the above defect density, the foreign matter removal efficiency was evaluated according to the following criteria. ○: 10 / cm 2 below △: 10 / cm 2 Super 50 / cm 2 below ×: 50 / cm 2 super

[0170] [Table 2]

[0171] As shown in Table 1 above, all of Examples 1 to 6 were evaluated favorably in terms of visible light transmission window range, infrared shielding range, heat resistance, chemical resistance, and suppression of coating defects after low-temperature storage, and also showed high suppression of coating defects after long-term low-temperature storage. [Industrial applicability]

[0172] The optical sensor composition of the present invention can be suitably used as a material for forming an optical filter of an optical sensor such as a solid-state image sensor.

Claims

1. (a1) A copolymer (P) of an unsaturated mixture containing at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and (a2) at least one selected from the group consisting of oxiranyl group-containing unsaturated compounds and oxetanyl group-containing unsaturated compounds, and a dye [Q] containing at least one polymethine compound, A composition for optical sensors, wherein the polymethine compound comprises a compound represented by the following formula (III). Cn + An - (III) [In formula (III), Cn+ is a monovalent cation represented by formula (IV) or formula (VI) below, and An- is a monovalent anion. 【Chemistry 1】 In formulas (IV) and (VI), Unit A is one of the following equations (A-I) to (A-III): Unit B is one of the following equations (B-I) to (B-III): Z A to Z C and Y A to Y I are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a nitro group, a -NR g R h group, an amide group, an imide group, a cyano group, a silyl group, -Q 1, -N=N-Q 1, -S-Q 2, -SSQ 2, or -SO 2 Q 3. Among Z A to Z C and YA A to Y I, two adjacent elements may be linked to each other to form a ring. Some groups in unit A may be bonded to Y A or Y F to form a cyclic hydrocarbon group having 5 or 6 carbon atoms, and some groups in unit B may be bonded to Y E or Y I to form a cyclic hydrocarbon group having 5 or 6 carbon atoms. R g and R h are independently a hydrogen atom, a -C(O)Ri group, or one of the following La to L h groups; Q 1 is independently one of the following La to L h groups; Q 2 is independently a hydrogen atom or one of the following La to L h groups; Q 3 is a hydroxyl group or one of the following La to L h groups; and Ri is one of the following La to L h groups. 【Chemistry 2】 In formulas (A-I) to (A-III), the -* indicates that YA or YF in formula (IV) forms a single bond with the carbon atom to which it is bonded. In formulas (B-I) to (B-III), the =** indicates that Y E or Y I in formula (IV) forms a double bond with the carbon atom to which it is bonded. In formulas (AI) to (B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR8-. R1 to R6 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, It is a nitro group, carboxyl group, phosphate group, -NR g R h group, -SR i group, -SO 2 Ri group, -OSO 2 Ri group, -C(O)R i group, or any of the following L a to L h groups. Adjacent R1 to R6 may bond to each other to form a 4-7 membered alicyclic group containing at least one C6-C14 aromatic hydrocarbon group, a nitrogen atom, an oxygen atom, or a sulfur atom, or a C3-C14 heteroaromatic group containing at least one nitrogen atom, an oxygen atom, or a sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may also have a hydroxyl group, a C1-C9 aliphatic hydrocarbon group, or a halogen atom, and the alicyclic group may also have =O. R8 is independently a hydrogen atom, a halogen atom, a -C(O)Ri group, or one of the following La to Lh. Ri is independently one of the following La to L h: (L a): Aliphatic hydrocarbon group having 1 to 15 carbon atoms (L b): Halogen-substituted alkyl group having 1 to 15 carbon atoms (L c): A cycloaliphatic hydrocarbon group having 3 to 14 carbon atoms, which may have a substituent K. (L d): A C6-C14 aromatic hydrocarbon group which may have a substituent K (L e): A heterocyclic group having 3 to 14 carbon atoms, which may have a substituent K. (L f): -OR (R is a C1-C12 hydrocarbon group which may have substituent L) (L g): Acyl group having 1 to 9 carbon atoms, which may have substituent L. (L h): A C1-C9 alkoxycarbonyl group which may have substituent L. The substituent K is at least one selected from L a to L b, and the substituent L is at least one selected from L a to L f.

2. The optical sensor composition according to claim 1, wherein a polymethine compound is contained in 20% by mass or more of the total dye [Q].

3. The optical sensor composition according to claim 1, wherein the mass ratio (a2) / (a1) of the constituent unit (a1) derived from (a1) in the copolymer (P) to the constituent unit (a2) derived from (a2) is 1 or more.

4. The optical sensor composition according to claim 1, wherein the constituent unit (a2) derived from (a2) is contained in an amount of 10% by mass or more relative to the total constituent units of the copolymer.

5. The optical sensor composition according to claim 1, wherein the copolymer (P) is a copolymer of an unsaturated mixture further containing an unsaturated compound having an alicyclic structure.

6. An optical sensor formed using the optical sensor composition described in claim 1.

7. A solid-state image sensor characterized by comprising the optical sensor described in claim 6.

8. A camera module characterized by comprising the optical sensor described in claim 6.

Images