KR20180038413A - Thermoreactive composition - Google Patents

Abstract

The heat-reactive composition of the present invention contains at least one cyanine compound (?), A resin (?) Having at least an ethylenic unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (?). It is preferable that the resin (?) Has a unit represented by the following formula (I-1), a unit represented by the following formula (I-2) and a unit represented by the following formula (I-3). It is also preferable that the thermal polymerization initiator (?) Is an azo thermal polymerization initiator. In the following formulas, the definitions of Y ¹ , X ¹ , and R ¹ to R ⁴ are described in the specification.

Description

Thermoreactive composition

The present invention relates to a heat-reactive composition containing a cyanine compound, a resin having an ethylenically unsaturated bond and a hydrophilic group in one molecule, and a thermal polymerization initiator, and a wavelength cut filter using the heat-reactive composition.

The sensitivity of a solid-state image pickup device (such as a CCD or a C-MOS) used in a digital still camera, a video camera, a camera for a cellular phone or the like extends from the ultraviolet region to the infrared region of the optical wavelength. On the other hand, human visibility is only the visible region of the light wavelength. For this reason, the sensitivity of the solid-state image pickup device is corrected so as to be close to human visibility by providing an infrared cut filter between the image pickup lens and the solid-state image pickup device.

As the infrared cut filter, it is possible to use a reflection type filter in which layers containing a substance having no absorption characteristic are combined and laminated in multiple layers, a difference in their refractive indexes, and an absorption type filter in which a light absorbent is contained in or bonded to a transparent substrate It is known.

Particularly, in the absorption type filter, deterioration of the light absorbent occurs due to heat treatment at the time of production, and deterioration of the infrared blocking ability is a problem.

Patent Documents 1 and 2 disclose a thermally reactive composition containing a thermal polymerization initiator. Patent Document 3 describes a composition containing a cyanine compound and a resin having an ethylenically unsaturated bond and a hydrophilic group in one molecule and a photopolymerization initiator.

Japanese Patent Application Laid-Open No. 2007-256865 US2010051883A1 Japanese Laid-Open Patent Publication No. 2013-173848

However, the compositions described in Patent Documents 1 to 3 can not be said to be sufficient from the standpoint of heat resistance.

Accordingly, an object of the present invention is to provide a thermoreactive composition excellent in heat resistance. Another object of the present invention is to provide a wavelength cut filter using the heat-reactive composition.

As a result of intensive investigations, the inventors of the present invention have found that a heat-sensitive composition containing a thermally-reactive composition containing a resin having a cyanine compound, an ethylenically unsaturated bond and a hydrophilic group in one molecule, The present invention has been accomplished on the basis of the knowledge that the filter is suitable for a wavelength cut filter used in an apparatus or the like.

The present invention provides a thermoreactive composition containing at least one cyanine compound (?), A resin (?) Having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (?).

The present invention also provides a wavelength cut filter obtained by using the heat-reactive composition, and a solid-state imaging device and a camera module using the same.

The thermoreactive composition of the present invention containing a cyanine compound, a resin having one ethylenic unsaturated bond and a hydrophilic group in one molecule, and a thermal polymerization initiator has excellent heat resistance. Further, the cured product is suitable for a wavelength cut filter.

1 is a schematic sectional view showing an example of a layer structure of a wavelength cut filter of the present invention.
2 is a schematic sectional view showing another example of the layer structure of the wavelength cut filter of the present invention.
3 is a cross-sectional view showing a configuration of a camera module which is one of the solid-state imaging devices of the present invention.
4 is a cross-sectional view showing another configuration of the camera module.
5 is a cross-sectional view showing another configuration of the camera module.
6 is a cross-sectional view showing still another configuration of the camera module.

Hereinafter, the heat-reactive composition of the present invention will be described on the basis of preferred embodiments.

The thermoreactive composition of the present invention is a thermoreactive composition comprising at least one cyanine compound (hereinafter also referred to as a cyanine compound (?)), A resin (?) Having at least an ethylenically unsaturated bond and a hydrophilic group ), A thermal polymerization initiator (?), And optionally a monomer (?) Having an unsaturated bond and a solvent (?). Hereinafter, each component will be described in order.

<Cyanine compound (?)>

The cyanine compound (?) Used in the thermoreactive composition of the present invention is not particularly limited and conventionally known ones can be used, but from the standpoint of availability, it is preferable that the cyanine compound (a) is represented by the following general formula (II).

(Wherein ring A and ring A 'each independently represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,

R ¹¹ and R ^{11 '} each independently represent a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, an amide group, a metallocenecyl group, An arylalkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms,

X ¹¹ and X ^{11 '} each independently represent an oxygen atom, a sulfur atom, a selenium atom, -CR ²³ R ²⁴ -, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms or -NR ²⁵ - And,

R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, , An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms,

Y ¹¹ and Y ^{11 '} each independently represent a hydrogen atom or a carbon atom which may be substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, an amide group or a metallocene group An aryl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms,

The aryl group, arylalkyl group and alkyl group in R ¹¹ , R ^{11 '} , Y ¹¹ , Y ^11' , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may be substituted with a substituent selected from the group consisting of a hydroxyl group, a halogen atom, R ¹¹ , R ¹¹ , Y ¹¹ , Y ^{11 '} , R ²¹ , R ²² , R ²³ , and R ²⁴ may be substituted with -SO ₃ H, a carboxyl group, an amino group, an amide group or a metallocene group. And the alkylene group in R ²⁵ and the methylene group in the alkyl group may be replaced by -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N = CH- or a carbon-carbon double bond,

Q represents a connecting group which may form a methine chain having 1 to 9 carbon atoms and may contain a ring structure in the chain, and the hydrogen atom in the methine chain may be a hydroxyl group, a halogen atom, a cyano group, -NRR ' , An arylalkyl group or an alkyl group, and the -NRR ', the aryl group, the arylalkyl group and the alkyl group may be further substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR', -O-, -S-, _{-CO-, -COO-, -OCO-, -SO 2} -, -NH-, -CONH-, -NHCO-, -N = CH-, and may be interrupted by or -CH = CH-,

R and R 'represent an aryl group, an arylalkyl group or an alkyl group,

r and r 'represent 0 or a substitutable number of a ring A and a ring A'

An ^q- represents an anion of q, q represents 1 or 2, and p represents a coefficient for keeping the charge (charge) neutral.

The general formula ^{(II) R 11, R 11} ' and X ¹¹ and X ^11' in R ^23, a halogen atom represented by R ²⁴ and R ²⁵ and R ^11, in ^{R 11 ', R 23, R} 24, R 25 , Y ¹¹ and Y ^{11 '} , an aryl group, an arylalkyl group or a halogen atom which may be substituted with an alkyl group, may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom,

The R ¹¹ in the formula (II), R ^{11 'and} X ¹¹ and X ^11' in the R ^23, an amino group represented by R ²⁴ and R ²⁵ and ^{R 11, R 11 ', R} 23, R 24, R 25, Examples of the amino group which may be substituted with an aryl group, an arylalkyl group and an alkyl group represented by Y ¹¹ and Y ^{11 '} include amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, Anilino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbamoyl, morpholinocarbamoyl, Amino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycar Wherein the arylsulfonylamino group is unsubstituted or substituted with at least one group selected from the group consisting of halogen, hydroxyl, cyano, trifluoromethyl, cyano, trifluoromethyl, cyano, trifluoromethyl, cyano, Phenylamino, phenylsulfonylamino and the like,

The R ¹¹ in the formula (II), R ¹¹ amide group represented by R ^23, R ²⁴ and R ²⁵ of the ^'and X ¹¹ and X ^11' and ^{R 11, R 11 ', R} 23, R 24, R 25 , An amide group which may be substituted with an aryl group, an arylalkyl group or an alkyl group represented by Y ¹¹ and Y ^{11 '} includes an amide group such as formamide, acetamide, ethylamide, isopropylamide, butylamide, octylamide, nonylamide, decylamide, (2-ethylhexyl) amide, benzamide, trifluoroacetamide, pentafluorobenzamide, diformamide, diacetamide, diethylamide, diisopropylamide, , Diisopropylamide, dibutylamide, dioctylamide, dinonylamide, didecylamide, diundecylamide, didodecylamide, di (2-ethylhexyl) amide, dibenzamide, ditrifluoroacetamide , Dipentafluorobenzamide, and the like.

The R ¹¹ in the formula (II), R ¹¹ metal to enyl group represented by ^' and X ¹¹ and X ^{11 'in} R ^23, R ²⁴ and R ²⁵ and ^{R 11, R 11', R} 23, R 24, Examples of the metallocenyl group which may be substituted with an aryl group, an arylalkyl group or an alkyl group represented by R ²⁵ , Y ¹¹ and Y ^{11 '} include ferrocenyl, nickelocenyl, zirconocenyl, titanocenyl, In addition,

The carbon atom (s) represented by R ²³ , R ²⁴ and R ²⁵ in R ¹¹ , R ^{11 '} , Z ¹¹ , Z ¹² , Z ¹³ and Y ¹¹ and Y ^11' and X ¹¹ and X ^{11 '} Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, Cyclohexylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, Dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- Di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5- 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like.

The arylalkyl group represented by R ¹¹ , R ^{11 '} , Y ¹¹ and Y ^11', and R ²³ , R ²⁴ and R ²⁵ in X ¹¹ and X ^{11 '} in the general formula (II) , Benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl and ferrocenylpropyl,

As the alkyl group having 1 to 8 carbon atoms represented by R ²³ , R ²⁴ and R ²⁵ in R ¹¹ , R ¹¹ and Y ^{11 '} , Y ^11' and X ¹¹ and X ^{11 '} in the general formula (II) Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert- amyl, hexyl, Cyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl and tert-octyl.

Wherein R ^11, R ^{11 'and} Y ^11, Y ^11' and X ¹¹ and X ^{11 'in} R ^23, R ²⁴ and hydroxy group in R ^25, a halogen atom, a nitro group, a cyano group, -SO ₃ H group, a carboxyl group with an alkyl group, an amino group, an amide group, or an aryl group of a metal enyl groups may be carbon atoms, 6 to 30 are substituted, carbon atoms, 7 to 30 arylalkyl group, and the number of carbon atoms of 1 to 20 of the description, such as the R ¹¹ An aryl group, an alkyl group, and a group in which a hydrogen atom in these groups is substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, a -SO ₃ H group, a carboxyl group, an amino group, an amide group or a metallocenecyl group And the position and the number of these substituents are not limited.

The arylalkyl group in R ²³ , R ²⁴ and R ²⁵ in R ¹¹ , R ^{11 '} and Y ¹¹ , Y ^11' and X ¹¹ and X ^{11 '} and the methylene group in the alkyl group are -O-, -S-, _{CO-, -COO-, -OCO-, -SO 2} -, -NH-, -CONH-, -NHCO-, -N = CH- or a carbon-carbon double bond which is substituted with, and the number of these substitutions and The position is arbitrary.

Examples of the group in which the above alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, nona Fluorobutyl, and the like,

Examples of the group in which the alkyl group having 1 to 8 carbon atoms is interrupted by -O- include methyloxy, ethyloxy, isopropyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, heptyloxy , Octyloxy, 2-ethylhexyloxy and the like, alkoxy groups such as 2- methoxyethyl, 2- (2-methoxy) ethoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, , 3-methoxybutyl and the like, and the like,

Examples of the group in which the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom and interrupted with -O- include chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, difluoro Methyloxy, trifluoromethyloxy, nonafluorobutyloxy, and the like.

In the above general formula (II), the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X ¹¹ and X ^{11 '} includes cyclopropane-1,1-diyl, cyclobutane- Dimethyl cyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl, cyclohexane- .

(Q-1) to (Q-11) which constitute a methine chain having 1 to 9 carbon atoms and which may contain a ring structure in the chain, represented by Q in the general formula (II) Is preferred since it is easy to manufacture. The number of carbon atoms in the methine chain of 1 to 9 carbon atoms represents a linking group which may contain a ring structure in the methine chain or chain and a group capable of further substituting the linking group (for example, R ¹⁴ to R ¹⁹ , Z ') (for example, carbon atoms at both terminals in the linking group (Q-1)).

(Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z 'each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an -NRR' An aryl group, an arylalkyl group and an alkyl group, which may be substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR ', -O-, -S-, -CO-, -COO _{-, -OCO-, -SO 2 -,} -NH-, -CONH-, -NHCO-, and may be interrupted by -N = CH- or -CH = CH-,

R and R 'represent an aryl group, an arylalkyl group or an alkyl group.

Examples of the halogen atom, aryl group, arylalkyl or alkyl group represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z 'include those exemplified as R ¹¹ , and as the aryl group, arylalkyl group, or an alkyl group represented by R 'include those exemplified in the description, such as R ^11.

Examples of the q-valent anion represented by pAn ^q- in the general formula (II) include methanesulfonic acid anion, dodecylsulfonic acid anion, benzenesulfonic acid anion, toluenesulfonic acid anion, trifluoromethanesulfonic acid anion, naphthalenesulfonic acid anion, Amino-4-methyl-5-chlorobenzenesulfonic acid anion, 2-amino-5-nitrobenzenesulfonic acid anion, naphthalene disulfonic acid anion, naphtholsulfonic acid anion, bis (trifluoromethanesulfonyl) Japanese Unexamined Patent Application Publication Nos. 10-235999, 10-337959, 11-102088, 2000-108510, 2000-168223 , Japanese Patent Laid-Open Publication No. 2001-209969, Japanese Laid-Open Patent Publication No. 2001-322354, Japanese Laid-Open Patent Publication No. 2006-248180, Japanese Laid-Open Patent Publication No. 2006-297907, Japanese Laid-Open Patent Publication No. 8-253705, Bulletin Bromide ion, iodide ion, fluoride ion, chlorate ion, thioether ion, bromide ion, bromide ion, bromide ion, bromide ion, Tetra fluoroboric acid ion, octylphosphoric acid ion, dodecylphosphoric acid ion, octadecylphosphoric acid ion, phenylphosphoric acid ion, nonylphenylphosphoric acid ion, 2,2 ' (Methylenebis (4,6-di-t-butylphenyl) phosphonic acid ion, tetrakis (pentafluorophenyl) boric acid ion, excited active molecule in the excited state A metallocene compound anion such as a ferrocene or ruthenocene having an anionic group such as a carboxyl group, a phosphonic acid group or a sulfonic acid group in a cyclic anion or a cyclopentadienyl ring having a function of quenching .

Specific examples of the cyanine compound (?) Used in the present invention include the following compounds No. 1 to 104. In the following examples, the cyanine cations exclude anions.

Among the compounds represented by the above general formula (II), the following compounds are preferred.

Ring A or ring A 'is a benzene ring or a naphthalene ring.

r or r 'is 0 to 2;

R ¹¹ and R ^{11 '} each independently represent a halogen atom, a nitro group, a carboxyl group, a ferrocenyl group, an unsubstituted alkyl group having 1 to 8 (particularly 1 to 4) carbon atoms, or an alkyl group having 1 to 8 carbon atoms To 8 (particularly 1 to 4) halogen substituted alkyl groups.

X ¹¹ and X ^{11 '} are an oxygen atom, a sulfur atom, -CR ²³ R ²⁴ [in particular, R ²³ and R ²⁴ may be unsubstituted or substituted with a halogen atom, or may be substituted with a carbon-carbon double bond May be substituted with an alkyl group having 1 to 8 carbon atoms (particularly 1 to 4 carbon atoms), an unsubstituted or halogen atom, and the number of carbon atoms may be 7 to 20, 15) or a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms. Further, an oxygen atom, a sulfur atom, -CR ²³ R ²⁴ - (particularly, an unsubstituted alkyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ ) is more preferable.

Y ¹¹ and Y ^{11 '} may be substituted with a halogen atom, a nitro group, a carboxyl group, or a ferrocenyl group, and the number of carbon atoms which may be substituted with an oxygen atom or -CO- may be 6 to 30 (particularly 6 to 12) An aryl group having 7 to 30 carbon atoms, particularly 7 to 15 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. Further, the alkyl group may be substituted with a halogen atom, and an arylalkyl group having 7 to 30 carbon atoms (particularly 7 to 15 carbon atoms) or an alkyl group having 1 to 8 carbon atoms, which may be substituted with an oxygen atom, is more preferable.

And Q is a methine chain having 7 or 9 carbon atoms. Further, a methine chain having 7 or 9 carbon atoms is constituted, and the hydrogen atom in the methine chain is substituted with a hydroxyl group, a halogen atom, a cyano group or an aryl group. A methine chain having 7 or 9 carbon atoms and having a ring structure in the chain.

The production method of the cyanine compound (?) Used in the present invention is not particularly limited, and it can be obtained by a method using the usual reaction, and examples thereof include a route described in Japanese Patent Application Laid-Open No. 2010-209191 , A method of synthesizing a compound having a corresponding structure by the reaction of an imine derivative.

The cyanine compound (?) Used in the present invention preferably has a maximum absorption wavelength (? Max) of the coating film (coating film) of 650 to 1200 nm, more preferably 650 to 900 nm. If the maximum absorption wavelength (max) of the coating film is 1200 nm or more of the present invention, the effect of the present invention is not exerted. If it is less than 650 nm, it is not preferable because it absorbs visible light.

In the heat-reactive composition of the present invention, the content of the cyanine compound (a) is 0.01 or more in total of at least one kind (?) Of the cyanine compound per 100 parts by mass of the solid content of the resin (? To 10 parts by mass. When the content of the cyanine compound (a) is less than 0.01 part by mass, the cured product of the present invention may not exhibit sufficient infrared ray shielding ability. When the content of the cyanine compound is more than 10 parts by mass, precipitation of the cyanine compound Precipitation) may occur.

<Resin (?)>

The resin (?) Is not particularly limited as long as it is a resin having an ethylenically unsaturated bond and a hydrophilic group in one molecule, and those conventionally used can be used.

Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group or a salt thereof, and a hydroxyl group and a carboxyl group are preferable because of high solubility of the resin (β) in alkali.

The preferable functional group equivalent (the mass of the resin including one equivalent of the hydrophilic group) of the hydrophilic group in the resin (?) Is 50 to 10,000.

The preferable mass average molecular weight of the resin (?) Is 1000 to 500000.

Among these resins, those having a unit represented by the following general formula (I-1), a unit represented by the following general formula (I-2) and a unit represented by the following general formula (I- And heat resistance are high.

Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms, wherein X ¹ is a hydrogen atom or a methyl group, Y ¹ is a divalent linking group, An alkyl group, an aryl group and an arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the methylene group in the alkyl group and the arylalkyl group may be replaced by -O-, -S-, -CO -, -COO-, -OCO- or -NH-, or a combination thereof, and R ² , R ³ and R ⁴ are each independently a hydrogen atom or a methyl group.

The divalent linking group represented by Y ¹ in the general formula (I-2) includes a structure represented by the following general formula (1).

(Wherein X ² represents -CR ⁵ R ⁶ -, -NR ⁷ -, divalent chain hydrocarbon group having 1 to 35 carbon atoms, divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, divalent carbon An aromatic hydrocarbon group having 6 to 35 atoms, a divalent heterocyclic group having 2 to 35 carbon atoms, or any one of substituents represented by the following (1-1) to (1-3), R ⁵ and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, Z ¹ and Z ² each independently represent a direct bond, _{-O-, -S-, -SO 2 -,} -SO-, -NR 7 - or -PR ⁸ - represents the, R ⁷ and R ⁸ are a hydrogen atom, an alkyl group having carbon atoms 1 to 8, carbon atoms, An aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms,

Wherein R ^5, R ^6, R exchanger ⁷ and the alkyl group in R ^8, aryl and alkyl groups, being optionally substituted with a halogen atom, a hydroxyl group or a nitro group, wherein R ^5, R ^6, R ⁷ and the alkyl group in R ⁸ And the methylene group in the arylalkyl group may be substituted with -O-, -S-, -CO-, -COO-, -OCO- or -NH- group. Provided that the number of carbon atoms of the group represented by the general formula (1) is in the range of 1 to 35.)

(Wherein R ⁷¹ represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group of 3 to 10 carbon atoms,

R ⁷² represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, or a halogen atom, and the alkyl group, alkoxy group and alkenyl group may have a substituent And,

f is an integer from 0 to 5.)

( ^Wherein R ⁷³ and R ⁷⁴ each independently represents an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 6 to 30 carbon atoms which may have a substituent, a carbon which may have a substituent An aryloxy group having 6 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, which may have a substituent, an arylalkenyl group having 6 to 30 carbon atoms, which may have a substituent, a number of carbon atoms An arylalkyl group of 7 to 30 carbon atoms, a heterocyclic ring-containing group of 2 to 20 carbon atoms which may have a substituent or a halogen atom,

The methylene group in the alkyl group and the arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-,

R ⁷³ may form a ring adjacent to R ⁷³ ,

d represents a number of 0 to 4,

f represents a number of 0 to 8, g represents a number of 0 to 4,

h represents a number of 0 to 4,

The sum of the numbers of g and h is 2 to 4.)

Examples of the aryl group having 6 to 30 carbon atoms or the arylalkyl group having 7 to 30 carbon atoms (preferably 7 to 20 carbon atoms) represented by R ¹ in the general formula (I-3) An aryl group or an arylalkyl group exemplified in the description of the cyanine compound.

Examples of the alkyl group having 1 to 20 carbon atoms include the alkyl groups exemplified in the description of the cyanine compound (?), The nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, heptadecyl , Octadecyl and the like.

Examples of the divalent chain hydrocarbon group having 1 to 35 carbon atoms represented by X ² in the general formula (1) include methane, ethane, propane, iso-propane, butane, sec-butane, tert- Heptane, isoheptane, 1-methyloctane, iso-octane, tert-octane and the like are preferable as Z ¹ and Z ² , &lt; / RTI &gt;

The alicyclic hydrocarbon group of the divalent carbon atoms, 3 to 35, this such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethyl-cyclobutane, 4-methyl-cyclohexane Z ¹ and Z ^2, , And the like,

Examples of the divalent aromatic hydrocarbon group having 6 to 35 carbon atoms include groups in which groups such as phenylene, naphthylene and biphenyl are substituted with Z ¹ and Z ² ,

Examples of the divalent heterocyclic group containing 3 to 35 carbon atoms include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrothriazine, furan, tetrahydrofuran, Thienophene, thiolane, etc. are substituted with Z ¹ and Z ² , and these groups may be combined in plural. These chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups may be substituted with a halogen atom, a hydroxyl group or a nitro group. The methylene groups in these chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups may be substituted with -O-, -S-, -CO-, -COO-, -OCO- or -NH- groups.

An alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1) Includes an alkyl group, an aryl group and an arylalkyl group exemplified in the description of the cyanine compound (?),

The alkyl group, aryl group and arylalkyl group in R ⁵ , R ⁶ , R ⁷ and R ⁸ may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the alkyl group and arylalkyl group in R ⁵ , R ⁶ and R ⁷ May be interrupted by groups of -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a combination of a plurality of these groups, and the substitution position and the interrupted position thereof are particularly limited It does not.

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷¹ in the substituent represented by the above (1-1) include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl,

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁷² include groups satisfying the predetermined number of carbon atoms among the groups exemplified as alkyl groups having 1 to 40 carbon atoms represented by R ¹ ,

Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁷² include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert -butyloxy, isobutyloxy, amyloxy, isoamyl Isobutyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyl, tertiary amyloxy, heptyloxy, heptyloxy, heptyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, Oxy, decyloxy and the like.

Examples of the substituent which the alkyl group, alkoxy group and alkenyl group represented by R ⁷² may have include a halogen atom, a hydroxyl group and a nitro group.

In the group represented by (1-3), examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include a group exemplified as an alkyl group having 1 to 20 carbon atoms represented by R ¹ , A group which satisfies the predetermined number of carbon atoms, and the like,

Examples of the aryl group having 6 to 30 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include groups exemplified as an aryl group having 6 to 30 carbon atoms represented by R ¹¹ ,

Examples of the aryloxy group having 6 to 30 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, Butylphenyloxy, 4-heptylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyloxy, 4-isopropylphenyloxy, 4-isopropylphenyloxy, , 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2,6-dimethylphenyloxy, 3,4-dimethylphenyl Butylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6- Di-tert-butylphenyloxy, 2,5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy and ferrocenyloxy,

Examples of the arylthio group having 6 to 30 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include a group in which an oxygen atom of an aryloxy group having 6 to 30 carbon atoms which may have the above substituent may be substituted with a sulfur atom , &Lt; / RTI &gt;

Examples of the arylalkenyl group having 8 to 30 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include an aryloxy group having 6 to 30 carbon atoms and optionally substituted with an oxygen atom such as vinyl, And groups substituted with an alkenyl group such as propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-

Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ⁷³ and R ⁷⁴ include groups exemplified as arylalkyl groups having 7 to 30 carbon atoms represented by R ⁷¹ and R ⁷² ,

Examples of the heterocyclic ring containing 2 to 20 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include pyridine, pyrazine, piperazine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, Furan, tetrahydrofuran, chroman, xanthene, thiophene, thiolane, and the like.

Examples of the above substituents which the various groups represented by R ⁷³ and R ⁷⁴ may have include a halogen atom, a hydroxyl group and a nitro group.

(I-1) :( I-2) :( I-3) = 0.1 to 0.65: 0.3 to 0.8: 0.001 to 2, and any arrangement such as random copolymerization, block copolymerization or graft copolymerization may be employed.

Among the resins (?) Having units represented by the general formulas (I-1), (I-2) and (I-3), the following are preferable.

R ¹ is preferably an alkyl group having 1 to 8 carbon atoms and an arylalkyl group having 7 to 30 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

When Y ¹ is a divalent linking group of the structure represented by the general formula (1), X ² is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 7 to 15 carbon atoms having a cycloalkylene group Rhenylene is more preferable. The hydrogen atom in these alkylene groups may be substituted with a halogen atom, a hydroxyl group or a nitro atom, and the methylene group in the chain alkylene part in the alkylene group may be replaced by -O-, -S-, -CO-, -COO-, OCO- or -NH- group.

Z ¹ and Z ² are preferably a direct bond.

The resin (?) Has an acid value of preferably 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, the alkali developability may not be sufficiently obtained. When the acid value is more than 200 mg / KOH, the resin () may be difficult to produce.

Here, acid clogging is based on JIS K0050 and JISK 0211.

In the heat-reactive composition of the present invention, the content of the resin (b) is preferably 30 to 99% by mass, particularly preferably 60 to 95% by mass, in the solid content of the heat-reactive composition of the present invention. If the content of the resin (b) is less than 30 mass%, the mechanical strength of the cured product may be insufficient to cause cracking. When the content of the resin (b) is more than 99 mass%, the curing by exposure may become insufficient, May occur.

&Lt; Thermal polymerization initiator (?) &Gt;

As the thermal polymerization initiator (γ), conventionally known compounds can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2, Azo-based polymerization initiators such as 2'-azobis-2,4-dimethylvaleronitrile and 1,1'-azobis (1-acetoxy-1-phenylethane); Based peroxide polymerization initiators such as benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxydicarbonate; peroxides such as ammonium persulfate, sodium persulfate, And persulfates such as potassium. These may be used alone or in combination of two or more.

Among the above thermal polymerization initiators (?), An azo-based polymerization initiator is preferable in view of heat resistance, and an azobis-based compound is more preferable. The azobis compound is preferably a compound represented by the following general formula (A) in view of industrial availability.

(Wherein R ₁₀₁ is a branched or straight chain alkyl group having 1 to 10 carbon atoms which may have a substituent and R ₁₀₂ is a branched or straight chain alkyl group having 1 to 10 carbon atoms which may have a substituent Or a group represented by the following general formula (B), wherein the methylene group in the alkyl group is -O-, -CO-O-, -O-CO-, -CO-NH-, -NH- And R ₁₀₁ and R _{102 which} are bonded to the same carbon atom may be connected to each other to form a ring. X ₁₀₁ represents a cyano group, -CONR ₁₀₃ R ₁₀₄ , -COOR ₁₀₅ , -C = NR ₁₀₆ And R ₁₀₃ , R ₁₀₄ , R ₁₀₅ and R ₁₀₆ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms which may have a substituent. )

(Wherein R ₁₁₁ , R ₁₁₂ and R ₁₁₃ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and R ₁₁₁ and R ₁₁₂ are connected to form a ring , And * denotes a bonding portion.)

_{R 101, R 102, X 101} , R 103, R 104, R 105, R 106, R 111, R a group represented by _112, and R ₁₁₃ is the specific carbon of the groups exemplified as the alkyl group represented by such as the above R ¹¹ And the number of atoms is satisfied.

The ring formed by connecting R ₁₀₁ and R ₁₀₂ to each other may be a cycloalkyl ring, and is preferably a cycloalkyl ring having 3 to 8 carbon atoms.

The ring formed by connecting R ₁₁₁ and R ₁₁₂ to each other may be an imidazole ring.

The substituent when the alkyl group represented by R ₁₀₁ , R ₁₀₂ , X ₁₀₁ , R ₁₁₁ , R ₁₁₂ and R ₁₁₃ has a substituent includes an alkoxy group having 1 to 4 carbon atoms, a carboxyl group or a hydroxyl group.

In the heat-reactive composition of the present invention, the content of the thermal polymerization initiator (γ) is preferably 0.1 to 30 mass%, particularly 0.5 to 10 mass%, based on the solid content of the heat-reactive composition of the present invention. When the content of the thermal polymerization initiator (γ) is less than 0.1% by mass, sufficient heat resistance may not be obtained. When the content is larger than 30% by mass, a thermal polymerization initiator (γ) may precipitate in the heat reactive composition.

<Monomer (ω) having an unsaturated bond>

The heat-reactive composition of the present invention may further contain a monomer (ω) having an unsaturated bond. Examples of the monomer having an unsaturated bond include acrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyacrylate Ethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid Butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, methyl methacrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, Bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z Diglycidyl ether (meth) acrylate, and tripropylene glycol di (meth) acrylate. Above all, a monomer having a plurality of unsaturated bonds is preferable because it can improve infrared ray shielding ability and heat resistance.

<Solvent (?)>

The heat-reactive composition of the present invention may further contain a solvent (?). The solvent is usually a solvent capable of dissolving or dispersing the above components (such as a cyanine compound (?)), If necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl Ketones such as isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, amyl alcohol and diacetone alcohol; Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, Ethers such as 1-t-butoxy-2-propanol, 3-methoxybutyl acetate and cyclohexanol acetate; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin solvents such as Mineral Spirit, Swazol # 310 (Cosmo Matsuyama Sekiyu Co., Ltd.) and Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; A solvent such as acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water These solvents can be used singly or as a mixed solvent of two or more kinds. Of these, ketones, ether ester solvents and the like, in particular, propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like are used in a thermoreactive composition with a resin (?) And a thermopolymerization initiator Solubility) is preferable.

In the heat-reactive composition of the present invention, the amount of the solvent (?) To be used is preferably such that the concentration of the composition other than the solvent (?) Is 5 to 30 mass%. When the concentration of the composition other than the solvent (?) Is less than 5% by mass, it may become difficult to increase the film thickness or the desired wavelength light may not be sufficiently absorbed. When the concentration exceeds 30% The storage stability of the composition due to precipitation may be deteriorated, or the viscosity may be improved and the handling may be lowered.

The heat-reactive composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; A layered clay mineral, milori blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates Silver sulfide, silver sulfide, selenide, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver and copper. Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the heat-reactive composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass based on 100 parts by mass of the resin (?), One or more of them may be used.

These inorganic compounds are used, for example, as fillers, antireflective agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbents, ink repellants and the like.

In the heat-reactive composition of the present invention, when a pigment and / or an inorganic compound is used, a dispersant may be added. The dispersing agent is not particularly limited as long as it can disperse or stabilize the pigment and / or the inorganic compound. Commercially available dispersing agents such as VICKEMY products and BYK series can be used. Among them, those having basic functional groups A polymer dispersant comprising a polyester, a polyether, and a polyurethane; a functional group having a nitrogen atom as a basic functional group and having a nitrogen atom as an amine and / or a quaternary salt thereof; and an amine value of 1 to 100 mgKOH / g .

The heat-reactive composition of the present invention may optionally contain thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine and the like; Plasticizers; Adhesion promoters; Fillers; Defoamer; Leveling agents; Surface modifiers; Antioxidants; Ultraviolet absorber; A dispersing aid; An anti-aggregation agent; catalyst; Curing accelerator; A crosslinking agent; Additives such as thickeners can be added.

In the heat-reactive composition of the present invention, any component other than the cyanine compound (?), The resin (?) And the thermopolymerization initiator (?) Except for the monomer (?) Having a unsaturated bond and the solvent ) Is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less based on 100 parts by mass of the resin (?).

In the heat-reactive composition of the present invention, by using another organic polymer together with the resin (?), The properties of the cured product of the heat-reactive composition of the present invention may be improved. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, Acrylonitrile, methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, Among them, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable. Among them, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, desirable.

When other organic polymers are used, the amount thereof is preferably 10 to 500 parts by mass based on 100 parts by mass of the resin (?).

A chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound and the like may be used in combination in the heat-reactive composition of the present invention.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. 3-mercaptopropionic acid, N- (2-mercaptopropionyl) glycine, 2-mercapto nicotinic acid, 3-mercaptopropionic acid, 3-mercaptopropionic acid and the like are exemplified by thioglycolic acid, thioferric acid, thiosalicylic acid, 2- mercaptopropionic acid, - [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanol Mercaptoethanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2- (2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) Mercapto compounds, disulfide compounds obtained by oxidizing the mercapto compounds, alkyl iodides such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid, trimethylolpropane tris (3 -Mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bistyropropionate, butanediol bisthioglycolate, Trimethylolpropane trisphosphate, ethyleneglycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiouropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, penta Erythritol tetrakisthioglycolate, tris hydroxyethyl tri Aliphatic polyfunctional thiol compounds such as stearoyl phonate, the following compounds C1 and trimercapto propionic acid tris (2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko Co., And the like.

Examples of the surfactant include fluorine surfactants such as perfluoroalkylphosphoric acid esters and perfluoroalkylcarboxylic acid salts, anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates, higher amine halides, Cationic surfactants such as quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, and silicone surfactants. And they may be used in combination.

As the silane coupling agent, for example, a silane coupling agent available from Shin-Etsu Chemical Co., Ltd. can be used. Of these, silane coupling agents such as KBE-9007, KBM-502 and KBE-403 having isocyanate groups, methacryloyl groups, A silane coupling agent is preferably used.

With the melamine compound, the (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzo guar active methylol group of the nitrogen compounds, such as namin, (poly) methylol urea (CH ₂ OH groups) (At least two) of all or some of them are alkyl-etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and they may be the same or different. In addition, the methylol group which is not alkyl-etherified may self-condense in one molecule, or may condense between two molecules, resulting in formation of an oligomer component. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Of these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred.

In the case of a solid state without solvent, the heat-reactive composition of the present invention may be dissolved or dispersed in a solvent, and then may be spin-coater, roll coater, bar coater, die coater, curtain coater, slit coater, dip coater, , Quartz glass, a semiconductor substrate, a metal, a paper, a plastic, or the like by a known means such as a soda-lime glass or the like. Further, the film may be once transferred onto a supporting substrate such as a film, and then transferred onto another supporting substrate.

The heating conditions for curing the heat-reactive composition of the present invention are 1 to 100 minutes at 70 to 250 ° C. After pre-baking, it may be post-baked by pressurization, or baked at several different temperatures.

The heating conditions vary depending on the kind of each component and the mixing ratio. For example, the heating condition is from 70 to 180 DEG C for 5 to 15 minutes in an oven and from 1 to 5 minutes in a hot plate. Thereafter, in order to cure the coated film, the coated film is subjected to heat treatment at 100 to 250 ° C, preferably 180 to 250 ° C, more preferably 200 to 250 ° C for 30 to 90 minutes in an oven and 5 to 30 minutes in a hot plate, Can be obtained.

The heat-reactive composition (or a cured product thereof) of the present invention can be used in a liquid-crystal display panel of a color display such as a heat-reactive paint or varnish, a heat-reactive adhesive, a printed board or a color TV, a PC monitor, a portable information terminal, A color filter, a color filter of a CCD image sensor, an electrode material for a plasma display panel, a powder coating, a printing ink, a printing plate, an adhesive, a dental composition, Inclusion of resists, electric and electronic parts for forming a structure in both liquid and dry films, solder resists, for producing color filters for various display applications, or for manufacturing plasma display panels, electroluminescence displays, and LCDs A solder resist, a magnetic recording material, a fine mechanical part, a waveguide, an optical switch, a plating solution An image recording material, a fine electronic circuit, a decolorizing material, and an image recording material are used as a material for forming a three-dimensional object by means of a stereolithography method, a screen printing method, an etching mask, a color tester, a glass fiber cable coating, A decolorizing material for an image recording material using a microcapsule, a photoresist material for a printed wiring board, a photoresist material for a UV and visible laser direct-image system, and a printed circuit board. A photoresist material, a protective film, and the like, and the use thereof is not particularly limited.

The heat-reactive composition of the present invention is used for the purpose of blocking specific infrared rays, and is particularly useful as a heat-reactive composition for forming a wavelength cut filter.

Next, the wavelength cut filter of the present invention will be described.

The wavelength cut filter of the present invention has a coating layer (B) obtained from the thermo-reactive composition of the present invention on one side of a glass substrate (A) and an infrared reflecting film (C) on the other side of the glass substrate will be. The coating layer (B) and the infrared reflective film (C) are laminated on each side of the glass substrate (A). As shown in Fig. 1, the side having the coating layer (B) obtained from the thermoreactive composition of the present invention may be the light incidence side, and the side having the infrared reflective film (C) . Hereinafter, each layer will be described in order.

&Lt; Glass Substrate (A) >

As the glass substrate (A) used in the wavelength cut filter of the present invention, a transparent glass material can be appropriately selected and used in a visible region, and it is possible to use a soda lime glass, a white plate glass, a borosilicate glass, a tempered glass, Among them, soda lime glass is preferable because it is inexpensive and easy to obtain, and white plate glass, borosilicate glass and tempered glass are preferable because they are easy to obtain, have high hardness and excellent workability.

When the coating layer (B) is formed by applying the coating composition comprising the thermally reactive composition of the present invention after the glass substrate (A) is pretreated with a silane coupling agent or the like, the coating layer (B ) To the glass substrate is enhanced.

Examples of the silane coupling agent include epoxy functionalities such as? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Amino functional alkoxysilanes such as alkoxysilane, N -? (Aminoethyl) -? - aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane and N-phenyl-? -Aminopropyltrimethoxysilane,? And mercapto-functional alkoxysilanes such as mercaptopropyltrimethoxysilane.

In addition, a base layer (lower layer) may be provided between the glass substrate (A) and the coating layer (B). The base layer is formed by dispersing an aggregate of fine metal oxide particles having an average secondary particle size of 20 to 250 nm obtained by agglomerating primary particles having an average primary particle diameter of 5 to 100 nm in a solvent shown below in the following manner , And has a thickness of 30 to 1000 nm. The aggregate of the metal oxide fine particles is preferably 0.1 to 50 mass% with respect to the total amount of the coating liquid.

The thickness of the glass substrate (A) is not particularly limited, but is preferably 0.05 to 8 mm, more preferably 0.05 to 1 mm in terms of weight reduction and strength.

In the present invention, since the substrate is a glass plate, it can be directly coated on the substrate, dried, and then cut, so that the structure and the process are simplified. Further, since the substrate is a glass plate, heat resistance (260 占 폚 reflow resistance) is higher than in the case of plastic.

&Lt; Coating layer (B) >

The coating layer (B) obtained from the heat-reactive composition of the present invention used in the wavelength cut filter of the present invention can be formed by applying the heat-reactive composition of the present invention onto the glass substrate (A) as described above. The obtained coating film is cured by heating as necessary.

The thickness of the coating layer (B) containing the dye is preferably 1 to 200 mu m because a uniform film can be obtained and it is advantageous to form a thin film. If it is less than 1 mu m, the function can not be sufficiently manifested. If it is more than 200 mu m, the solvent may remain at the time of coating.

&Lt; Infrared reflective film (C) >

The infrared reflective film (C) used in the wavelength cut filter of the present invention has a function of blocking light in a wavelength range of 700 to 1200 nm and is formed by a dielectric multilayer film in which a low refractive index layer and a high refractive index layer are alternately laminated do.

As the material constituting the low refractive index layer, a material having a refractive index of 1.2 to 1.6 can be used. Examples of the material include silica, alumina, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride and the like.

As the material constituting the high refractive index layer, a material having a refractive index of 1.7 to 2.5 can be used. For example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide , And indium oxide. In addition, titanium oxide, tin oxide, cerium oxide or the like may be contained in a small amount as a main component.

The method of laminating the low refractive index layer and the high refractive index layer is not particularly limited as long as a dielectric multilayer film in which these layers are laminated is formed. For example, a method of forming a dielectric multilayer film by a CVD method, a sputtering method, And a method of forming a dielectric multilayer film in which a low refractive index layer and a high refractive index layer are alternately laminated. Alternatively, a dielectric multi-layer film may be formed in advance and then adhered to a glass substrate with an adhesive.

The number of laminated layers is preferably from 10 to 80 and preferably from 25 to 50 in terms of process and strength.

The thicknesses of the low refractive index layer and the high refractive index layer are usually 1/10 to 1/2 of the wavelength? (Nm) of the light beam to be intercepted, respectively. If the thickness is less than 0.1? Or larger than 0.5 ?, the product of the refractive index (n) and the physical film thickness (d) is significantly different from the optical film thickness represented by a multiple of? / 4, There is a concern.

Examples of the infrared reflective film (C) include a film containing a dye having a maximum absorption wavelength of 700 to 1100 nm, a laminate of polymers, a film formed by coating a cholesteric liquid crystal, etc., May be used.

It is preferable that the wavelength cut filter of the present invention satisfies the following (i) - (iii). The transmittance was measured by an infrared spectrophotometer V-570 manufactured by Nihon Bunko Co., Ltd.

(I) the average value of the transmittance in the wavelength range of 430 to 580 nm measured from the vertical direction of the wavelength cut filter (the direction perpendicular to the plate surface of the glass substrate, the same shall apply hereinafter) is 75% or more.

(Ii) the average value of the transmittance when measured from the vertical direction of the wavelength cut filter at a wavelength of 800 to 1000 nm is 5% or less.

(Iii) a value (Ya) of the wavelength at which the transmittance is 80% when measured from the vertical direction of the wavelength cut filter in a wavelength range of 560 to 800 nm and an angle of 35 degrees with respect to the vertical direction of the wavelength cut filter The absolute value of the difference in the value (Yb) of the wavelength at which the transmittance becomes 80% when measured is 30 nm or less.

In the wavelength cut filter, when the average value of the transmittance in the range of 430 to 580 nm of (i) is less than 75%, almost no light in the visible light region is transmitted. The average value of the transmittance in the wavelength range of 430 to 580 nm of (i) is more preferably 80% or more. If the average value of the transmittances at wavelengths of 800 to 1000 nm in (ii) above exceeds 5%, the light in the infrared region is hardly cut, and it may be difficult to correct the sensitivity so as to approach the human visibility . And the average value of the transmittance at a wavelength of 800 to 1000 nm in (ii) is more preferably 1% or less.

If the absolute value of the difference between Ya and Yb in (iii) exceeds 30 nm, the dependence of the light on the incident angle increases, and the characteristics of the wavelength cut filter are changed by the incident angle of light. There is a possibility that harmful effects such as a change in color tone may occur. The absolute value of the difference between Ya and Yb in (iii) is more preferably 5 nm or less, and still more preferably 3 nm or less.

Specific examples of the use of the wavelength cut filter of the present invention include a heat ray cut filter mounted on a window glass of a vehicle or a building; For visibility correction for solid-state image pickup devices such as CCD and CMOS in solid-state image pickup devices such as digital still cameras, digital video cameras, surveillance cameras, vehicle-mounted cameras, web cameras, and cellular phones; Automatic exposure meter; And a display device such as a plasma display.

Next, the solid-state imaging device and camera module of the present invention will be described.

The solid-state image pickup device of the present invention is configured similarly to the conventional solid-state image pickup device except that the wavelength cut filter of the present invention is provided on the front surface of the image pickup device. As shown in Fig. 5 and Fig. 6, the wavelength cut filter 1 of the present invention may be fixed to a portion other than the solid-state image pickup element on the light incidence side of the solid-state image pickup element 2, State imaging element 2, as shown in Fig.

In the solid-state imaging device of the present invention, an optical low-pass filter, an antireflection filter, a color filter, or the like can be disposed as needed, and there is no particular limitation on the order of lamination.

As shown in Figs. 3 and 4, the wavelength cut filter 1 of the present invention is mounted on the solid-state image pickup device at the light incidence side of the solid-state image pickup device 2 with respect to the camera module, which is one of the solid- The case where the layers are stacked will be described in detail.

3 and 4 are cross-sectional views showing one configuration of a camera module which is one of the solid-state imaging devices of the present invention. The camera module includes a solid-state imaging element 2 formed in a rectangular shape when viewed from the plane of the semiconductor substrate and a light-emitting portion (light-receiving portion) 3 on the opposite side of the solid- A wavelength cut filter 1 (FIG. 3) and / or an infrared ray reflective film (C), a glass substrate (A), and a dye-containing layer 2 which are laminated in this order from a coating layer B, a glass substrate A and an infrared- And the coating layer B are laminated in this order on the surface of the solid state image pickup device 2 and the wavelength cut filter 1 (FIG. 4) formed on the surface of the solid state image pickup device 2 except for the light receiving portion 3, The cut filter 1 is bonded with the adhesive 4. The camera module as a solid-state imaging device collects light from the outside through the wavelength cut filter 1 and receives the light by a light-receiving element disposed in the light-receiving section 3 of the solid-

As shown in Figs. 5 and 6, the wavelength cut filter 1 of the present invention is applied to a camera module, which is one of the solid-state image pickup devices of the present invention, on the light incidence side of the solid- Is fixed to a portion of the display device.

5 and 6 are cross-sectional views showing one configuration of a camera module which is one of the solid-state imaging devices of the present invention. The camera module comprises a solid-state imaging element 2 formed in a rectangular shape when viewed from the plane of the semiconductor substrate and a coating layer B containing a dye from the light incidence side on the opposite side of the light- The wavelength cut filter 1 (Fig. 5) and / or the infrared ray reflection film (C), the glass substrate (A), the coating layer (B) containing the dye, the glass substrate (A) (FIG. 6) laminated in this order on the surface of the solid-state image sensor 2, and a region excluding the light-receiving portion 3 on one surface of the solid-state image sensor 2. The camera module as a solid-state imaging device collects light from the outside through the wavelength cut filter 1 and receives the light by a light-receiving element disposed in the light-receiving section 3 of the solid-

As the adhesive 4, a UV-curable adhesive such as an acrylic resin or an epoxy resin, or a thermosetting resin can be used. After the adhesive 4 is uniformly applied, 4) are patterned and bonded by thermal curing. When bonding, vacuum application may be performed after being stuck in a vacuum environment.

The mounting substrate 8 is a rigid substrate using a glass epoxy substrate, a ceramic substrate, or the like, and is provided with a control circuit for controlling the solid-state image pickup device 2. [

The solid state imaging element 2 is arranged on the mounting substrate 8 and then the adhesive 4 is applied in advance to the position where the lens holder 7 of the mounting substrate 8 is fixed.

The lens cap 6 protects the lens 5. The lens holder 7 holds the lens 5 and includes a box-shaped base portion 7a provided on the mounting substrate 8 and covering the solid-state image pickup device 2, And a lens barrel portion 7b having a cylindrical shape.

The lens holder 7 is arranged on the mounting substrate 8 so that the lens holder 7 is brought into contact with the applied adhesive 4 and the light receiving portion 7 of the solid- The position of the lens holder 7 is adjusted so that the distance between the lens holder 7 and the lens 5 in the lens holder 7 coincides with the focal length of the lens 5.

After adjusting the position of the lens holder 7, the adhesive 4 is irradiated with ultraviolet rays, and the adhesive 4 is cured to manufacture a camera module.

The entire mounting substrate 8 to which the lens holder 7 is fixed may be heated at about 85 캜 and the adhesive 4 may be hardened sufficiently by thermal curing.

The lens holder 7, the lens 5, and the wavelength cut filter 1 are both provided on both sides of the mounting substrate 8, since the manufacturing method of the camera module includes a step of heating the entire mounting substrate 8 after the step of irradiating ultraviolet rays. It is necessary to use a material having high heat resistance. Concretely, as described above, in addition to the heating for thermosetting of the adhesive 4, a plurality of solders disposed on the lower surface of the mounting substrate 8 are heated and melted at about 260 캜 and soldered to another substrate, And is preferably formed of a material having reflow resistance.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples and the like.

[Preparation Example 1] Preparation of resin (?) No. 1

40 parts by mass of acrylic acid and 50 parts by mass of butyl methacrylate were dissolved in 200 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA). To this solution were added azobisisobutyronitrile 4 And the mixture was stirred at 80 占 폚 for 3 hours. Subsequently, 10 parts by mass of Celloxide 2021P modified with acrylic acid (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.) was added, and the mixture was stirred at 120 占 폚 for 3 hours to obtain a resin (?) No. 1.

Wherein X ¹ is a hydrogen atom or a methyl group and Y ¹ is a divalent linking group represented by the general formula (1) (X ² is a group represented by the following formula (n) ) is a group represented by, and Z ¹ and Z ² is a direct bond Im), R ¹ is an alkyl group of a carbon atom number of ^{1 ~ 8, R 2 ~ R} 3 is a hydrogen atom, R ⁴ is a methyl group in the resin (β )to be.

[Preparation Example 2] Preparation of resin (?) No. 2

20 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate and 50 parts by mass of benzyl methacrylate were dissolved in 500 parts by mass of cyclohexanone, and 4 parts by mass of azobisisobutyronitrile as a radical polymerization initiator was added to obtain 80 C &lt; / RTI &gt; for 3 hours. Subsequently, 20 parts by mass of acrylic acid was added and the mixture was stirred at 120 占 폚 for 3 hours to obtain a resin (?) No. 2.

[Production Example 3] Preparation of resin (?) No. 3

50 parts by weight of glycidyl methacrylate, 5 parts by weight of benzyl methacrylate and 40 parts by weight of styrene were dissolved in 500 parts by weight of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) (t-butylperoxy) -3,3,5-trimethylcyclohexane (1 part by mass), and the mixture was stirred at 140 ° C for 2 hours. Subsequently, 20 parts by mass of acrylic acid was added, and the mixture was stirred at 120 占 폚 for 3 hours to obtain a resin (?) No. 3.

[Production Example 4] Preparation of resin (?) No. 4

40 parts by mass of glycidyl methacrylate, 5 parts by mass of benzyl methacrylate and 40 parts by mass of styrene were dissolved in 500 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA), and azobisisobutyronitrile And 10 parts by mass of butyronitrile were stirred at 80 占 폚 for 3 hours. Subsequently, 20 parts by mass of acrylic acid was added and the mixture was stirred at 120 占 폚 for 3 hours to obtain a resin (?) No. 4.

[Preparation Example 5] Preparation of resin (?) No. 5

40 parts by mass of glycidyl methacrylate, 5 parts by mass of benzyl methacrylate and 40 parts by mass of styrene were dissolved in 500 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA), and azobisisobutyronitrile And 5 parts by mass of butyronitrile were added, and the mixture was stirred at 80 占 폚 for 3 hours. Subsequently, 20 parts by mass of acrylic acid was added, followed by stirring at 120 ° C for 3 hours. Subsequently, 5 parts by mass of tetrahydrophthalic anhydride was added and stirred at 120 ° C for 3 hours to obtain a resin (?) No. 5.

[Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-5] Preparation of heat-reactive compositions No. 1 to 11 and Comparative compositions No. 1 to No. 5

<Step 1> Preparation of dye solutions No. 1 to No. 10 and Comparative dye solutions No. 1 to No. 5

(?) Was added to the cyanine compound (?) Shown in [Table 1] to [Table 3] as a component (A) and dissolved by stirring to obtain Dye Liquids No.1 to No.10 and Comparative Dye Liquids No.1 to No.10, No.5 was obtained.

&Lt; Step 2 > 10 and comparative compositions No.1 to No.5

(?), A polymerization initiator (?) (Or (? (?), Or (?)) Was added to the above dye liquids No. 1 to No. 10 and Comparative dye liquids No. 1 to No. 5 according to the blending of [ (ω)) and a monomer (ω) having an unsaturated bond and a solvent (σ) were added and stirred to prepare heat-reactive compositions No. 1 to No. 10 and Comparative Compositions No. 1 to No. 5.

A-1: Hexafluorophosphate of Compound No. 76

A-2: Hexafluorophosphate of Compound No. 100

A-3: Synthesis of bis (trifluoromethanesulfonyl) imide acid salt of Compound No. 100

A-4: Synthesis of bis (trifluoromethanesulfonyl) imide acid salt of Compound No. 102

A-5: Synthesis of bis (trifluoromethanesulfonyl) imide acid salt of Compound No. 103

B-1: Resin (?) Obtained in Production Example 1 No. 1

B-2: ACA Z251 (acrylated acrylate manufactured by Daicelonex)

B-3: ACA Z250 (acrylated acrylate manufactured by Daicelonex)

B-4: ACA 200M (acrylated acrylate manufactured by Daicelonex)

B-5: SPC-1000 (acrylic resin manufactured by Showa Denko KK)

B-6: SPC-3000 (acrylic resin manufactured by Showa Denko KK)

B-7: Resin (?) Obtained in Production Example 2 No. 2

B-8: Resin (?) Obtained in Production Example 3 No. 3

B-9: Resin (?) Obtained in Production Example 4 No. 4

B-10: Resin (?) Obtained in Production Example 5 No. 5

C-1: V-60 (oil-soluble azo polymerization initiator available from Wako Pure Chemical Industries, Ltd.)

C-2: V-70 (azo polymerization initiator available from Wako Pure Chemical Industries, Ltd.)

C-3: V-65 (available azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.)

C-4: V-59 (azo polymerization initiator available from Wako Pure Chemical Industries, Ltd.)

C-5: V-40 (azo polymerization initiator available from Wako Pure Chemical Industries, Ltd.)

C-6: VAm-110 (available azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.)

C'-1: Irg-907 (a photopolymerization initiator manufactured by BASF)

C'-2: SP-246 (photopolymerization initiator manufactured by ADEKA)

C'-3: OXE-01 (photopolymerization initiator manufactured by BASF)

C'-4: OXE-02 (photopolymerization initiator manufactured by BASF)

D-1: Aronix M450 (acrylic monomer manufactured by Toagosei Co., Ltd.)

D-2: Aronix M315 (acrylic monomer manufactured by Toagosei Co., Ltd.)

E-1: Cyclohexanone

E-2: Diacetone alcohol

E-3: methyl ethyl ketone

[Evaluation Examples 1-1 to 1-10 and Comparative Evaluation Examples 1-1 to 1-5]

The comparative compositions No.1 to No.5 obtained in the heat-reactive compositions No.1 to No.10 and Comparative Examples 1-1 to 1-5 obtained in Examples 1-1 to 1-10 were placed on a glass substrate at 410 rpm 7 seconds, and dried (90 DEG C, 10 minutes) on a hot plate. After drying, the coating film was cured by heating on a hot plate at 150 ° C for 10 minutes. The cured coating film was heated at 150 ° C for 1 hour to evaluate the heat resistance. The evaluation was carried out by calculating the change in transmittance of the maximum absorption wavelength before and after heating. The amount of change in transmittance was obtained by the following equation.

Transmittance variation (%) = (X-Y) / X x 100 where X is the transmittance of the maximum absorption wavelength before heating and Y is the transmittance at the wavelength measured after heating.

The results are shown in Table 4.

(In Table 4, &quot; - &quot; indicates that films can not be evaluated uniformly because they can not be formed uniformly.)

From the results of the above Table 4, it is clear that the heat-reactive composition of the present invention shows little change in color difference and high heat resistance.

[Examples 2-1 to 2-10] Production of wavelength cut filters No. 1 to No. 10

A silica (SiO ₂ ) layer and a titanium oxide (TiO ₂ ) layer were alternately laminated on one surface of a glass substrate (A) having a thickness of 100 μm by vacuum vapor deposition to form an infrared ray reflective film (C).

The thermoreactive compositions (coating liquids) No. 1 to No. 10 obtained in Examples 1-1 to 1-10 were laminated on the surface different from the infrared reflecting film of the glass substrate (A) coated with the obtained infrared ray reflective film (C) Coater # 30 (film thickness: 10 mu m) was applied and then dried at 100 DEG C for 10 minutes to prepare wavelength cut filters No. 1 to No. 10. [

[Evaluation Examples 2-1 to 2-10]

The wavelength cut filters No. 1 to No. 10 of the present invention obtained in Examples 2-1 to 2-10 were evaluated for i) the transmittance when measured from the vertical direction of the wavelength cut filter in the wavelength range of 430 to 580 nm , Ii) an average value of the transmittance measured from the vertical direction of the wavelength cut filter at a wavelength of 800 to 1000 nm, and iii) a transmittance measured from the vertical direction of the wavelength cut filter at a wavelength of 560 to 800 nm The absolute value of the difference between the value of the wavelength (Ya) of 80% and the value of the wavelength (Yb) at which the transmittance becomes 80% when measured from an angle of 35 ° with respect to the vertical direction of the wavelength cut filter . The results are shown in Table 5. The transmittance was measured by an infrared spectrophotometer V-570 manufactured by Nihon Bunko Co., Ltd.

From the results in Table 5, it can be seen that the wavelength cut filter of the present invention has a high transmittance in a wavelength range of 430 to 580 nm, a low transmittance in a wavelength of 800 to 1000 nm, and a low incident angle dependency.

From the above results, it can be seen that the coating layer (B) containing a dye is formed on one side of the glass substrate (A) and the infrared reflecting film (C) is provided on the other side of the glass substrate The wavelength cut filter has a low incident angle dependency. Therefore, the wavelength cut filter of the present invention is useful for a solid-state imaging device and a camera module.

Claims (8)

(?) Of a cyanine compound, a resin (?) Having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (?). The method according to claim 1,
The resin (b) having at least an ethylenically unsaturated bond and a hydrophilic group is a unit represented by the following general formula (I-1), a unit represented by the following general formula (I-2) &Lt; / RTI &gt;

Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms, wherein X ¹ is a hydrogen atom or a methyl group, Y ¹ is a divalent linking group, The alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the methylene group in the alkyl group and the arylalkyl group may be replaced by -O-, -S-, - CO-, -COO-, -OCO- or -NH-, or a combination thereof, and R ² , R ³ and R ⁴ are each independently a hydrogen atom or a methyl group. 3. The method according to claim 1 or 2,
Wherein the thermal polymerization initiator (?) Is an azo thermal polymerization initiator. 4. The method according to any one of claims 1 to 3,
(A) of a cyanine compound in a total amount of 0.01 to 10.0 parts by mass based on 100 parts by mass of a solid content of a resin (?) Having at least an ethylenically unsaturated bond and a hydrophilic group. (B) obtained from the reactive composition according to any one of claims 1 to 4 on one side of a glass substrate (A) and an infrared reflective film (C) on the other side of the glass substrate Wherein the wavelength cut filter comprises: 6. The method of claim 5,
And the transmittance satisfies the following (i) - (iii).
(I) an average value of the transmittance measured from the vertical direction of the wavelength cut filter in the range of 430 to 580 nm is 75% or more
(Ii) the average value of the transmittance when measured from the vertical direction of the wavelength cut filter at a wavelength of 800 to 1000 nm is 5% or less
(Iii) a value (Ya) of the wavelength at which the transmittance is 80% when measured from the vertical direction of the wavelength cut filter in the wavelength range of 560 to 800 nm and an angle of 35 DEG with respect to the vertical direction of the wavelength cut filter The absolute value of the difference in the value Yb of the wavelength at which the transmittance becomes 80% in one case is 30 nm or less. A solid-state imaging device comprising the wavelength cut filter according to claim 5 or 6. A camera module comprising the wavelength cut filter according to claim 5 or 6.

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