KR20230001531A - Composition for optical sensor and optical sensor, and solid state image pickup device using optical filter and camera module - Google Patents

Abstract

Provided is a composition for an optical sensor capable of forming an optical filter for an optical sensor, which has good properties with respect to a visible light transmission window range, an infrared shielding range, heat resistance, drug resistance, coating defect suppression after low-temperature storage, and coating defect suppression after long-term low-temperature storage. According to the present invention, the composition for an optical sensor comprises: (a1) at least one member selected from a group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides; (a2) a copolymer (P) of an unsaturated mixture containing at least one member selected from a group consisting of an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound; and a pigment (Q) containing at least one polymethine-based compound.

Description

Composition for optical sensor, optical sensor, and solid-state imaging device and camera module using corresponding optical filter

The present invention relates to a composition for an optical sensor and an optical sensor.

BACKGROUND OF THE INVENTION [0002] Video cameras, digital cameras, mobile phones with camera functions, and the like are equipped with solid-state imaging elements that are optical sensors. As the solid-state imaging element, specifically, a CCD (Charge-Coupled Device) image sensor, a CMOS (Complementary MOS) image sensor, or the like is known. The sensitivity of the photodiode provided in these solid-state imaging devices ranges from the visible light region to the infrared region. For this reason, in the solid-state imaging element, a filter for blocking infrared rays is provided. With this optical filter (infrared cutoff filter), the sensitivity of the solid-state imaging device can be corrected so as to approximate human visibility. In an optical sensor other than a solid-state imaging device, a filter for blocking infrared rays may be similarly provided.

The optical filter contains a dye or pigment as an infrared ray shielding agent. The infrared ray shielding agent is required to have a property of absorbing infrared rays while sufficiently transmitting visible light. As one of these infrared shielding agents, especially as a good near-infrared shielding agent, using a phthalocyanine compound has been studied (see Japanese Patent Laid-Open No. 2008-201952).

Further, a composition for pattern formation containing a squarylium compound together with an acrylic polymer is disclosed (Japanese Patent No. 6903143) for the purpose of improving the development residue suppression property, pattern formability, and heat resistance.

Japanese Unexamined Patent Publication No. 2008-201952 Japanese Patent No. 6903143

However, with the recent high performance of required optical characteristics, it has become difficult to obtain sufficient characteristics, and further improvement is desired. In addition, along with the diversification of the uses of optical sensors, optical filters that can withstand even harsher environments are desired. On the other hand, from the viewpoint of the production process margin, it is also desired to obtain an infrared shielding film with few defects such as foreign matter even if it is cured after being left for a while after coating in the production process. In view of the above situation, a composition for an optical sensor that achieves both optical properties, heat resistance, and storage stability has been desired.

The present invention has been made based on the above circumstances, and its object is to provide good characteristics with respect to visible light transmission window range, infrared shielding range, heat resistance, chemical resistance, coating defect suppression after low temperature storage, and coating defect suppression after long-term low temperature storage. It is to provide a composition for an optical sensor capable of forming an optical filter for an optical sensor having an optical sensor.

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

According to the present invention, an optical filter for an optical sensor having good properties in terms of visible light transmission window range, infrared shielding range, heat resistance, chemical resistance, coating defect suppression after low temperature storage, and coating defect suppression after long-term low temperature storage can be formed. A composition for an optical sensor can be provided.

Hereinafter, a composition for an optical sensor according to an embodiment of the present invention will be described in detail.

<Composition for optical sensor>

The composition for an optical sensor 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) an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound. A copolymer (P) of an unsaturated mixture containing at least one selected from the group consisting of

A pigment [Q] containing at least one polymethine-based compound is contained.

(pigment [Q])

(Polymethine compound)

The polymethine-based compound used in the present invention is a polymethine dye and is a compound other than a squarylium-based compound, a croconium-based compound, and a cyanine-based compound, and is not particularly limited as long as it does not impair the effects of the present invention. For example, For example, the compound described in Unexamined-Japanese-Patent No. 2019-164269 is mentioned, What is necessary is just to synthesize|combine by a generally known method.

ㆍPolymethine compound (iii)

As the polymethine-based compound, a compound represented by the following formula (III) is preferable from the viewpoint of easily obtaining an optical filter exhibiting the above effects more.

Cn⁺An^- (III)

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

Of formula (IV) and formula (VI),

Unit A is any of the following formulas (A-I) to (A-III),

Unit B is any of the following formulas (B-I) to (B-III),

Z _A to Z _C and Y _A to Y _I are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy 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=NQ ¹ , -SQ ² , -SSQ ² or -SO ₂ Q ³ ,

Among Z _A to Z _C and Y _A to Y _I , two adjacent ones may be bonded to each other to form a ring,

Some groups in unit A may combine with Y _A or Y _F to form a cyclic hydrocarbon group having 5 or 6 carbon atoms, and some groups in unit B may combine with Y _E or Y _I to form a cyclic hydrocarbon group having 5 or 6 carbon atoms. A group may be formed.

R ^g and R ^h are each independently a hydrogen atom, a -C(O)R ⁱ group, or any of the following ^La to L ^h , Q ¹ is independently any of the following ^La to L ^h , and Q ² is independently is a hydrogen atom or any of the following La to L ^h , Q ³ is ^a hydroxyl group or any of the following ^La to L ^h , and R ⁱ is any of the following ^La to L ^h .

-* in formulas (AI) to (A-III) represents a single bond with the carbon bonded to Y _A or Y _F in formula (IV);

=** in formulas (BI) to (B-III) represents a double bond with the carbon to which Y _E or Y _I in the formula (IV) is bonded;

In Formulas (A-I) to (B-III),

X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ -;

R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R ⁱ group, - OSO ₂ R ⁱ group, -C(O)R ⁱ group or any of the following L ^a to L ^h ,

Adjacent R ¹ to R ⁶ are bonded to each other, an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4 to 7 membered alicyclic group which may contain at least one nitrogen atom, an oxygen atom or a sulfur atom, or a nitrogen atom, an oxygen atom, or A heteroaromatic group containing at least one sulfur atom and having 3 to 14 carbon atoms may be formed, and these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a halogen atom. , In addition, the aerator may have = O,

R ⁸ is independently a hydrogen atom, a halogen atom, a -C(O)R ⁱ group, any of the following L ^a to L ^h ;

R ⁱ is independently any of the following L ^a to L ^h ,

(L ^a ): An aliphatic hydrocarbon group having 1 to 15 carbon atoms

(L ^b ): A halogen-substituted alkyl group having 1 to 15 carbon atoms

(L ^c ): An alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K

(L ^d ): An aromatic hydrocarbon group having 6 to 14 carbon atoms 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 a substituent L)

(L ^g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L

(L ^h ): An alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L

The substituent K is at least one selected from ^{La to L b ,} and the substituent L is at least one selected from ^La to L ^f .

In addition, the -NR ⁸ - is a group represented by the following formula (a), the -NR ^g R ^h group is a group represented by the following formula (b), and the -SR ⁱ group is represented by the following formula (c) The -SO ₂ R ⁱ group is a group represented by the following formula (d), the -OSO ₂ R ⁱ group is a group represented by the following formula (e), and the -C(O)R ⁱ group is represented by the following formula It is the group represented by (f).

In addition, -SSQ ² is a group represented by -SSQ ² , and -SO ₂ Q ³ is a group represented by the following formula (d) in which R ⁱ is substituted with Q ³ .

Further, when the unit A is the formula (AI) and the unit B is the formula (BI), Cn ⁺ is represented by the following formula (IV-1) or the following formula (VI-1). That is, the single bond (-) of “*-” in the above formulas (AI) to (A-III) is the carbon to which Y _A in the above formula (IV) or Y _F in the following formula (VI) is bonded Corresponds to a single bond between the atom and unit A, and the double bond (=) of "**=" in the formulas (BI) to (B-III) is Y _E in the formula (IV) or the following formula It corresponds to the double bond between the carbon atom to which Y _I of (VI) is bonding and unit B.

Y _B and Y _D , Y _G and Y _H are each independently, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, and a 4 to 6 membered alicyclic ring formed by bonding Y _B and Y _D to each other. It is a formula hydrocarbon group (the alicyclic hydrocarbon group may have a substituent R ⁹ selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a hydroxyl group, a halogen atom, and =O).

Further, when Y _B and Y _D are 4 to 6 membered alicyclic hydrocarbon groups formed by bonding to each other, formula (IV) can be preferably represented by the following formulas (IV-A) to (IV-C), respectively, , When Y _G and Y _H are a 4 to 6 membered alicyclic hydrocarbon group formed by bonding with each other, formula (VI) can be preferably represented by the following formulas (VI-A) to (VI-B), respectively.

As the substituent R ⁹ , a hydrogen atom, a hydroxyl group, =O, 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, and a cyclohexyl group are preferable, and a hydrogen atom is , a hydroxyl group, =O, a methyl group, an ethyl group, and a tert-butyl group are more preferable.

Y _A , Y _C , Y _E and Z _A to Z _C are each independently selected from each other, preferably a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, a -NR ^g R ^h group, an amide group, an imide group, or a cyanide group. No group, silyl group, -Q ¹ , -N=NQ ¹ , -SQ ² , -SSQ ² , -SO ₂ Q ³ , or adjacent two of Y _A , Y _C , Y _E and Z _A to Z _C are mutually Combined, 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; Alternatively, a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom, or sulfur atom; may be formed, and these alicyclic groups, aromatic hydrocarbon groups, and heteroaromatic groups are aliphatic hydrocarbon groups having 1 to 9 carbon atoms. Or you may have a halogen atom,

The L ^a is preferably 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 ), pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, more preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- It is a butyl group.

L ^a is an alkenyl group such as a vinyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, a 1,3-butadienyl group, a 2-methyl-1-propenyl group, a 2-pentenyl group, and a hexenyl group; An alkynyl group such as an ethynyl group, a propynyl group, a butynyl group, a 2-methyl-1-propynyl group, or a hexynyl group may be used.

Examples of the halogen-substituted alkyl group having 1 to 15 carbon atoms in L ^b include groups in which at least one hydrogen atom in the alkyl group having 1 to 15 carbon atoms is substituted with a halogen atom, and preferably trichloromethyl group and trifluoro A methyl group, a 1,1-dichloroethyl group, a pentachloroethyl group, a pentafluoroethyl group, a heptachloropropyl group, and a heptafluoropropyl group.

As the alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have the substituent K in the above L ^c , it is preferably a cyclopropyl group, a cyclopropylmethyl group, a methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group. Cycloalkyl groups, such as a methylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Polycyclic alicyclic groups, such as a norbornane group and an adamantyl group, are mentioned.

As the aromatic hydrocarbon group having 6 to 14 carbon atoms which may have the substituent K in the above L ^d , preferably a phenyl group, a tolyl group, a xylyl group, a mesityl group (trimethylphenyl group), cumenyl group, bis(trifluoromethyl) ) Phenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, phenanthryl group, benzyl group (CH ₂ Ph).

As the heterocyclic group having 3 to 14 carbon atoms which may have the substituent K in the above L ^e , preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, morpholine, pyridine to be.

As -OR in said L ^f , Preferably, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a methoxymethyl group, a methoxyethyl group, a pentyloxy group, a hexyloxy group, an octyloxy group is selected. , a phenoxy group (OPh), a 4-methylphenoxy group, and a cyclohexyloxy group.

The acyl group having 1 to 9 carbon atoms which may have the substituent L in the above L ^g is preferably an acetyl group, propionyl group, butyryl group, isobutyryl group, benzoyl group, 4-propylbenzoyl group, trifluoro It is a methylcarbonyl group.

The alkoxycarbonyl group having 1 to 9 carbon atoms which may have the substituent L in the above L ^h is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, and 2-trifluoro. They are a methylethoxycarbonyl group and a 2-phenylethoxycarbonyl group.

Said X is preferably an oxygen atom, a sulfur atom, or -NR ⁸ -, and is particularly preferably an oxygen atom.

In the formulas (IV) and (VI), the units A and B on the left and right may be the same or different, but the same unit is preferable because it is synthetically easy.

In addition, here, the combination of the same unit A and B is formula (A-I) and formula (B-I), formula (A-II) and formula (B-II), formula (A-III) and formula (B-III) to be.

R ¹ to R ⁶ are each independently selected from, 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, and tert -Butyl group, 1,1-dimethylbutyl group, cyclopropyl group, cyclopropylmethyl group, cyclohexyl group, adamantyl group, phenyl group, 2,4,6-trimethylphenyl group, 3,5-bis(trifluoromethyl) Phenyl group, hydroxyl group, amino group, dimethylamino group (NMe ₂ ), diethylamino group (NEt ₂ ), dibutylamino group (N(n-Bu) ₂ ), cyano group, nitro group, acetylamino group, propionylamino group, N-methyl Acetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, tert-butanoylamino group, cyclohexynoylamino group, n-butylsulfonyl group, benzyl group, diphenylmethyl group, trifluoromethyl group, difluoro A methyl group or a methoxy group, more 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, or 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, and a methoxy group.

At least one of the R ¹ to R ⁶ has high near-infrared ray cutting performance and high visible light transmission performance at an absorption maximum in the vicinity of a wavelength of 700 to 750 nm or a wavelength of 720 to 900 nm, and has excellent optical properties, From the viewpoint of easily obtaining a compound having sufficient resistance to light, the above L ^a , L ^c or L ^d is preferable. In addition, when the unit A is the formula (A-III) and the unit B is the formula (B-III), "at least one of R ¹ to R ⁶ is L ^a , L ^c or L ^d " means , "at least one of R ¹ , R ² , R ⁴ , and R ⁵ is L ^a , L ^c or L ^d ".

As said ^R8 , Preferably they are a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, a benzyl group, n-pentyl group, n-hexyl group, or tert-butyl group, More preferably Preferably, they are a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a benzyl group.

The An ⁻ is not particularly limited as long as it is a monovalent anion, but is preferably a chloride ion, a bromine ion, an iodine ion, PF ₄ ⁻ , a perchlorate anion, a tristrifluoromethanesulfonylmethide anion, a tetrafluoroborate anion, and a hexavalent anion. Fluorophosphate anion, bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonic acid anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(3,5-bis(trifluoromethyl) phenyl) borate anion and the like, more preferably bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonic acid anion, tritrifluoromethanesulfonylmethide anion, tetrakis(pentafluoro A phenyl) borate anion or a tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion, from the viewpoint of easily obtaining a compound having better heat resistance, more preferably bis(trifluoromethyl) methanesulfonyl)imide anion, tritrifluoromethanesulfonylmethide anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion, particularly Preferred is tetrakis(pentafluorophenyl)borate anion.

Specific examples of the compound (III) having a monovalent cation represented by the formula (IV) include the following compounds (III-1) to (III-3) and the like.

Specific examples of compound (III) having a monovalent cation represented by formula (VI) include the following compounds (III-4) to (III-6) and the like.

In the present invention, as the dye [Q], the polymethine-based compound described above is included as an essential component.

The polymethine-based compound is contained in an amount of 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more, of the total dye [Q]. In this way, by including a predetermined amount of the polymethine-based compound, it is possible to obtain a composition for an optical sensor having excellent characteristics such as long-term low-temperature storage, heat resistance, and chemical resistance.

Dye [Q] may further contain a squarylium-based compound.

(Squallium-based compound)

The squarylium-based compound used in the present invention is 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) It is desirable to be

ㆍCompound (I)

In formula (I), R ^a , R ^b and Y satisfy the following conditions (i) or (ii).

(i) A plurality of R ^a are independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^e R ^f group (R ^e and R ^f are Each independently represents a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ),

A plurality of R ^b 's are independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^g R ^h group (R ^g and R ^h are each independently Hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e , -SO ₂ R ⁱ group or -C(O)R ⁱ group (R ⁱ is -L ^a , -L ^b , Represents -L ^c , -L ^d or -L ^e , provided that a plurality of R ⁱ in R ^g and R ^h bonded to the same N atom may be bonded to each other to form a ring).

A plurality of Y's are independently -NR ^j R ^k groups (R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e .) represents,

L ¹ is,

(L ^a ) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent L;

(L ^b ) A halogen-substituted alkyl group having 1 to 20 carbon atoms which may have a substituent L;

(L ^c ) an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent L;

(L ^d ) An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent L;

(L ^e ) a heterocyclic group having 3 to 20 carbon atoms which may have a substituent L;

(L ^f ) an alkoxy group having 1 to 20 carbon atoms which may have a substituent L;

(L ^g ) An acyl group having 1 to 20 carbon atoms which may have a substituent L, or

(L ^h ) An alkoxycarbonyl group having 1 to 20 carbon atoms which may have a substituent L

, and the substituent L is 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 complex carbon atom having 3 to 20 carbon atoms. At least one member selected from the group consisting of ventilation, and L ^a to L ^h are at least one atom selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, and an amino group, or You can have more gear. The total number of carbon atoms including the substituents of L ^a to L ^h is preferably 50 or less, more preferably 40 or less carbon atoms, and particularly preferably 30 or less carbon atoms. When the number of carbon atoms is greater than this range, the synthesis of the dye may be difficult, and the absorption intensity per unit mass tends to decrease.

(ii) At least one of the two R ^a on one benzene ring bonds with Y on the same benzene ring to form a heterocycle containing at least one nitrogen atom and having 5 or 6 constituent atoms, and the heterocycle may have a silver substituent,

R ^b and R ^a not involved in formation of the above heterocycle are each independently synonymous with R ^b and R ^a in the above condition (i).

ㆍCompound (II)

In formula (II), a plurality of R ^c 's independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;

A plurality of R ^d' s independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^e R ^f group, and adjacent R ^d' s are linked to each other to have a substituent. You may also form a ring,

X represents O, S, Se, NR ^c or CR ^d R ^d ,

La to L ^e , L ¹ , ^Re and R ^f are synonymous with ^La to L ^e , L ¹ , ^Re and R ^{f defined} in the above formula (I).

As R ^c in the formula (II), preferably a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n -A hexyl group, a cyclohexyl group, a phenyl group, a trifluoromethyl group, and a pentafluoroethyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

As R ^d in the formula (II), preferably a hydrogen atom, a chlorine atom, a fluorine 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, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, 4-aminocyclohexyl group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, They are a methyl group, an ethyl group, n-propyl group, an isopropyl group, a trifluoromethyl group, and a pentafluoroethyl group.

The X is preferably O, S, Se, N-Me, N-Et, CH ₂ , C-Me ² , C-Et ₂ , more preferably S, C-Me ₂ , C-Et ₂ to be.

In the formula (II), adjacent R ^ds may be connected to form a ring. Examples of such a ring include a benzoindolenine ring, an α-naphthoimidazole ring, a β-naphthoimidazole ring, an α-naphthoxazole ring, a β-naphthoxazole ring, an α-naphthothiazole ring, and a β-nap Thothiadazole ring, α-naphthoselenazole ring, β-naphthoselenazole ring, etc. are mentioned.

Compound (I) and compound (II) may take a resonance structure as described in international patent publication WO2013/054864.

Specific examples of the compound (I) and the compound (II) include the following compounds (I-D-1) to (I-D-4) and the like.

(other organic pigments)

The composition may contain other known organic dyes in addition to the polymethine-based compound and the squarylium-based compound. Examples of other organic dyes include phthalocyanine compounds, diiminium compounds, cyanine compounds, naphthalocyanine compounds, quaterrylene compounds, aminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, and oxonol. compounds, croconium compounds, hexapyrine compounds and the like (excluding those containing copper atoms).

(Copolymer (P))

The copolymer (P) used in the present invention is (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) is a copolymer of 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 a copolymer can be produced by radically copolymerizing an unsaturated mixture containing compounds (a1) and (a2) in a solvent in the presence of a polymerization initiator.

Compound (a1) is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride having radical polymerizability, for example, monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, and monocarboxylic acids of polyhydric carboxylic acids. [(meth)acryloyloxyalkyl] esters, mono(meth)acrylates of polymers having carboxy groups and hydroxyl groups at both ends, polycyclic compounds having carboxy groups, and anhydrides thereof.

Specific examples of these include, for example, acrylic acid, methacrylic acid, crotonic acid and the like as monocarboxylic acids;

As dicarboxylic acids, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;

As anhydrides of dicarboxylic acids, for example, anhydrides of compounds exemplified as dicarboxylic acids;

Examples of mono[(meth)acryloyloxyalkyl] esters of polyhydric carboxylic acids include mono[2-(meth)acryloyloxyethyl succinate] and mono[2-(meth)acryloyloxyethyl phthalate]. ] etc;

Examples of the mono(meth)acrylate of a polymer having a carboxy group and a hydroxyl group at both terminals include omega-carboxypolycaprolactone mono(meth)acrylate and the like;

Polycyclic compounds having a carboxy group and their anhydrides, such as 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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. each can be heard.

Among these, anhydrides of monocarboxylic acids and dicarboxylic acids are preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used in terms of improving the copolymerization reactivity, heat resistance and drug resistance of the film, and being easily available. do. These compounds (a1) are used individually or in combination of 2 or more types.

The compound (a2) is an unsaturated compound having an oxiranyl group and/or an unsaturated compound having an oxetanyl group. Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, and α-ethylacrylic acid. Glycidyl, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-acrylic acid Epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexyl, acrylic acid- 3,4-epoxycyclohexylmethyl, methacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. can be heard Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid Acid-3,4-epoxycyclohexyl, methacrylic-acid-3,4-epoxycyclohexylmethyl, etc. are preferably used from the viewpoint of enhancing the copolymerization reactivity and the heat resistance and chemical resistance of the resulting film.

As an unsaturated compound which has an oxetanyl group, for example, 3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)- 3-ethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyl Oxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2,2-difluorooxetane, 3-(acryloyloxymethyl)-2,2,4-trifluorooxetane Cetane, 3-(acryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(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, 3-(2-acryloyloxyethyl)-2,2,4, Acrylic acid esters such as 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, 3-(2-methacryloyloxyethyl) -2-ethyloxetane, 3-(2-methacryloyloxyethyl)-3-ethyloxetane, 3-(2-methacryloyloxyethyl)-2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloyloxyethyl)-2-phenyloxetane, 3-(2-methacryloyloxyethyl) )-2,2-difluorooxetane, 3-(2-methacryloyloxyethyl)-2,2,4-trifluorooxetane, 3-(2-methacryloyloxyethyl)- and methacrylic acid esters such as 2,2,4,4-tetrafluorooxetane.

Among these, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-methyloxetane , 3-(methacryloyloxymethyl)-3-ethyloxetane and the like are preferably used from the viewpoint of copolymerization reactivity.

These compounds (a2) are used alone or in combination.

In the copolymer (P), the mass ratio (a2)/(a1) of the repeating unit derived from the compound (a1) to the repeating unit derived from the compound (a2) is 1 or more, preferably 1.1 or more, and more preferably At least 1.2 or higher. In this ratio, a composition having high low-temperature storage stability, long-term storage, and excellent heat resistance and drug resistance can be obtained.

It is preferable that the structural unit (a2) derived from (a2) is contained in an amount of 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more, based on all the structural units constituting the copolymer. . Within this range, a composition having high low-temperature storage stability, long-term storage, and excellent heat resistance and chemical resistance can be obtained.

The copolymer (P) used in the present invention is a copolymer of the compounds (a1) and (a2). Copolymers of other unsaturated compounds copolymerizable with these (hereinafter sometimes referred to as “compound (a3)”) may also be used.

The compound (a3) is not particularly limited as long as it is an unsaturated compound having radical polymerization, but examples include alkyl methacrylates, cyclic alkyl methacrylates, alkyl acrylates, cyclic alkyl acrylates, and aryl methacrylates. Esters, acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, methacrylic acid esters having a hydroxyl group, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, unsaturated compounds having a pyran skeleton or a (poly)alkylene glycol skeleton, unsaturated compounds having a phenolic hydroxyl group, and other unsaturated compounds.

Specific examples of these include methacrylic acid alkyl esters, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like; As the methacrylic acid cyclic ester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-ylmethacrylate (hereinafter referred to as "dicyclopentanyl methacrylate”), tricyclo[5.2.1.0 ^2,6 ]decan-8-yloxyethyl methacrylate, isoboronyl methacrylate, adamantan-1-yl methacrylate and the like; Examples of acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate and the like; As the acrylic acid cyclic ester, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate (hereinafter referred to as “dicyclopentanyl acrylate”) ), tricyclo[5.2.1.0 ^2,6 ]decan-8-yloxyethyl acrylate, isoboronyl acrylate, adamantan-1-ylacrylate and the like; As an aryl ester of acrylic acid, For example, phenyl acrylate, benzyl acrylate, etc.; As methacrylic acid aryl ester, For example, phenyl methacrylate, benzyl methacrylate, etc.; as unsaturated dicarboxylic acid diesters, for example, diethyl maleate, diethyl fumarate, diethyl itaconate and the like; As methacrylic acid ester having a hydroxyl group, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol mono methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, etc.;

As bicyclo unsaturated compounds, for example bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene 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 -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-carboxy- 5-ethylbicyclo[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-phenoxycarbonylbi Cyclo[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 and the like;

As the maleimide compound, for example, 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 pro cionate, N-(9-acridinyl) maleimide, etc.;

As an unsaturated aromatic compound, For example, styrene, (alpha)-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc.; As the conjugated diene, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like; As an unsaturated compound containing a tetrahydrofuran skeleton, for example, tetrahydrofurfuryl (meth)acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3-(meth)acryloyloxytetrahydro furan-2-one and the like; As an unsaturated compound containing a furan skeleton, for example, 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)-2-methyl-1-hexen-3-one, 6-furan -2-yl-hexy-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl ester of acrylic acid, 6-(2-furyl)-6-methyl-1-hepten-3-one etc; As an unsaturated compound containing a tetrahydropyran skeleton, for example, (tetrahydropyran-2-yl)methyl methacrylate, 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1 -en-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1-(tetrahydropyran-2-oxy)-butyl-3-en-2-one, etc.; As an unsaturated compound containing a pyran skeleton, for example, 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyrone, 4-(1,5-dioxa- 6-oxo-7-octenyl)-6-methyl-2-pyrone and the like;

Examples of the unsaturated compound having a (poly)alkylene glycol backbone include polyethylene glycol (n=2 to 10) mono(meth)acrylate, polypropylene glycol (n=2 to 10) mono(meth)acrylate, and the like;

As the unsaturated compound having a phenolic hydroxyl group, 4-hydroxybenzyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxy Oxystyrene, N-(4-hydroxybenzyl)(meth)acrylamide, N-(3,5-dimethyl-4-hydroxybenzyl)(meth)acrylamide, N-(4-hydroxyphenyl)(meth) ) acrylamide and the like;

Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate, respectively.

Among these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid cyclic alkyl esters, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, pyran skeletons, (poly ) An unsaturated compound having an alkylene glycol skeleton and an unsaturated compound having a phenolic hydroxyl group are preferably used.

In particular, it is preferable from the viewpoint of heat resistance that an unsaturated compound having an alicyclic structure is included. Examples of the unsaturated compound having an alicyclic structure include cyclic alkyl methacrylates and cyclic alkyl acrylates.

These compounds (a3) are used individually or in combination of 2 or more types.

In the copolymer (P) used in the present invention, the repeating units derived from compound (a1) are preferably 5 based on the sum of repeating units derived from compounds (a1), (a2) and (a3). to 40% by mass, particularly preferably 5 to 25% by mass. When it is within the above range, the heat resistance and chemical resistance of the film tend to be improved.

In addition, the copolymer (P) used in the present invention preferably has repeating units derived from compound (a2) based on the sum of repeating units derived from compounds (a1), (a2) and (a3). is 10 to 80% by mass, particularly preferably 20 to 60% by mass. When it is within the above range, the heat resistance and chemical resistance of the film tend to be improved.

In addition, in the case where an unsaturated compound having an alicyclic structure is used as the compound (a3), the copolymer (P) used in the present invention further enhances the heat resistance of the film. ), preferably 10 to 80% by mass, particularly preferably 20 to 60% by mass, based on the total of repeating units derived from (a2) and (a3).

The polystyrene-reduced mass average molecular weight (hereinafter referred to as “Mw”) of the copolymer (P) used in the present invention is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 ×10 ⁴ . Further, the molecular weight distribution (hereinafter referred to as "Mw/Mn") is preferably 5.0 or less, more preferably 3.0 or less.

The copolymer (P) can be synthesized by, for example, polymerizing the compound (a1), the compound (a2) and the compound (a3) in a suitable solvent in the presence of a radical polymerization initiator.

Examples of the solvent used in the production of the copolymer [A] include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, and propylene glycol alkyl ether pro. cionates, aromatic hydrocarbons, ketones, esters and the like.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol; tetrahydrofuran etc. as ether;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.;

as ethylene glycol alkyl ether acetates, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like;

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 the propylene glycol alkyl ether propionate include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate;

as propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like;

As aromatic hydrocarbons, for example, toluene, xylene and the like;

As ketones, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

As an ester, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylethylpropionate, hydroxyacetic acid Methyl, hydroxyethyl acetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methylmethylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, et Butyl hydroxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate , 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2-methoxybutylpropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate, 2-ethoxypropylpropionate, 2-ethoxybutylpropionate, 2-butoxymethylpropionate, 2-butoxyethylpropionate, 2-butoxypropylpropionate, 2-butoxybutylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-methoxypropylpropionate, 3 -Methoxybutylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-ethoxypropylpropionate, 3-ethoxybutylpropionate, 3-propoxymethylpropionate, 3-propoxyethylpropionate, 3- and esters such as propyl propoxylate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferred, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol ethyl ether are particularly preferred. , propylene glycol methyl ether acetate and methyl 3-methoxypropionate are preferred.

As the polymerization initiator used in the production of the copolymer (P), those known as radical polymerization initiators can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2, azo compounds such as 4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, and 1,1'-bis-(t-butyl peroxy)cyclohexane; and hydrogen peroxide. When using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator using a peroxide together with a reducing agent.

In the production of the copolymer (P), a molecular weight adjusting agent may be used to adjust the molecular weight. Specific examples thereof 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; Terpinolene, α-methylstyrene dimer, etc. are mentioned.

The lower limit of the content of the copolymer (P) in the total solid content of the composition is preferably 60% by mass, more preferably 70% by mass, still more preferably 80% by mass. By setting the content of the copolymer (P) within the above range, heat resistance and the like can be improved while sufficiently exhibiting the properties related to visible light transmittance and infrared ray shielding properties of the resulting optical filter. In addition, the composition may use a polymer other than the copolymer (P) in combination within a range that does not impair physical properties.

([C] other infrared shielding agents)

The composition may further contain [C] other infrared ray shielding agents. Other infrared ray shielding agents are infrared ray shielding agents other than the above-mentioned squarylium, polymethine, and other organic dyes, and it is preferable that they are metal oxides, copper compounds, or combinations thereof. [C] As the other infrared shielding agent, a compound having a maximum absorption wavelength in the range of 800 nm or more and 2000 nm or less is preferable. [C] Other infrared shielding agents may be used individually by 1 type, or may be used in mixture of 2 or more types.

[C] Examples of metal oxides as other infrared shielding agents include tungsten oxide compounds, quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), and zirconia ( ZrO ₂ ), spinel (MgAl ₂ O ₄ ), and the like.

[C] As other infrared shielding agents, metal oxides are preferable, and tungsten oxide-based compounds are more preferable. A tungsten oxide-based compound is an infrared ray shielding agent that has high absorption of infrared rays (in particular, infrared rays having a wavelength of about 800 nm or more and less than or equal to 1200 nm) (that is, high infrared ray shielding property) and low absorption of visible light.

As a tungsten oxide type compound, it is more preferable that it is a tungsten oxide type compound represented by following formula (3).

A _x WO _y . . . (3)

In Formula (3), A is a metal element. 0.001≤x≤1.1. 2.2≤y≤3.0.

As the metal element represented by A in the formula (3), an alkali metal, an alkaline earth metal, 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 and the like. 1 type or 2 or more types may be sufficient as the metal element represented by A.

As said A, an alkali metal is preferable, Rb and Cs are more preferable, and Cs is still more preferable. That is, the metal oxide is more preferably cesium tungsten oxide.

When x in Formula (3) is 0.001 or more, infrared rays can be sufficiently shielded. 0.01 is preferable and, as for the minimum of x, 0.1 is more preferable. On the other hand, when x is 1.1 or less, generation of an impurity phase in the tungsten oxide-based compound can be avoided more reliably. 1 is preferable and, as for the upper limit of x, 0.5 is more preferable.

Chemical stability as a material can be further improved because y in said Formula (3) is 2.2 or more. As for the lower limit of y, 2.5 is preferable. On the other hand, when y is 3.0 or less, infrared rays can be shielded sufficiently.

Specific examples of the tungsten oxide-based compound represented by the formula (3) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO ₃ and the like, Cs _0.33 WO ₃ and Rb _0.33 WO ₃ is preferred, and Cs _0.33 WO ₃ is more preferred.

[C] As a copper compound as another infrared shielding agent, a copper complex is preferable. As a copper complex, the complex of copper and the compound (ligand) which has a coordination site|part with respect to copper is preferable. As the coordination site for copper, a coordination site coordinated with an anion and a coordination atom coordinated with an unshared electron pair are exemplified. The copper complex may have two or more ligands. In the case of having two or more ligands, each ligand may be the same or different. The copper complex is exemplified by 4-coordinate, 5-coordinate and 6-coordinate, more preferably 4-coordinate and 5-coordinate, and still more preferably 5-coordinate.

A copper complex can be obtained, for example, by mixing and reacting a compound (ligand) having a coordination site for copper with a copper component (copper or a compound containing copper). The compound (ligand) having a copper coordination site may be a low molecular weight compound or a polymer. You may use both together.

The copper component is preferably a compound containing divalent copper. As for a copper component, only 1 type may be used and 2 or more types may be used. As a copper component, copper oxide and a copper salt can be used, for example. Copper salts include, for example, copper carboxylate (eg, copper acetate, copper ethylacetoacetate, copper formate, copper benzoate, copper stearate, copper naphthenate, copper citrate, copper 2-ethylhexanoate, etc.), Copper sulfonate (eg, copper methanesulfonate, etc.), copper phosphate, copper phosphate ester, copper phosphonate, copper phosphonate ester, copper phosphinate, copper amide, copper sulfonamide, copper imide, copper acylsulfonimide, Bissulfonimide copper, methide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper perchlorate, copper fluoride, copper chloride, copper bromide are preferred, copper carboxylate, copper sulfonate , sulfonamide copper, imide copper, acylsulfonimide copper, bissulfonimide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper fluoride, copper chloride, copper sulfate, copper nitrate are more preferred, Copper boxylate, acylsulfonimide copper, phenoxy copper, copper chloride, copper sulfate, and copper nitrate are more preferable, and copper carboxylate, acylsulfonimide copper, copper chloride, and copper sulfate are particularly preferable.

[C] The other infrared ray shielding agent is preferably fine particles. [C] The upper limit of the average particle diameter (D50) of the other infrared shielding agent is preferably 500 nm, more preferably 200 nm, still more preferably 50 nm, and still more preferably 30 nm. When the average particle size is equal to or less than the above upper limit, the visible light transmittance can be further improved. On the other hand, from reasons such as ease of handling during production, [C] the average particle diameter of the other infrared shielding agent is usually 1 nm or more, and may be 10 nm or more.

[C] Other infrared shielding agents can also be synthesized by known methods, but are available as commercially available products. When the metal oxide is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained, for example, by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. The tungsten oxide-based compound is also available as a dispersion of tungsten fine particles, such as "YMF-02" from Sumitomo Kinzoku Kozan Co., Ltd., for example.

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

([D] Dispersant)

The composition may further contain [D] a dispersing agent. The [D] dispersant improves the uniform dispersibility of [C] other infrared shielding agents (particularly, metal oxides), and the resulting optical filter has better visible light transmittance and infrared shielding properties.

[D] Examples of dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, and polyesters. A type dispersing agent, a (meth)acrylic type dispersing agent, etc. are mentioned. Among these, a (meth)acrylic dispersing agent is preferable. [D] The dispersant is preferably a block copolymer.

([E] polymerizable compound)

The composition may further contain [E] a polymerizable compound. When the composition contains the [E] polymerizable compound, good curability and good heat resistance of the resulting optical filter can be exhibited. [E] The polymerizable compound refers to a compound having two or more polymerizable groups. As a group which can superpose|polymerize, an ethylenically unsaturated group, oxiranyl group, oxetanyl group, N-alkoxymethylamino group etc. are mentioned, for example. [E] The polymerizable compound is preferably a compound having two or more (meth)acryloyl groups, a compound having two or more oxiranyl groups, and two or more N-alkoxymethylamino groups, and two or more (meth)acryloyl groups. A compound having a loyl group and a compound having two or more oxiranyl groups are more preferred. [E] The polymerizable compound can be used alone or in combination of two or more.

Examples of the compound having two or more (meth)acryloyl groups include ethylene glycol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, and poly(meth)acrylate. Propylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxyethanol fluorenedi(meth)acrylate, bisphenoxyethanol fluorenedi(meth)acrylate, trimethylolpropane Tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl) phosphate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate , dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

As a compound which has 2 or more oxiranyl groups, an aliphatic epoxy compound etc. are mentioned.

These can be obtained as commercial items. 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, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase ChemteX Co., Ltd.), Celloxide 2021P, 20813000, EHPE3150, Eporide GT401, Cervinus B0134, B0177 (manufactured by Daicel Co., Ltd.) and the like.

[E] The content of the polymerizable compound is preferably 20% by mass or more and 120% by mass or less with respect to 100% by mass of the total amount of the copolymer (P) component.

([F] polymerization initiator)

The composition may contain [F] a polymerization initiator. [F] Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, but a photopolymerization initiator is preferable. Thereby, photosensitivity (radiation sensitivity) can be provided to the said composition. A photopolymerization initiator refers to a compound that generates an active species capable of initiating polymerization of a [E] polymerizable compound by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, or X-ray. [F] The polymerization initiator can be used alone or in combination of two or more.

([G] acid generator)

The composition may contain [G] an acid generator. [G] The acid generator is a compound that generates an acid by irradiation with radiation. By including the [G] acid generator, the composition can exhibit, for example, positive radiation sensitive properties with respect to an alkaline developer. [G] The acid generator is not particularly limited as long as it is a compound that generates an acid (eg, carboxylic acid, sulfonic acid, etc.) upon irradiation with radiation. Examples of the [G] acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinonediazide. A compound etc. are mentioned. Among these, quinonediazide compounds are preferred.

(additive)

The composition may contain various additives as needed in addition to the components described above.

Examples of additives include surfactants, adhesion accelerators, antioxidants, ultraviolet absorbers, aggregation inhibitors, residue improvers, developability improvers, and reaction modifiers.

As surfactant, a fluorosurfactant, silicone surfactant, etc. are mentioned.

Examples of adhesion accelerators include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-(2-methoxyethoxysilane). -Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3, 4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Toxysilane etc. are mentioned.

Examples of antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and pentaerythritol tetrakis[3-(3,5-di-t-butylphenol). -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, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ] and the like.

As the ultraviolet absorber, any conventionally known ones capable of exhibiting ultraviolet absorbency can be used. Among these ultraviolet absorbers, it is preferable to use a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber from the viewpoint of obtaining ultraviolet ray absorbing ability (ultraviolet ray cutting ability). In addition, in order to widen the absorption width of ultraviolet rays, two or more types of ultraviolet absorbers having different maximum absorption wavelengths may be used in combination. As the ultraviolet absorber, specifically, for example, the compound described in paragraphs [0258] to [0259] of Japanese Patent Laid-Open No. 2012-18395, paragraphs [0055] to [0105] of Japanese Patent Laid-Open No. 2007-72163 The compounds described and the like are exemplified. In addition, as a commercial item, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577 (all manufactured by BASF), etc. can be used.

As an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

As the residue improver, 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, 4-amino-1,2-butanediol, etc. are mentioned.

As the developability improver, succinate mono[2-(meth)acryloyloxyethyl], phthalate mono[2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate agents, etc. can be heard

As a reaction modifier, polyfunctional thiol etc. are mentioned.

(menstruum)

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

As such a solvent, for example

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, tri (poly)alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

lactate alkyl 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;

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, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;

ketones such as chain ketones such as methyl ethyl ketone, 2-heptanone and 3-heptanone, and cyclic ketones such as cyclopentanone and cyclohexanone;

diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxy carboxyls such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate acid esters,

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 Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate,

Aromatic hydrocarbons such as toluene and xylene;

amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and the like.

The content of the solvent 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, as an upper limit of this solid content concentration, 50 mass % is preferable and 40 mass % is more preferable. By setting the solid content concentration within the above range, dispersibility, stability, coatability, and the like become better.

(preparation method)

It does not specifically limit as a preparation method of the said composition, It can prepare by mixing each component. The composition may be subjected to a filtration treatment as necessary to remove aggregates.

<Infrared shielding film>

From the composition of the present invention, an infrared shielding film for an optical filter can be formed. This infrared shielding film has good properties regarding a visible light transmission window range, an infrared shielding range, heat resistance, and chemical resistance.

The said infrared shielding film can be formed by the following method, for example. First, after apply|coating the said composition on a support body, prebaking is performed and the solvent is evaporated and a coating film is formed. Then, an infrared shielding film is obtained by post-baking. In the case of performing the development treatment, after the coating film is formed, the coating film is exposed to light, and then developed using a developing solution to dissolve and remove the unexposed portion of the coating film. After that, by post-baking, an infrared shielding film patterned into a predetermined shape is obtained.

Examples of the support to which the composition is applied include the transparent substrate, microlens, and color filter. For the coating, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method can be employed.

Conditions for heat drying in the prebaking are, for example, 70°C or more and 110°C or less, about 1 minute or more and 10 minutes or less.

In the case of performing the development treatment, as a light source of radiation used for exposure of the coating film, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or an argon Laser light sources, such as an ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser, etc. are mentioned. As an exposure light source, an ultraviolet LED can also be used. The wavelength is preferably radiation in the range of 190 nm or more and 450 nm or less. The exposure amount of radiation is generally about 10 J/m 2 or more and 50,000 J/m 2 or less.

As the developer, an alkali developer is common. As an alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5- Aqueous solutions such as diazabicyclo-[4.3.0]-5-nonene are preferred. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developing solution, for example. In addition, after image development, it is normally washed with water.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid pool) developing method, or the like can be applied. The developing conditions are about 5 seconds or more and 300 seconds or less at room temperature.

As conditions for post-baking, they are usually 180°C or more and 280°C or less, about 1 minute or more and 60 minutes or less.

The lower limit of the average film thickness of the infrared shielding film thus formed is usually 0.5 µm, and preferably 1 µm. On the other hand, as an upper limit of this average film thickness, it is 20 micrometers normally, and 10 micrometers is preferable. When the average film thickness of infrared shielding is within the above range, the balance between visible light transmittance and infrared shielding properties becomes better.

<Optical filter>

An infrared shielding film formed from the composition according to one embodiment of the present invention can be used for an optical filter. The optical filter having the infrared shielding film has fewer defects such as foreign matter and has good visible light transmittance and infrared shielding properties. The said optical filter is used as an optical filter of optical sensors, such as a solid-state imaging element.

The optical filter may include only the infrared shielding film, or may include components other than the infrared shielding film. For example, the optical filter may be a laminate having a layer different from the infrared shielding film.

The infrared shielding film is preferably incorporated in an optical sensor such as a solid-state imaging device as a constituent member. In this case, the said infrared shielding film functions as an optical filter (infrared cut filter) single-piece|unit. By incorporating the infrared shielding film into the optical sensor, it is possible to obtain a large process margin and the like, which is preferable. When the infrared shielding film is built into the solid-state imaging device, the infrared shielding film can be disposed, for example, on the outer surface side of the microlens of the solid-state imaging device, between the microlens and the color filter, between the color filter and the photodiode, and the like. The infrared shielding film is preferably laminated between a microlens and a color filter or between a color filter and a photodiode.

The optical filter may be formed by laminating the infrared shielding film on the surface of a transparent substrate. As the transparent substrate, glass, transparent resin, or the like is employed. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. As the optical filter, a dielectric multilayer film may be provided on the infrared shielding film or on the transparent substrate in order to shield light from a wider range of near-infrared to infrared ranges. Examples of the dielectric multilayer film include laminates in which high refractive index material layers and low refractive index material layers are alternately laminated. In addition, instead of providing a dielectric multilayer film directly on 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 ray cut filter or the like in a solid-state imaging device.

An optical sensor such as a solid-state imaging device having the optical filter is used in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, personal digital assistants, personal computers, video games, medical devices, and the like. useful.

<Optical sensor>

The optical filter is used for an optical sensor such as a solid-state imaging device. Since the optical filter has few defects such as foreign matter and has good properties regarding visible light transmittance and infrared ray shielding, an optical sensor such as a solid-state imaging device having the optical filter has high sensitivity, color reproducibility, etc., and is excellent in practicality. .

Hereinafter, a solid-state imaging device will be described as an example of an optical sensor. The solid-state imaging device generally has a structure in which a layer in which a plurality of photodiodes are disposed, a color filter, and a microlens are laminated in this order. In addition, a flattening layer may be provided between these layers. In the solid-state imaging device, light enters from the microlens side. The incident light passes through the microlens and the color filter to reach the photodiode. Further, as for the color filters, for example, each of the R (red), G (green), and B (blue) filters is configured so that only light in a specific wavelength range is transmitted.

In the solid-state imaging device, the optical filter (infrared ray shielding film) may be provided on an outer surface side of the microlens, between the microlens and the color filter, between the color filter and a layer on which the plurality of photodiodes are disposed, etc. there is. The optical filter is preferably laminated between a microlens and a color filter or between a color filter and a photodiode. Moreover, another layer (flattening layer etc.) may be further provided between the said optical filter, a microlens, a color filter, a photodiode, etc.

As a specific example of the said solid-state imaging element, CCD, CMOS, etc. as a camera module are mentioned. The solid-state imaging device is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, monitoring cameras, automobile cameras, personal digital assistants, personal computers, video games, medical equipment, and the like.

<Example>

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

The symbol of the compound is as follows. In addition, below, the compound represented by formula (X) may be simply referred to as "compound (X)".

M1: methacrylic acid

M2: acrylic acid

M3: succinic acid mono[2-(meth)acryloyloxyethyl]

M4: glycidyl methacrylate

M5: methacrylic acid-3,4-epoxycyclohexyl

M6: 3-(methacryloyloxymethyl)-2-methyloxetane

M7: Styrene

M8: tricyclo[5.2.1.0 ^2,6 ]decan-8-yl methacrylate

M9: methyl methacrylate

M10: benzyl methacrylate

M11: cyclohexyl methacrylate

M12: 1-adamantyl methacrylate

Squalylium 1: Compound represented by the above formula (I-D-1)

Squallium 2: Compound represented by the above formula (I-D-2)

Squallium 3: Compound represented by the above formula (I-D-4)

Polymethine 1: Compound represented by the above formula (III-6)

Polymethine 2: Compound represented by the above formula (III-2)

Polymethine 3: a compound represented by the above formula (III-3)

Polymerizable compound 1: Celloxide 2021P manufactured by Daicel Co., Ltd.

Other organic pigment 1: Daito chmix 1371F manufactured by Daito Chemix Co., Ltd.

Other organic dye 2: a compound represented by the following formula (color-2)

Ultraviolet absorber 1: a compound represented by the following formula (UVA-1)

Ultraviolet absorber 2: a compound represented by the following formula (UVA-2)

Surfactant 1: Shin-Etsu Chemical Co., Ltd. KF-643 (silicone type)

Surfactant 2: DIC Corporation Megapack F-474 (fluorine-based)

Adhesion promoter 1: γ-glycidoxypropyltrimethoxysilane

Adhesion promoter 2: 3-aminopropyltriethoxysilane

Antioxidant 1: Irganox 1010 manufactured by BASF

Solvent 1: Cyclopentanone

(Synthesis Example 1)

In a flask equipped with a cooling tube and a stirrer, when the mass of the unsaturated mixture is 100% by mass, 7% by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 diethylene glycol ethylmethyl ether It injected|threw-in in advance so that it might become mass %. To this, an unsaturated mixture containing 20% by mass of methacrylic acid, 30% by mass of glycidyl methacrylate, and 50% by mass of methyl methacrylate, totaling 100% by mass was introduced, and after nitrogen substitution, gentle stirring was started. did The temperature of the solution was raised to 70° C., and the temperature was maintained at this temperature for 4 hours to terminate the polymerization. Thereafter, the reaction product solution was added dropwise to a large amount of methanol to solidify the reactant. After washing with water, this coagulum was redissolved in tetrahydrofuran and coagulated again with a large amount of methanol. After this redissolution-solidification operation was performed three times in total, the obtained coagulum was vacuum dried at 60°C for 48 hours to obtain the target [Polymer 1].

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 as shown in Table 1 were used as monomer components.

[Example 1]

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

[Examples 2 to 6, Comparative Examples 1 to 9]

Each composition of Examples 2 to 6 and Comparative Examples 1 to 9 was obtained in the same manner as in Example 1, except that the types and compounding ratios (mass%) of polymers, pigments, various additives and solvents were shown in Table 1. .

[evaluation]

The following evaluation was performed using each obtained composition. Table 1 shows the evaluation results.

Each composition was applied onto a glass substrate by spin coating to a predetermined film thickness. Thereafter, the coating film was heated at 100° C. for 120 seconds and then heated at 200° C. for 300 seconds to prepare an infrared shielding film having an average film thickness of 10 μm on the glass substrate. In addition, the film thickness was measured with a stylus step meter ("Alpha Step IQ" by Yamato Chemical Co., Ltd.). Next, the transmittance in each wavelength region of the infrared shielding film prepared on the glass substrate was measured in comparison with the glass substrate using a spectrophotometer ("V-7300" manufactured by Bunko Co., Ltd., Japan). From the obtained spectrum, evaluation was performed according to the following evaluation criteria.

(Visible light transmission window range)

The range in which the transmittance|permeability in the range of 400-700 nm becomes 70% or more continuously was calculated|required. When the range of 70% or more continuously is 180 nm or more, it is estimated that practicality is high because it has high sensitivity when used as an infrared shielding film. In addition, the range of the visible transmission window was evaluated according to the following criteria.

○: 180 nm or more

△: 170 nm or more and less than 180 nm

×: less than 170 nm

(infrared shielding range)

A range in which the transmittance in the range of 600 to 1200 nm is continuously 20% or less was determined. When the range of 20% or less continuously is 70 nm or more, it is estimated that practicality is high because it has a high noise shielding function when used as an infrared shielding film. In addition, the infrared shielding range was evaluated according to the following criteria.

○: 70 nm or more

×: 40 nm or more and less than 70 nm

× ×: less than 40 nm

(heat resistance)

The infrared shielding film prepared on the glass substrate was heated at 220° C. for 30 minutes using a hot plate, and the transmittance in each wavelength range before and after heating was measured using a spectrophotometer ("V-7300" manufactured by Bunko Corporation, Japan). was used and measured in comparison to the glass substrate. At this time, the absorbance at the wavelength at which the transmittance is lowest in the range of 600 to 1200 nm of the prepared infrared shielding film is (A1), the absorbance after heating at 220 ° C. in the same wavelength (A2), and the absorbance retention rate = 100 × (A2) )/(A1), heat resistance at 220°C was evaluated according to the following criteria. When the retention rate is 50% or more, when used as an infrared shielding film, it is possible to maintain high heat resistance, and it is presumed that the practicality is high. In addition, the retention rate was evaluated according to the following criteria.

◎: 80% or more

○: 50% or more and less than 80%

△: 30% or more and less than 50%

×: less than 30%

(tolerability)

The infrared shielding film prepared on the glass substrate was immersed in N-methyl-2-pyrrolidone at room temperature for 10 minutes using a petri dish, and the transmittance in each wavelength range before and after immersion was measured using a spectrophotometer (Nippon Bunko company "V-7300") was used, and measured in comparison with a glass substrate. At this time, the absorbance at the wavelength at which the transmittance is lowest in the range of 600 to 1200 nm of the prepared infrared shielding film is (A1), the absorbance after N-methyl-2-pyrrolidone immersion at the same wavelength (A2), and the absorbance Retention rate = 100 x (A2) / (A1), and tolerability was evaluated according to the following criteria. When the retention rate is 50% or more, when used as an infrared shielding film, it is possible to maintain high chemical resistance, and it is presumed that the practicality is high. In addition, the retention rate was evaluated according to the following criteria.

○: 50% or more

△: 30% or more and less than 50%

×: less than 30%

(Coating defect after storage at low temperature)

After standing still at -15°C for one week, the infrared absorbing composition was applied onto a silicon substrate using a spinner to form a coating film having a thickness of 1 µm. The defect density of the coating film was measured using a defect/foreign material inspection device ("KLA2351" from KLA-Tencor). It can be judged that the foreign matter removability is high, that is, the foreign matter is sufficiently removed, so that the value of this defect density is small. Based on the above defect density, foreign material removability was evaluated according to the following criteria.

○: 10/cm2 or less

△: More than 10/cm2 and 50/cm2 or less

×: more than 50/cm2

(Coating defects after long-term low-temperature storage)

After standing at -15°C for 2 months, the infrared absorbing composition was applied onto a silicon substrate using a spinner to form a coating film having a thickness of 1 µm. The defect density of the coating film was measured using a defect/foreign material inspection device ("KLA2351" from KLA-Tencor). It can be judged that the foreign matter removability is high, that is, the foreign matter is sufficiently removed, so that the value of this defect density is small. Based on the above defect density, foreign material removability was evaluated according to the following criteria.

○: 10/cm2 or less

△: More than 10/cm2 and 50/cm2 or less

×: more than 50/cm2

As shown in Table 1, in all of Examples 1 to 6, the evaluation of the visible light transmission window range, infrared ray shielding range, heat resistance, drug resistance, and coating defect suppression after low temperature storage was good, and the coating defect suppression after long-term low temperature storage was also high.

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

Claims (9)

(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 A composition for an optical sensor, comprising a copolymer (P) of an unsaturated mixture containing and a pigment [Q] containing at least one polymethine-based compound. The composition for an optical sensor according to claim 1, wherein the polymethine-based compound is contained in an amount of 20% by mass or more in the total pigment [Q]. The composition for an optical sensor according to claim 1 or 2, wherein the polymethine-based compound contains a compound represented by the following formula (III) or a compound represented by the following formula (V).
Cn⁺An^- (III)
[in Formula (III), Cn⁺is a monovalent cation represented by the following formula (IV) or the following formula (VI), and An^-is a monovalent anion.]

Of formula (IV) and formula (VI),
Unit A is any of the following formulas (A-I) to (A-III),
Unit B is any of the following formulas (B-I) to (B-III),
Z_A to Z_C and Y_A to Y_Iare each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, -NR^gR^hgroup, amide group, imide group, cyano group, silyl group, -Q^One, -N=N-Q^One, -S-Q², -SSQ² or -SO₂Q³ego,
Z_A to Z_C and Y_A to Y_I Among them, two adjacent ones may be bonded to each other to form a ring,
Some of the groups in unit A are Y_A or Y_Fmay be combined with to form a cyclic hydrocarbon group having 5 or 6 carbon atoms, and some of the groups in unit B are Y_E or Y_Iand may form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
R^g and R^hare each independently a hydrogen atom, -C(O)RⁱGroup or L^a to L^hwhich one, Q^Oneis independently L^a to L^hwhich one, Q²is independently a hydrogen atom or L^a to L^hwhich one, Q³is a hydroxyl group or L^a to L^hwhich one, Rⁱis L^a to L^hwhich one of

-* in formulas (A-I) to (A-III) is Y in formula (IV)_A or Y_Frepresents a single bond with the carbon to which
=** in formulas (B-I) to (B-III) is Y in the formula (IV)_E or Y_Irepresents a double bond with the carbon to which is bonded,
In Formulas (A-I) to (B-III),
X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR⁸-ego,
R^One to R⁶are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -NR^gR^hGroup, -SRⁱgroup, -SO₂RⁱGroup, -OSO₂Rⁱgroup, -C(O)RⁱGroup or L^a to L^hwhich one of
Adjacent R^One to R⁶is bonded to each other, an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4 to 7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a nitrogen atom, oxygen atom or sulfur atom containing at least one , may form a heteroaromatic group having 3 to 14 carbon atoms, and these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a halogen atom, and the alicyclic group is =O can have,
R⁸is independently a hydrogen atom, a halogen atom, -C (O) RⁱKi, L^a to L^hwhich one of
Rⁱis independently L^a to L^hwhich one of
(L^a): an aliphatic hydrocarbon group having 1 to 15 carbon atoms
(L^b): halogen-substituted alkyl group having 1 to 15 carbon atoms
(L^c): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K
(L^d): An aromatic hydrocarbon group having 6 to 14 carbon atoms 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 a substituent L)
(L^g): an acyl group having 1 to 9 carbon atoms which may have a substituent L
(L^h): an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L
The substituent K is the L^a to L^bAt least one selected from, and the substituent L is, the L^a to L^fIt is at least one selected from.] The optical composition according to claim 1, wherein the mass ratio (a2)/(a1) of the structural unit (a1) derived from (a1) in the copolymer (P) and the structural unit (a2) derived from (a2) is 1 or more. A composition for a sensor. The composition for an optical sensor according to claim 1, wherein the structural unit (a2) derived from (a2) is contained in an amount of 10% by mass or more based on all structural units constituting the copolymer. The composition for an optical sensor according to claim 1, wherein the copolymer (P) is a copolymer of an unsaturated mixture containing an unsaturated compound having an alicyclic structure. An optical sensor formed using the composition for an optical sensor according to claim 1. A solid-state imaging device comprising the optical sensor according to claim 7 . A camera module comprising the optical sensor according to claim 7 .