CN107531857B

CN107531857B - Thermally reactive composition

Info

Publication number: CN107531857B
Application number: CN201680025737.6A
Authority: CN
Inventors: 前田洋介
Original assignee: Adeka Corp
Current assignee: Adeka Corp
Priority date: 2015-08-06
Filing date: 2016-08-01
Publication date: 2021-06-18
Anticipated expiration: 2036-08-01
Also published as: WO2017022708A1; TWI738660B; TW201708366A; CN107531857A; JPWO2017022708A1; KR20180038413A; JP6908522B2

Abstract

The heat reactive composition of the present invention comprises: at least one kind (alpha) of cyanine compounds, a resin (beta) having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (gamma). The resin (. beta.) preferably contains 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-3). The thermal polymerization initiator (γ) is preferably an azo thermal polymerization initiator. In the following formula, X¹、Y¹、R¹～R⁴The definition of (A) refers to the specification.

Description

Thermally reactive composition

Technical Field

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 heat polymerization initiator, and a wavelength cut filter using the heat-reactive composition.

Background

The sensitivity of a solid-state imaging device (such as a CCD or a C-MOS) used in a digital camera, a video camera, or a camera for a mobile phone is from an ultraviolet region to an infrared region of a wavelength of light. On the other hand, the visibility of a human is only a visible region of the wavelength of light. Therefore, by providing an infrared cut filter between the imaging lens and the solid-state imaging element, the sensitivity of the solid-state imaging element is corrected so as to be close to the visibility of a human.

As the infrared cut filter, a reflection type filter in which layers containing substances having no absorption property are combined and laminated in a multilayer and the difference in refractive index between them is utilized, or an absorption type filter in which a light absorbing agent is contained or bonded in a transparent substrate is known.

In particular, in the absorption filter, there is a problem that the infrared ray blocking ability is lowered due to deterioration of the light absorbing agent caused by heat treatment or the like at the time of manufacturing.

Patent documents

1 and 2 describe heat-reactive compositions containing a heat polymerization initiator. Patent document 3 describes a composition containing a cyanine compound, a resin having an ethylenically unsaturated bond and a hydrophilic group in one molecule, and a photopolymerization initiator.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2007 and 256865

Patent document 2: US2010051883a1

Patent document 3: japanese patent laid-open publication No. 2013-173848

Disclosure of Invention

Problems to be solved by the invention

However, the compositions described in patent documents 1 to 3 are insufficient in heat resistance.

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

Means for solving the problems

As a result of intensive studies, the present inventors have found that a wavelength cut filter obtained using 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 is suitable for a wavelength cut filter used in a solid-state imaging device or the like without lowering the heat resistance, and have completed the present invention.

The present invention provides a heat reactive composition comprising: at least one kind (alpha) of cyanine compounds, a resin (beta) having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (gamma).

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

Effects of the invention

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

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of the layer structure of the wavelength cut filter of the present invention.

Fig. 2 is a schematic cross-sectional view showing another example of the layer structure of the wavelength cut filter of the present invention.

Fig. 3 is a sectional view showing one embodiment of a configuration of a camera module which is one of the solid-state imaging devices of the present invention.

Fig. 4 is a sectional view showing another embodiment of the configuration of the camera module.

Fig. 5 is a cross-sectional view showing still another embodiment of the configuration of the camera module.

Fig. 6 is a cross-sectional view showing still another embodiment of the configuration of the camera module.

Detailed Description

The heat reactive composition of the present invention will be described below based on preferred embodiments.

The heat reactive composition of the present invention comprises: the composition comprises at least one of a cyanine compound (α) (hereinafter also referred to as cyanine compound (α)), a resin (β) (hereinafter also referred to as resin (β)) having at least an ethylenically unsaturated bond and a hydrophilic group, a thermal polymerization initiator (γ), and a monomer (ω) having an unsaturated bond and a solvent (σ) which are further added as necessary. The respective components are explained in turn below.

< Cyanine Compound (. alpha.)

The cyanine compound (α) used in the thermally reactive composition of the present invention is not particularly limited, and conventionally known cyanine compounds can be used, but a compound represented by the following general formula (II) is preferable from the viewpoint of availability.

[ solution 1]

(wherein, ring A and ring A' each independently represents a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,

R¹¹and R^11’Each independently represents a hydroxyl group, a halogen atom, a nitro group, a cyano group or-SO₃H. A carboxyl group, an amino group, an amide group, a metallocene group (metallocenyl), an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms,

X¹¹and X¹¹' independently represent an oxygen atom, a sulfur atom, a selenium atom, -CR²³R²⁴A C3-6 cycloalkane-1, 1-diyl group or-NR²⁵-，

R²¹、R²²、R²³、R²⁴And R²⁵Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group or a-SO group₃H. A carboxyl group, an amino group, an amide group, a metallocene group, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms,

Y¹¹and Y¹¹' independently represent a hydrogen atom, or may be substituted by a hydroxyl group, a halogen atom, a nitro group, a cyano group or an-SO group₃H. An aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms, which is substituted with a carboxyl group, an amino group, an amide group or a metallocene group,

r is as defined above¹¹、R^11’、Y¹¹、Y¹¹'、R²¹、R²²、R²³、R²⁴And R²⁵The aryl, aralkyl and alkyl groups in (1) may be substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group or a-SO group₃H. Substituted by carboxyl, amino, amido or metallocene groups, the above R¹¹、R^11’、Y¹¹、Y¹¹'、R²¹、R²²、R²³、R²⁴And R²⁵The methylene group in the aralkyl group and alkyl group in (A) is also sometimes represented by-O-, -S-, -CO-, -COO-, -OCO-, -SO₂-, -NH-, -CONH-, -NHCO-, -N-CH-or a carbon-carbon double bond substitution,

q represents the number of constituent carbon atoms1 to 9 methine chains each of which may contain a linking group having a ring structure, wherein the hydrogen atom in the methine chain may be substituted with a hydroxyl group, a halogen atom, a cyano group, -NRR ', an aryl group, an aralkyl group or an alkyl group, and the-NRR ', the aryl group, the aralkyl group or the alkyl group may be further substituted with a hydroxyl group, a halogen atom, a cyano group or a-NRR ', or may be substituted with-O-, -S-, -CO-, -COO-, -OCO-, -SO-, -₂-, -NH-, -CONH-, -NHCO-, -N-CH-or-CH-is interrupted,

r and R' represent aryl, aralkyl or alkyl,

r and r 'represent 0 or a number substitutable on ring A and ring A',

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

As R in the above general formula (II)¹¹、R^11’And X¹¹And X^11’R in (1)²³、R²⁴And R²⁵A halogen atom represented by the formula (I), and may be represented by the formula (I)¹¹、R^11’、R²³、R²⁴、R²⁵、Y¹¹、Y¹¹Examples of the halogen atom substituted with the aryl, aralkyl and alkyl groups of the formula' include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R in the above general formula (II)¹¹、R^11’And X¹¹And X^11’R in (1)²³、R²⁴And R²⁵Amino group represented by the formula and may be represented by R¹¹、R^11’、R²³、R²⁴、R²⁵、Y¹¹、Y¹¹Examples of the "amino group substituted with an aryl group, an aralkyl group or an alkyl group" include an amino group, an ethylamino group, a dimethylamino group, a diethylamino group, a butylamino group, a cyclopentylamino group, a 2-ethylhexylamino group, a dodecylamino group, an anilino group, a chlorophenylamino group, a toluylamino group, a methoxyanilino group, an N-methylanilino group, a diphenylamino group, a naphthylamino group, a 2-pyridylamino group, a methoxycarbonylamino group, a phenoxycarbonylamino group, an acetylamino group, a benzoylamino group, a formylamino group, a pivaloylamino group, a lauroyl groupAmino, carbamoylamino, N-dimethylaminocarbonylamino, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, N-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino and the like.

As R in the above general formula (II)¹¹、R^11’And X¹¹And X^11’R in (1)²³、R²⁴And R²⁵The amide group and may be represented by¹¹、R^11’、R²³、R²⁴、R²⁵、Y¹¹、Y¹¹Examples of the amide group substituted with the aryl, aralkyl or alkyl group include a carboxamide group, an acetamide group, an ethylamide group, an isopropylamide group, a butylamide group, an octylamide group, a nonylamide group, a decylamide group, an undecylamide group, a dodecylamide group, a hexadecylamide group, an octadecylamide group, (2-ethylhexyl) amide group and a benzamide group, trifluoroacetamide group, pentafluorobenzamide group, dimethylamide group, diacetamido group, diethylamide group, diisopropylamide group, dibutylamide group, dioctylamide group, dinonylamide group, didecylamide group, diundecylamide group, didodecylamide group, di (2-ethylhexyl) amide group, dibenzoamide group, di (trifluoroacetyl) amide group, di (pentafluorobenzamide) amide group, and the like.

As R in the above general formula (II)¹¹、R^11’And X¹¹And X^11’R in (1)²³、R²⁴And R²⁵The metallocene group represented, and can be represented by R¹¹、R^11’、R²³、R²⁴、R²⁵、Y¹¹、Y¹¹Examples of the metallocene group substituted with the aryl, aralkyl or alkyl group include ferrocenyl, nickelocene, zirconocene, titanocene and hafnocene groups.

As R in the above general formula (II)¹¹、R^11’、Z¹¹、Z¹²、Z¹³And Y¹¹、Y¹¹' and X¹¹And X^11’R in (1)²³、R²⁴And R²⁵Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearoylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2, 4-di-tert-butylphenyl, 2, 5-di-tert-butylphenyl, 2-tert-butylphenyl, 4-cyclohexylphenyl, 4-, 2, 6-di-t-butylphenyl, 2, 4-di-t-pentylphenyl, 2, 5-di-t-octylphenyl, 2, 4-dicumylphenyl, 4-cyclohexylphenyl, (1, 1' -biphenyl) -4-yl, 2,4, 5-trimethylphenyl, ferrocenyl and the like.

As R in the above general formula (II)¹¹、R^11’And Y¹¹、Y¹¹' and X¹¹And X^11’R in (1)²³、R²⁴And R²⁵Examples of the aralkyl group having 7 to 30 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl, ferrocenylpropyl and the like.

As R in the above general formula (II)¹¹、R^11’And Y¹¹、Y¹¹' and X¹¹And X¹¹R in `²³、R²⁴And R²⁵Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, 1-octyl, isooctyl, and tert-octyl.

As the above-mentioned R¹¹、R^11’And Y¹¹、Y¹¹' and X¹¹And X¹¹R in `²³、R²⁴And R²⁵In (1), which may be substituted by hydroxy, halogen, nitro, cyano, -SO₃An aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms and an alkyl group having 1 to 20 carbon atoms, which are substituted with an H group, a carboxyl group, an amino group, an amide group or a metallocene group, are listed as R¹¹Etc. the aryl group, aralkyl group, alkyl group and hydrogen atom in these groups are exemplified by hydroxy, halogen atom, nitro, cyano, -SO₃H group, carboxyl group, amino group, amide group or metallocene group, and the position and number of these substituents are not limited.

In addition, when the above-mentioned R is¹¹、R^11’And Y¹¹、Y¹¹' and X¹¹And X¹¹R in `²³、R²⁴And R²⁵In (b) the aralkyl group and the methylene group in the alkyl group are represented by-O-, -S-, -CO-, -COO-, -OCO-, -SO₂-, -NH-, -CONH-, -NHCO-, -N ═ CH-or a carbon-carbon double bond substitution, the number and position of these substitutions are arbitrary.

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

Examples of the group in which the alkyl group having 1 to 8 carbon atoms is interrupted by-O-include alkoxy groups such as methoxy, ethoxy, isopropoxy, propoxy, butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, and 2-ethylhexyloxy, and alkoxyalkyl groups such as 2-methoxyethyl, 2- (2-methoxy) ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl, and 3-methoxybutyl.

Examples of the group in which the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom and interrupted by-O-include chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy and nonafluorobutoxy.

In the above general formula (II), as X¹¹And X^11’Examples of the cycloalkane-1, 1-diyl group having 3 to 6 carbon atoms include cyclopropane-1, 1-diyl group, cyclobutane-1, 1-diyl group, 2, 4-dimethylcyclobutane-1, 1-diyl group, 3-dimethylcyclobutane-1, 1-diyl group, cyclopentane-1, 1-diyl group, cyclohexane-1, 1-diyl group and the like.

As the linking group which constitutes the methine chain having 1 to 9 carbon atoms and which may contain a ring structure, represented by Q in the above general formula (II), any of the following groups (Q-1) to (Q-11) is preferable because of ease of production. The number of carbon atoms in the methine chain having 1 to 9 carbon atoms is not included in the group in which the methine chain or the ring structure contained in the methine chain is further substituted (for example, the carbon atoms at both ends of the linker (Q-1), R described below¹⁴～R¹⁹Carbon atom of Z').

[ solution 2]

(in the formula, R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And Z 'independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, -NRR', an aryl group, an aralkyl group or an alkyl group, and the-NRR ', the aryl group, the aralkyl group and the alkyl group may be substituted with a hydroxyl group, a halogen atom, a cyano group or-NRR', or may be substituted with-O-, -S-, -CO-, -COO-, -OCO-, -SO-, -S-, -CO-, -COO-, -C-O-or-NRR₂-, -NH-, -CONH-, -NHCO-, -N ═ CH-, or-CH ═ CH-, interrupted, R and R' represent aryl, aralkyl or alkyl. )

As the above-mentioned R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And Z' represents a halogen atom, an aryl group, an aralkyl group or an alkyl group, and examples thereof include those represented by R¹¹Examples of the group exemplified in the description of the above include the aryl, aralkyl and alkyl groups represented by R and R¹¹And the like as exemplified in the description.

As pAn in the above general formula (II)^q-Examples of the q-valent anion include methanesulfonate anion, dodecylsulfonate anion, benzenesulfonate anion, toluenesulfonate anion, trifluoromethanesulfonate anion, naphthalenesulfonate anion, diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion, 2-amino-5-nitrobenzenesulfonate anion, naphthalenedisulfonic acid anion, naphtholsulfonate anion, bis (trifluoromethanesulfonyl) imide anion, Japanese patent application laid-open No. 10-235999, Japanese patent application laid-open No. 10-337959, Japanese patent application laid-open No. 11-102088, Japanese patent application laid-open No. 2000-108510, Japanese patent application laid-open No. 2000-168223, Japanese patent application laid-open No. 2001-209969, Japanese patent application laid-open No. 2001 322-354, Examples of the organic sulfonic acid anion such as a sulfonic acid anion described in Japanese patent laid-open Nos. 2006-248180, 2006-297907, 8-253705, 2004-503379, 2005-336150, 2006/28006 and the like, and further examples of the organic sulfonic acid anion include a chloride ion, a bromide ion, an iodide ion, a fluoride ion, a chlorate ion, a thiocyanate ion, a hexafluorophosphate ion, a hexafluoroantimonate ion, a tetrafluoroborate ion, an octylphosphate ion, a dodecylphosphate ion, an octadecylphosphate ion, a phenylphosphate ion, a nonylphenylphosphate ion, 2' -methylenebis (4, 6-di-t-butylphenyl) phosphonate ion, a tetrakis (pentafluorophenyl) borate ion, and a quencher anion having a function of deactivating (quenching) an active molecule in an excited state, Anions of metallocene compounds such as ferrocene and ruthenocene having an anionic group such as a carboxyl group, a phosphonic acid group or a sulfonic acid group in the cyclopentadiene ring.

Specific examples of the cyanine compound (α) used in the present invention include the following compound nos. 1 to 104. In the following examples, the cyanine cations are shown without the anions. [ solution 3]

[ solution 4]

[ solution 5]

[ solution 6]

[ solution 7]

[ solution 8]

[ solution 9]

[ solution 10]

[ solution 11]

[ solution 12]

[ solution 13]

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

A compound in which ring A or ring A' is a benzene ring or a naphthalene ring.

r or r' is 0 to 2.

When R or R' is 1 or more, R¹¹And R^11’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 a haloalkyl group having 1 to 8 (particularly 1 to 4) carbon atoms.

X¹¹And X^11'Is an oxygen atom, a sulfur atom, -CR²³R²⁴[ in particular, R ]²³And R²⁴A C1-8 (particularly 1-4) alkyl group which may be unsubstituted or substituted with a halogen atom or a carbon-carbon double bond, an aralkyl group which may be unsubstituted or substituted with a halogen atom or a carbon-carbon double bond and has 7-20 (particularly 7-15) carbon atoms, or a cycloalkane-1, 1-diyl group having 3-6 carbon atoms. Further, oxygen atom, sulfur atom, -CR are more preferable²³R²⁴- [ in particular, R²³And R²⁴An unsubstituted alkyl group having 1 to 4 carbon atoms.

Y¹¹And Y^11'A C6-30 (particularly 6-12) aryl group, a C7-30 (particularly 7-15) aralkyl group or a C1-8 alkyl group, which may be substituted with a halogen atom, a nitro group, a carboxyl group or a ferrocenyl group, or may be substituted with an oxygen atom or-CO-. Further, an aralkyl 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 a halogen atom or an oxygen atom is more preferable.

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

The method for producing the cyanine compound (α) used in the present invention is not particularly limited, and can be obtained by a method utilizing a well-known general reaction, and for example, a method of synthesizing the cyanine compound (α) by a reaction between a compound having a corresponding structure and an imine derivative, as in the route described in jp 2010-209191 a, can be mentioned.

The maximum absorption wavelength (. lamda.max) of the coating film of the cyanine compound (. alpha.) used in the present invention is preferably 650 to 1200nm, more preferably 650 to 900 nm. If the maximum absorption wavelength (λ max) of the coating film is 1200nm or more of the present invention, the effects of the present invention cannot be exhibited, and if it is less than 650nm, visible light is absorbed, which is not preferable.

In the thermally reactive composition of the present invention, the content of the cyanine compound (α) is 0.01 to 10 parts by mass in total, based on 100 parts by mass of the solid content of the resin (β) described later, in terms of one or more of the cyanine compounds (α). If the content of the cyanine compound (α) is less than 0.01 parts by mass, a sufficient infrared shielding function may not be obtained in the cured product of the present invention, and if it is more than 10 parts by mass, the cyanine compound (α) may be precipitated in the thermally reactive composition.

< resin (. beta.) >

As the resin (β), any conventionally used resin may be used without particular limitation as long as it has an ethylenically unsaturated bond and a hydrophilic group in one molecule.

Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group, and salts thereof, and the hydroxyl group and the carboxyl group are preferable because they can make the resin (β) highly soluble in alkali.

The hydrophilic group in the resin (. beta.) preferably has a functional group equivalent (mass of the resin containing 1 equivalent of the hydrophilic group) of 50 to 10000.

The resin (. beta.) preferably has a mass average molecular weight of 1000 to 500000.

Among the above resins (. beta.), resins 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-3) are preferable because of their high developability and heat resistance.

[ solution 14]

(in the formula, X¹Represents a hydrogen atom or a methyl group, Y¹Is a divalent binding radical, R¹Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, the alkyl group, the aryl group and the aralkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, the methylene group in the alkyl group and the aralkyl group may be substituted with a bonding group of-O-, -S-, -CO-, -COO-, -OCO-or-NH-, or a combination thereof, and R²、R³And R⁴Each independently is a hydrogen atom or a methyl group. )

As Y in the above general formula (I-2)¹Examples of the divalent binding group include those represented by the following general formula (1).

[ solution 15]

*-Z¹-X²-Z²-＊ (1)

(in the formula, X²represents-CR⁵R⁶-、-NR⁷A divalent chain hydrocarbon group having 1 to 35 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 35 carbon atoms, a divalent heterocyclic group having 2 to 35 carbon atoms, or any of the substituents represented by the following (1-1) to (1-3), R⁵And R⁶Z represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 30 carbon atoms¹And Z²Independently represent a direct bond, -O-, -S-, -SO₂-、-SO-、-NR⁷-or-PR⁸-，R⁷And R⁸Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms.

R is as defined above⁵、R⁶、R⁷And R⁸The alkyl group, aryl group and aralkyl group in (1) may be substituted with a halogen atom, a hydroxyl group or a nitro group, the above-mentioned R⁵、R⁶、R⁷And R⁸The methylene group in the alkyl group and the aralkyl group in (a) is sometimes replaced by an-O-, -S-, -CO-, -COO-, -OCO-or-NH-group. However, the number of carbon atoms of the group represented by the above general formula (1) is in the range of 1 to 35. )

[ solution 16]

(in the above formula, R⁷¹Represents a hydrogen atom, an optionally substituted phenyl group or a cycloalkyl group having 3 to 10 carbon atoms, R⁷²Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, the alkyl group, the alkoxy group and the alkenyl group may have a substituent, and f is an integer of 0 to 5. )

[ solution 17]

[ solution 18]

(in the above formula, R⁷³And R⁷⁴Independently represent an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an aryloxy group having 6 to 30 carbon atoms which may have a substituent, an arylthio group having 6 to 30 carbon atoms which may have a substituentA group, an arylalkenyl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, a heterocycle-containing group having 2 to 20 carbon atoms which may have a substituent, or a halogen atom, and the methylene group in the alkyl group and the arylalkyl group may be interrupted by an unsaturated bond, -O-or-S-, wherein R represents⁷³May be through adjacent R⁷³Form a ring with each other, 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, and the sum of the numbers of g and h is 2 to 4. )

As R in the above general formula (I-3)¹The aryl group having 6 to 30 carbon atoms or the aralkyl group having 7 to 30 carbon atoms (preferably 7 to 20 carbon atoms) is exemplified by the aryl groups and aralkyl groups exemplified in the description of the cyanine compound of the component (α).

Examples of the alkyl group having 1 to 20 carbon atoms include nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, heptadecyl, and octadecyl groups, in addition to the alkyl groups listed in the description of the cyanine compound (α).

In the above general formula (1), X is²Examples of the divalent chain hydrocarbon group having 1 to 35 carbon atoms include a group represented by Z-substituted hydrocarbon group such as methane, ethane, propane, isopropane, butane, sec-butyl-butane, tert-butyl-butane, isobutane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, isoheptane, tert-heptane, 1-methyloctane, isooctane, and tert-octane¹And Z²Substituted radicals.

Examples of the divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms include a group Z such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2, 4-dimethylcyclobutane and 4-methylcyclohexane¹And Z²Substituted groups, and the like.

Examples of the divalent aromatic hydrocarbon group having 6 to 35 carbon atoms include a group represented by Z such as phenylene, naphthylene and biphenyl¹And Z²Substituted groups, and the like.

The number of carbon atoms being divalentExamples of the heterocyclic group of 3 to 35 include a group represented by formula Z such as pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene and tetrahydrothiophene¹And Z²As the substituted group, a plurality of combinations of the above groups are also possible. The chain hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxyl group or a nitro group. Furthermore, methylene groups in the above-mentioned chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups may be replaced by-O-, -S-, -CO-, -COO-, -OCO-or-NH-groups.

As R in the above general formula (1)⁵、R⁶、R⁷And R⁸Examples of the alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 30 carbon atoms, or the aralkyl group having 7 to 30 carbon atoms include the alkyl group, the aryl group, and the aralkyl group listed in the description of the cyanine compound (α).

R is as defined above⁵、R⁶、R⁷And R⁸The alkyl group, aryl group and aralkyl group in (1) may be substituted with a halogen atom, a hydroxyl group or a nitro group, the above-mentioned R⁵、R⁶And R⁷The methylene group in the alkyl group and the aralkyl group in (1) may be interrupted by-O-, -S-, -CO-, -COO-, -OCO-, -NH-or a combination of plural of these groups, and the substitution position and the interruption position thereof are not particularly limited.

Among the substituents represented by the above (1-1), R is⁷¹Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, and cyclooctyl.

As R⁷²The alkyl group having 1 to 10 carbon atoms is represented by R¹And a group having a predetermined carbon number among the groups listed as the alkyl group having 1 to 40 carbon atoms.

As R⁷²Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxyAn alkyl group, an isoheptyloxy group, a tert-heptyloxy group, a n-octyloxy group, an isooctyloxy group, a tert-octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group and the like.

As R⁷²Examples of the substituent which the alkyl group, the alkoxy group and the alkenyl group may have include a halogen atom, a hydroxyl group and a nitro group.

In the group represented by the above (1-3), R is⁷³And R⁷⁴The alkyl group having 1 to 10 carbon atoms which may have a substituent(s) is represented by R¹And a group having a predetermined carbon number among the groups listed as the alkyl group having 1 to 20 carbon atoms.

As R⁷³And R⁷⁴The aryl group having 6 to 30 carbon atoms which may have a substituent(s) is represented by R¹¹And aryl groups having 6 to 30 carbon atoms represented by the formula (I).

As R⁷³And R⁷⁴The aryloxy group having 6 to 30 carbon atoms which may have a substituent(s) includes phenoxy, naphthoxy, 2-methylphenoxy, 3-methylphenoxy, 4-vinylphenoxy, 3-isopropylphenoxy, 4-butylphenoxy, 4-tert-butylphenoxy, 4-hexylphenoxy, 4-cyclohexylphenoxy, 4-octylphenoxy, 4- (2-ethylhexyl) phenoxy, 2, 3-dimethylphenoxy, 2, 4-dimethylphenoxy, 2, 5-dimethylphenoxy, 2, 6-dimethylphenoxy, 3, 4-dimethylphenoxy, 3, 5-dimethylphenoxy, 2, 4-di-tert-butylphenoxy, 2-methylphenoxy, 4-dimethylphenoxy, 2-isopropylphenoxy, 4-butylphenoxy, 4-tert-butylphenoxy, 4-butylphenoxy, 2, 5-di-tert-butylphenoxy group, 2, 6-di-tert-butylphenoxy group, 2, 4-di-tert-pentylphenoxy group, 2, 5-tert-pentylphenoxy group, 4-cyclohexylphenoxy group, 2,4, 5-trimethylphenoxy group, ferrocenyloxy group and the like.

As R⁷³And R⁷⁴The optionally substituted arylthio group having 6 to 30 carbon atoms includes a group obtained by substituting an oxygen atom of the optionally substituted aryloxy group having 6 to 30 carbon atoms with a sulfur atom.

As R⁷³And R⁷⁴May have a substituentExamples of the arylalkenyl group having 8 to 30 carbon atoms include groups obtained by substituting an oxygen atom of the aryloxy group having 6 to 30 carbon atoms, which may have a substituent, with an alkenyl group such as a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a1, 3-butadienyl group, a 2-pentenyl group, or a 2-octenyl group.

As R⁷³And R⁷⁴The aralkyl group having 7 to 30 carbon atoms is represented by R⁷¹And R⁷²And aralkyl groups having 7 to 30 carbon atoms.

As R⁷³And R⁷⁴Examples of the heterocyclic group having 2 to 20 carbon atoms which may have a substituent include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene and tetrahydrothiophene.

As R⁷³And R⁷⁴Examples of the substituent which the various groups described above may have include a halogen atom, a hydroxyl group and a nitro group.

The constituent ratio (molar ratio) of the units represented by the above general formulae (I-1) to (I-3) is (I-1): (I-2): (I-3) 0.1 to 0.65: 0.3-0.8: 0.001 to 2, and may be arranged in any of random copolymerization, block copolymerization, graft copolymerization, and the like.

Among the resins (. beta.) having units represented by the above general formulae (I-1), (I-2) and (I-3), the following resins are preferred.

R¹Preferably an alkyl group having 1 to 8 carbon atoms and an aralkyl group having 7 to 30 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

Y¹Is a divalent binding group, and X is a bond represented by the general formula (1)²Preferably an alkylene group having 1 to 15 carbon atoms, and more preferably an alkylene group having 7 to 15 carbon atoms and having a cycloalkylene group. The hydrogen atom in the above alkylene group may be substituted with a halogen atom, a hydroxyl group or a nitro atom, and the methylene group in the chain alkylene moiety in the alkylene group may be substituted with an-O-, -S-, -CO-, -COO-, -OCO-or-NH-group.

Z¹And Z²Direct bonding is preferred.

The acid value of the resin (. beta.) is preferably 10 to 200mg/KOH, more preferably 30 to 150 mg/KOH. If the acid value is less than 10mg/KOH, sufficient alkali developability may not be obtained, and if it exceeds 200mg/KOH, the production of the resin (. beta.) may be difficult.

Here, the acid value refers to a value obtained according to JIS K0050 and JIS K0211.

In the heat reactive composition of the present invention, the content of the resin (β) is preferably 30 to 99% by mass, and 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 (β) is less than 30% by mass, the cured product may have insufficient mechanical strength and cracks, and if it exceeds 99% by mass, the curing by exposure may be insufficient and sticky.

< thermal polymerization initiator (. gamma.)

As the thermal polymerization initiator (γ), conventionally known compounds can be used, and examples thereof include azo polymerization initiators such as 2,2 '-azobisisobutyronitrile, 2' -azobis (methyl isobutyrate), 2 '-azobis-2, 4-dimethylvaleronitrile, and 1, 1' -azobis (1-acetoxy-1-phenylethane); peroxide polymerization initiators such as benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. These may be used singly or in combination.

Among the thermal polymerization initiators (γ), azo polymerization initiators are preferred, and azodicarbonyl compounds are more preferred, from the viewpoint of heat resistance. The azo-bis-based compound is preferably a compound represented by the following general formula (a) from the viewpoint of easy industrial availability.

[ solution 18A ]

(in the formula, R₁₀₁A branched or straight-chain alkyl group having 1 to 10 carbon atoms which may have a substituent, R₁₀₂A 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 a methylene group in the alkyl group may be replaced by-O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, or a carbon-carbon double bond, and R bonded to the same carbon atom₁₀₁And R₁₀₂Or may be connected to each other to form a ring. X₁₀₁Is cyano, -CONR₁₀₃R₁₀₄、-COOR₁₀₅、-C＝N-R₁₀₆Or a branched or straight-chain alkyl group having 1 to 10 carbon atoms which may have a substituent, R₁₀₃、R₁₀₄、R₁₀₅And R₁₀₆Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

[18B]

(in the formula, R₁₁₁、R₁₁₂And R₁₁₃Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, R₁₁₁、R₁₁₂Or may be connected to each other to form a ring, which represents a bonding portion. )

As R₁₀₁、R₁₀₂、X₁₀₁、R₁₀₃、R₁₀₄、R₁₀₅、R₁₀₆、R₁₁₁、R₁₁₂And R₁₁₃Examples of the alkyl group represented by the above-mentioned group R¹¹And the like, and those satisfying the above-specified number of carbon atoms among the alkyl groups represented by the above-mentioned groups.

As R₁₀₁And R₁₀₂The ring formed by connecting them to each other includes a cycloalkyl ring, and preferably a cycloalkyl ring having 3 to 8 carbon atoms.

As R₁₁₁、R₁₁₂Examples of the ring formed by linking to each other include an imidazole ring.

As R₁₀₁、R₁₀₂、X₁₀₁、R₁₁₁、R₁₁₂And R₁₁₃Examples of the substituent in the case where the alkyl group has a substituent include an alkoxy group having 1 to 4 carbon atoms, a carboxyl group and a hydroxyl group.

In the heat reactive composition of the present invention, the content of the heat polymerization initiator (γ) is preferably 0.1 to 30% by mass, and particularly preferably 0.5 to 10% by mass, in the solid content of the heat reactive composition of the present invention. If the content of the thermal polymerization initiator (γ) is less than 0.1% by mass, sufficient heat resistance may not be obtained, and if it exceeds 30% by mass, the thermal polymerization initiator (γ) may precipitate in the thermally reactive composition.

< monomer having unsaturated bond (ω) >

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 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, and mixtures thereof, Bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z diglycidyl ether (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like. Among the above compounds, monomers having a plurality of unsaturated bonds are preferable because they can improve infrared shielding performance and heat resistance.

< solvent (. sigma.)

The heat-reactive composition of the present invention may further contain a solvent (σ). The solvent is usually a solvent capable of dissolving or dispersing the above components (the cyanine compound (α) and the like) as required, and examples thereof include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (texanol); cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, pentanol, diacetone alcohol, etc.; ether ester solvents such as 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, 1-tert-butyl-2-propanol, 3-methoxybutyl acetate, and cyclohexanol acetate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene and pinene; paraffinic solvents such as mineral spirits, SWAZOL #310(Cosmo Songshan oil Co., Ltd.), SOLVESSO #100(Exxon chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1, 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, and the like, and 1 kind of these solvents may be used, or a mixed solvent of 2 or more kinds may be used. Among them, ketones, ether ester solvents, and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because they provide a thermally reactive composition having good compatibility between the resin (β) and the thermal polymerization initiator (γ).

In the heat-reactive composition of the present invention, the solvent (σ) is preferably used in an amount such that the concentration of the composition other than the solvent (σ) is 5 to 30% by mass. When the concentration of the composition other than the solvent (σ) is less than 5% by mass, the film thickness may be difficult to increase, or the desired wavelength light may not be sufficiently absorbed, and when it exceeds 30% by mass, the storage stability of the composition may be reduced due to precipitation of the composition, or the handling property may be reduced due to an increase in viscosity.

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, silicon oxide, and aluminum oxide; the inorganic filler is selected from the group consisting of layered clay minerals, milori blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, and the like, and among them, titanium oxide, silica, layered clay minerals, 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, per 100 parts by mass of the resin (β), and 1 or 2 or more of these inorganic compounds may be used.

The inorganic compound can be used as, for example, a filler, an antireflection agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength improver, a specific wavelength absorber, an ink repellent, 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 dispersant is not particularly limited as long as it can disperse or stabilize the pigment and/or the inorganic compound, and a commercially available dispersant, for example, a BYK series manufactured by BYK-Chemie, etc., may be used, and among them, a polymer dispersant composed of polyester, polyether, or polyurethane having a basic functional group, and a dispersant having a functional group having a nitrogen atom as a basic functional group and a nitrogen atom as an amine and/or a quaternary ammonium salt thereof and having an amine value of 1 to 100mgKOH/g may be preferably used.

Further, in the heat-reactive composition of the present invention, a heat polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine, or the like; a plasticizer; an adhesion promoter; a filler; defoaming agents; leveling agent; a surface conditioner; an antioxidant; an ultraviolet absorber; a dispersing aid; an anti-agglomeration agent; a catalyst; a curing accelerator; a crosslinking agent; thickeners and the like.

In the heat-reactive composition of the present invention, the content of any component other than the cyanine compound (α), the resin (β), and the thermal polymerization initiator (γ) (excluding the monomer (ω) having an unsaturated bond and the solvent (σ)) may be appropriately selected depending on the purpose of use thereof, and is not particularly limited, but it is preferable that the total amount is set to 50 parts by mass or less with respect to 100 parts by mass of the resin (β).

In the heat-reactive composition of the present invention, the characteristics of the cured product formed from the heat-reactive composition of the present invention can be improved by using another organic polymer together with the resin (β). Examples of the organic polymer include polystyrene, polymethyl methacrylate, a methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, a styrene- (meth) acrylic acid copolymer, a (meth) acrylic acid-methyl methacrylate copolymer, an ethylene-vinyl chloride copolymer, an ethylene-vinyl copolymer, a polyvinyl chloride resin, an ABS resin, nylon 6, nylon 66, nylon 12, a polyurethane resin, polycarbonate polyvinyl butyral, a cellulose ester, polyacrylamide, a saturated polyester, a phenol resin, a phenoxy resin, a polyamideimide resin, a polyamic acid resin, an epoxy resin, and the like, and among them, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and an epoxy resin are preferable.

When another organic polymer is used, the amount thereof is preferably 10 to 500 parts by mass based on 100 parts by mass of the resin (. beta.).

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

As the chain transfer agent or sensitizer, a compound containing a sulfur atom is generally used. Examples thereof include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptobutanoic acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [ N- (2-mercaptoethyl) carbamoyl ] propionic acid, 3- [ N- (2-mercaptoethyl) amino ] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, thiosalicylic acid, 2-mercaptopropionic acid, and the like, Mercapto compounds such as mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-hydroxypyridine, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), disulfides obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, iodoalkyl compounds such as 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, and the like, Aliphatic polyfunctional thiol compounds such as butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trithiopropionate, the following compounds C1, tris (2-hydroxyethyl) trimercaptopropionate isocyanurate, and KARENZ MT BD1, PE1, NR1, manufactured by SHOWA DENKO K.K.K..

[ solution 19]

Compound No. C1

As the surfactant, fluorine-containing surfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali metal salts, alkylsulfonates, and alkylsulfates; cationic surfactants such as higher amine halides and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; an amphoteric surfactant; surfactants such as silicone surfactants may also be used in combination.

As the silane coupling agent, for example, silane coupling agents manufactured by shin-Etsu chemical Co., Ltd can be used, and among them, silane coupling agents having an isocyanate group, a methacryloyl group, and an epoxy group such as KBE-9007, KBM-502, and KBE-403 can be preferably used.

Examples of the melamine compound include active methylol groups (CH) in nitrogen compounds such as (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, and (poly) methylolurea₂OH groups) are etherified with alkyl groups. Among them, 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. The methylol group not etherified with an alkyl group may be self-condensed in one molecule or may be condensed between two molecules, and as a result, an oligomer component is formed. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, or the like can be used. Among them, melamine after alkyl etherification, such as hexamethoxymethylmelamine and hexabutoxymethylmelamine, is preferable.

When the heat reactive composition of the present invention is in a solid state without a solvent, it can be dissolved or dispersed in a solvent and then applied to a support substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, plastic, or the like by a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, a slit coater, a dip coater, various printing, dipping, or the like. Further, the transfer agent may be temporarily applied to a support substrate such as a film and then transferred to another support substrate, and the application method is not limited.

The heat-reactive composition of the present invention is cured under a heating condition of 70 to 250 ℃ for 1 to 100 minutes. The pre-baking may be followed by pressurization and then by post-baking, or the baking may be carried out at different temperatures in several stages.

The heating conditions vary depending on the type and mixing ratio of each component, and for example, the heating is carried out at 70 to 180 ℃ for 5 to 15 minutes in an oven or 1 to 5 minutes in a hot plate. Then, in order to cure the coating film, the cured film can be obtained by heat treatment for 30 to 90 minutes in an oven or 5 to 30 minutes in a hot plate at 100 to 250 ℃, preferably 180 to 250 ℃, and more preferably 200 to 250 ℃.

The heat-reactive composition (or a cured product thereof) of the present invention can be used for heat-reactive coatings or varnishes, heat-reactive adhesives, color filters in color display liquid crystal display panels such as printed circuit boards or color televisions, PC monitors, personal digital assistants, digital cameras, and the like, color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, stereolithography resins, gel coats, photoresists for electronic engineering, plating resists, etching resists, both liquid and dry films, solder resists, resists for forming structures in the manufacturing processes of color filters for various display applications or plasma display panels, electroluminescent display devices, and LCDs, compositions for sealing electric or electronic parts, and the like, The use thereof is not particularly limited in various applications such as a solder resist, a magnetic recording material, a micromachine component, a waveguide, an optical switch, a plating mask, an etching mask, a color test system, a glass fiber cable coating, a stencil for screen printing, a material for producing a three-dimensional object by stereolithography, a material for hologram recording, an image recording material, a fine circuit, a decoloring material for an image recording material using microcapsules, a photoresist material for a printed wiring board, a photoresist material for a UV and visible laser direct image system, a photoresist material for forming a dielectric layer in a sequential lamination of a printed wiring board, or a protective film.

The heat-reactive composition of the present invention is used for the purpose of shielding a specific infrared ray, 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 explained.

In the wavelength cut filter of the present invention, the coating layer (B) obtained from the heat reactive composition of the present invention is provided on one surface of the glass substrate (a), and the infrared ray reflective film (C) is provided on the other surface of the glass substrate (a). The coating layer (B) and the infrared reflection film (C) are laminated on the respective surfaces of the glass substrate (a). As shown in fig. 1, the side having the coating layer (B) obtained from the heat reactive composition of the present invention may be the light incident side, and as shown in fig. 2, the side having the infrared ray reflective film (C) may be the light incident side. Hereinafter, each layer will be described in order.

< glass substrate (A) >

The glass substrate (a) used in the wavelength cut filter of the present invention may be suitably selected from glass materials transparent in the visible region, and soda lime glass, white plate glass, borosilicate glass, tempered glass, quartz glass, phosphate glass, and the like may be used, and among these, soda lime glass is inexpensive and easily available, and is preferred, and white plate glass, borosilicate glass, and tempered glass are easily available, have high hardness, and are excellent in processability.

Further, if the coating layer (B) is formed by applying the coating liquid composed of the heat-reactive composition of the present invention after the glass substrate (a) is subjected to pretreatment such as silane coupling agent, the adhesion of the coating layer (B) containing the dye after the coating liquid is dried to the glass substrate is improved.

Examples of the silane coupling agent include epoxy-functional alkoxysilanes such as γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropylmethyldiethoxysilane, and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, amino-functional alkoxysilanes such as N- β (aminoethyl) - γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, and N-phenyl- γ -aminopropyltrimethoxysilane, and mercapto-functional alkoxysilanes such as γ -mercaptopropyltrimethoxysilane.

Further, a primer layer may be provided between the glass substrate (a) and the coating layer (B). The bottom layer was obtained as follows: an aggregate of metal oxide fine particles having an average secondary particle diameter of 20 to 250nm, which is obtained by aggregating primary particles having an average primary particle diameter of 5 to 100nm, is dispersed in a solvent as described below to obtain a coating liquid, and the coating liquid is applied by a coating method as described below to obtain a primer layer having a thickness of 30 to 1000 nm. The aggregate of the metal oxide fine particles is preferably 0.1 to 50% by mass based on the total amount of the coating liquid.

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

In the present invention, since the substrate is a glass plate, the substrate can be directly coated and dried and then cut, and the structure and process are simplified. Further, since the substrate is a glass plate, the heat resistance (soft melt resistance at 260 ℃) is higher than that of plastic.

< 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 a dye is preferably 1 to 200. mu.m, since a uniform film can be obtained and the film can be advantageously made thin. If the particle diameter is less than 1 μm, the function cannot be sufficiently exhibited, and if the particle diameter exceeds 200 μm, a solvent may remain during coating.

< Infrared reflective film (C) >

The infrared reflection film (C) used in the wavelength cut filter of the present invention has a function of cutting light in a wavelength region of 700 to 1200nm, and is formed of a dielectric multilayer film in which low refractive index layers and high refractive index layers are alternately laminated.

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

As the material constituting the high refractive index layer, a material having a refractive index of 1.7 to 2.5 can be used, and examples thereof include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc sulfide, indium oxide, and the like, and further include materials containing these as main components and a small amount of titanium oxide, tin oxide, cerium oxide, and the like.

The method of laminating the low refractive index layer and the high refractive index layer is not particularly limited as long as the dielectric multilayer film obtained by laminating the layers can be formed, and examples thereof include a method of forming a dielectric multilayer film by alternately laminating a low refractive index layer and a high refractive index layer on a glass substrate by using a CVD method, a sputtering method, a vacuum deposition method, and the like. Alternatively, a dielectric multilayer film may be formed in advance and bonded to a glass substrate with an adhesive.

The number of layers is preferably 10 to 80, and 25 to 50, from the viewpoint of process and strength.

The thicknesses of the low refractive index layer and the high refractive index layer are 1/10-1/2 of the wavelength lambda (nm) of the light to be intercepted. If the thickness is less than 0.1 λ or more than 0.5 λ, the product (nd) of the refractive index (n) and the physical film thickness (d) is greatly different from the optical film thickness expressed by a multiple of λ/4, and hence there is a possibility that the light blocking/transmission of a specific wavelength cannot be performed.

As the infrared reflecting film (C), in addition to the dielectric multilayer film, a film using an organic material, such as a film containing a dye having a maximum absorption wavelength of 700 to 1100nm, a film in which a polymer is laminated, or a film formed by coating cholesteric liquid crystal, can be used.

The wavelength cut filter of the present invention preferably has a transmittance satisfying the following (i) to (iii). The transmittance was measured using an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by Nippon spectral Co., Ltd.

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

(ii) The average value of the transmittance measured from the vertical direction of the wavelength cut filter within the wavelength range of 800-1000 nm is 5% or less.

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

In the wavelength cut filter, if the average value of the transmittance in the wavelength range of 430 to 580nm of the above (i) is less than 75%, light in the visible light region hardly transmits. The average value of the transmittance in the wavelength range of 430 to 580nm of (i) is more preferably 80% or more. If the average value of the transmittance at the wavelength of 800 to 1000nm in the above (ii) exceeds 5%, the light in the infrared region is hardly cut off, and therefore, it may be difficult to correct the sensitivity so as to be close to the visibility of human. (ii) The average value of the transmittance at a wavelength of 800 to 1000nm is more preferably 1% or less.

Further, if the absolute value of the difference between Ya and Yb in (iii) above exceeds 30nm, the dependence on the incident angle of light becomes high, and the characteristics of the wavelength cut filter change with the change in the incident angle of light, so that there is a possibility that the color changes in the center and the periphery of the screen. (iii) The absolute value of the difference between Ya and Yb of (2) is more preferably 5nm or less, and still more preferably 3nm or less.

Specific applications of the wavelength cut filter of the present invention include a heat ray cut filter attached to a window glass of an automobile or a building; visibility correction for solid-state imaging elements such as CCDs and CMOSs in solid-state imaging devices such as digital cameras, digital video cameras, surveillance cameras, in-vehicle cameras, network cameras, and mobile phone cameras; an automatic exposure meter; a display device such as a plasma display, and the like.

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

The solid-state imaging device of the present invention is configured in the same manner as the conventional solid-state imaging device except that the wavelength cut filter of the present invention is provided on the front surface of the imaging element. The wavelength cut filter 1 of the present invention may be fixed to a portion other than the solid-state imaging element on the light incident side of the solid-state imaging element 2 as shown in fig. 5 and 6, or may be directly fixed to the front surface of the solid-state imaging element 2 as shown in fig. 3 and 4.

The solid-state imaging device of the present invention may further include an optical low-pass filter, an antireflection filter, a color filter, and the like as necessary, and the order of laminating them is not particularly limited.

As shown in fig. 3 and 4, a camera module, which is one of the solid-state imaging devices according to the present invention, will be specifically described below in which the wavelength cut filter 1 according to the present invention is laminated on the solid-state imaging element 2 on the light incident side.

Fig. 3 and 4 are sectional views showing one embodiment of the configuration of a camera module which is one of the solid-state imaging devices according to the present invention. The camera module has: a solid-state imaging element 2 formed on a semiconductor substrate in a rectangular shape in a plan view; and a wavelength cut filter 1 (fig. 3) in which a coating layer (B) containing a dye, a glass substrate (a), and an infrared reflection film (C) are laminated in this order from the light incident side on the opposite side of the light receiving part 3 of the solid-state imaging element 2, or a wavelength cut filter 1 (fig. 4) in which an infrared reflection film (C), a glass substrate (a), and a coating layer (B) containing a dye are laminated in this order, and the solid-state imaging element 2 and the wavelength cut filter 1 are joined by an adhesive 4 formed on one surface of the solid-state imaging element 2 except for the light receiving part 3. A camera module as a solid-state imaging device takes in light from the outside through a wavelength cut filter 1 and receives the light through a light receiving element arranged in a light receiving unit 3 of a solid-state imaging element 2.

As shown in fig. 5 and 6, a camera module, which is one of the solid-state imaging devices according to the present invention, will be specifically described below in which the wavelength cut filter 1 according to the present invention is fixed to a portion other than the solid-state imaging device 2 on the light incident side.

Fig. 5 and 6 are sectional views showing one embodiment of the configuration of a camera module which is one of the solid-state imaging devices according to the present invention. The camera module has: a solid-state imaging element 2 formed on a semiconductor substrate in a rectangular shape in a plan view; and a wavelength cut filter 1 (fig. 5) in which a coating layer (B) containing a dye, a glass substrate (a), and an infrared reflection film (C) are laminated in this order from the light incident side on the opposite side of the light receiving part 3 of the solid-state imaging element 2, or a wavelength cut filter 1 (fig. 6) in which an infrared reflection film (C), a glass substrate (a), and a coating layer (B) containing a dye are laminated in this order is formed on one surface of the solid-state imaging element 2 except for the light receiving part 3. A camera module as a solid-state imaging device takes in light from the outside through a wavelength cut filter 1 and receives the light through a light receiving element arranged in a light receiving unit 3 of a solid-state imaging element 2.

As the adhesive 4, a UV curable adhesive such as an acrylic resin or an epoxy resin or a thermosetting resin is used, and after the adhesive 4 is uniformly applied, the adhesive is patterned by a known photolithography technique as needed, and is thermally cured to be bonded. In the bonding, vacuum pressurization may be performed after bonding in a vacuum environment.

The mounting board 8 is a hard board using a glass epoxy board, a ceramic board, or the like, and is provided with a control circuit for controlling the solid-state imaging element 2.

The solid-state imaging element 2 is disposed on the mounting substrate 8, and the adhesive 4 is applied in advance to the mounting substrate 8 at a position where the lens holder 7 is fixed.

The lens cover 6 is for protecting the lens 5. The lens holder 7 holds the lens 5, and includes a box-shaped base portion 7a attached to the mounting board 8 and covering the solid-state imaging element 2, and a cylindrical barrel portion 7b holding the lens 5.

Then, the lens holder 7 is disposed on the mounting board 8 so that the lower end surface of the lens holder 7 comes into contact with the applied adhesive 4, and the position of the lens holder 7 is adjusted so that the distance between the light receiving unit 3 of the solid-state imaging element 2 and the lens 5 in the lens holder 7 matches the focal distance of the lens 5.

After the position of the lens holder 7 is adjusted, the adhesive 4 is irradiated with ultraviolet rays to cure the adhesive 4, thereby manufacturing a camera module.

The entire mounting substrate 8 to which the lens holder 7 is fixed may be heated at about 85 ℃ to be thermally cured, thereby sufficiently curing the adhesive 4.

In the method for manufacturing a camera module, since the step of heating the entire mounting substrate 8 is included after the step of irradiating ultraviolet rays, it is necessary to use materials having high heat resistance for each of the lens holder 7, the lens 5, and the wavelength cut filter 1. Specifically, in addition to the heating for thermosetting of the adhesive 4 as described above, the solder material disposed on a plurality of places on the lower surface of the mounting board 8 is preferably formed of a material having soft-melt resistance because the solder material is subjected to a heat-melting treatment at about 260 ℃.

Examples

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.

Production example 1 preparation of resin (. beta.) 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), 4 parts by mass of azobisisobutyronitrile was added to the solution as a radical polymerization initiator, and the mixture was stirred at 80 ℃ for 3 hours. Then, 10 parts by mass of CELLOXIDE 2021P (alicyclic epoxy resin manufactured by Daicel chemical Co., Ltd.) modified with acrylic acid was added thereto, and the mixture was stirred at 120 ℃ for 3 hours to obtain resin (. beta.) No. 1.

The resin (. beta.) No.1 is the following resin (. beta.): in the above general formula (I), X¹Is a hydrogen atom or a methyl group, Y¹Is a divalent binding group (X) represented by the general formula (1)²Is a group represented by the following formula (n), Z¹And Z²Is a direct bond), R¹Is an alkyl group having 1 to 8 carbon atoms, R²～R³Is a hydrogen atom, R⁴Is methyl.

[ solution 20]

Production example 2 preparation of resin (. beta.) 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, 4 parts by mass of azobisisobutyronitrile was added as a radical polymerization initiator, and stirred at 80 ℃ for 3 hours. Then, 20 parts by mass of acrylic acid was added thereto, and the mixture was stirred at 120 ℃ for 3 hours to obtain resin (. beta.) No. 2.

Production example 3 preparation of resin (. beta.) No.3

50 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), 1 part by mass of 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane was added as a radical polymerization initiator, and the mixture was stirred at 140 ℃ for 2 hours. Then, 20 parts by mass of acrylic acid was added thereto, and the mixture was stirred at 120 ℃ for 3 hours to obtain resin (. beta.) No. 3.

Production example 4 preparation of resin (. beta.) 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 10 parts by mass of azobisisobutyronitrile was used as a radical polymerization initiator, and the mixture was stirred at 80 ℃ for 3 hours. Then, 20 parts by mass of acrylic acid was added thereto, and the mixture was stirred at 120 ℃ for 3 hours to obtain resin (. beta.) No. 4.

Production example 5 preparation of resin (. beta.) 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 5 parts by mass of azobisisobutyronitrile was added as a radical polymerization initiator, followed by stirring at 80 ℃ for 3 hours. Then, 20 parts by mass of acrylic acid was added thereto, and the mixture was stirred at 120 ℃ for 3 hours. Then, 5 parts by mass of tetrahydrophthalic anhydride was added thereto, and the mixture was stirred at 120 ℃ for 3 hours to obtain resin (. beta.) No. 5.

[ examples 1-1 to 1-10 and comparative examples 1-1 to 1-5] preparation of Heat-reactive compositions Nos. 1 to 11 and comparative compositions Nos. 1 to 5

< step 1> preparation of dye solutions No.1 to No.10 and comparative dye solutions No.1 to No.5

A solvent (sigma) was added to the cyanine compounds (alpha) shown in [ Table 1] to [ Table 3] as the component (A), and the cyanine compounds were dissolved by stirring to obtain dye solutions Nos. 1 to 10 and comparative dye solutions Nos. 1 to 5.

< step 2> preparation of Heat-reactive compositions No.1 to No.10 and comparative compositions No.1 to No.5

According to the compounding ratios of [ Table 1] to [ Table 3], a resin (. beta.), a polymerization initiator (. gamma.) (or (. gamma.')) and a monomer (. omega.) having an unsaturated bond and a solvent (. sigma.) were added to the above-mentioned dye solutions Nos. 1 to 10 and comparative dye solutions Nos. 1 to 5 and stirred to prepare heat-reactive compositions Nos. 1 to 10 and comparative compositions Nos. 1 to 5.

TABLE 1

A-1: hexafluorophosphate salt of Compound No.76

A-2: hexafluorophosphate salt of Compound No.100

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

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

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

B-1: resin (. beta.) No.1 obtained in production example 1

B-2: ACA Z251 (acrylic acid acrylate manufactured by Daicel-Allnex Co., Ltd.)

B-3: ACA Z250 (acrylic acid acrylate manufactured by Daicel-Allnex Co., Ltd.)

B-4: ACA 200M (acrylated acrylate manufactured by Daicel-Allnex Co., Ltd.)

B-5: SPC-1000 (acrylic resin manufactured by SHOWA AND ELECTRIC WORKING CO.)

B-6: SPC-3000 (acrylic resin manufactured by SHOWA AND ELECTRIC WORKING CO. Co., Ltd.)

B-7: resin (. beta.) No.2 obtained in production example 2

B-8: resin (. beta.) No.3 obtained in production example 3

B-9: resin (. beta.) No.4 obtained in production example 4

B-10: resin (. beta.) No.5 obtained in production example 5

C-1: v-60 (oil-soluble azo polymerization initiator manufactured by Wako pure chemical industries, Ltd.)

C-2: v-70 (oil-soluble azo polymerization initiator manufactured by Wako pure chemical industries, Ltd.)

C-3: v-65 (oil-soluble azo polymerization initiator manufactured by Wako pure chemical industries, Ltd.)

C-4: v-59 (oil-soluble azo polymerization initiator manufactured by Wako pure chemical industries, Ltd.)

C-5: v-40 (oil-soluble azo polymerization initiator manufactured by Wako pure chemical industries, Ltd.)

C-6: VAm-110 (oil-soluble azo polymerization initiator manufactured by Wako pure chemical industries, Ltd.)

C' -1: irg-907 (photopolymerization initiator manufactured by BASF Co., Ltd.)

C' -2: SP-246 (photopolymerization initiator manufactured by ADEKA Co., Ltd.)

C' -3: OXE-01 (photopolymerization initiator manufactured by BASF Co., Ltd.)

C' -4: OXE-02 (photopolymerization initiator manufactured by BASF Co., Ltd.)

D-1: aronix M450 (acrylic monomer manufactured by Toyo Synthesis Co., Ltd.)

D-2: aronix M315 (acrylic monomer manufactured by Toyo Synthesis Co., Ltd.)

E-1: cyclohexanone

E-2: diacetone alcohol

E-3: methyl ethyl ketone

TABLE 2

TABLE 3

[ evaluation examples 1-1 to 1-10 and comparative evaluation examples 1-1 to 1-5]

The heat-reactive compositions Nos. 1 to 10 obtained in examples 1-1 to 1-10 and the comparative compositions Nos. 1 to 5 obtained in comparative examples 1-1 to 1-5 were applied to a glass substrate at 410rpm × 7 seconds, respectively, and dried on a hot plate (90 ℃ C., 10 minutes). After drying, the coating film was cured by heating at 150 ℃ for 10 minutes on a hot plate. The cured coating film was heated at 150 ℃ for 1 hour to evaluate heat resistance. The evaluation was performed by calculating the transmittance change at the maximum absorption wavelength before and after heating. The transmittance change amount is obtained by the following equation.

(X-Y)/X100 (X is the transmittance at the maximum absorption wavelength before heating, Y is the transmittance at that wavelength measured after heating)

The above results are shown in Table 4.

TABLE 4

	Composition comprising a metal oxide and a metal oxide	Amount of change in transmittance (%)
			Evaluation examples 1-1	No.1	1.2
Evaluation examples 1 and 2	No.2	1.3
			Evaluation examples 1 to 3	No.3	0.9
Evaluation examples 1 to 4	No.4	1.2
			Evaluation examples 1 to 5	No.5	1.3
Evaluation examples 1 to 6	No.6	1.2
			Evaluation examples 1 to 7	No.7	1.2
Evaluation examples 1 to 8	No.8	1.0
			Evaluation examples 1 to 9	No.9	0.8
Evaluation examples 1 to 10	No.10	1.4
			Comparative evaluation example 1-1	Comparative No.1	6.8
Comparative evaluation examples 1 to 2	Comparative No.2	7.7
			Comparative evaluation examples 1 to 3	Comparative No.3	9.6
Comparative evaluation examples 1 to 4	Comparative No.4	10.4
			Comparative evaluation examples 1 to 5	Comparative No.5	-

(in Table 4, "-" indicates that the film was not uniformly formed and thus the evaluation was impossible.)

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

[ examples 2-1 to 2-10] production of wavelength cut filters Nos. 1 to 10

On one surface of a glass substrate (A) having a thickness of 100 μm, silicon dioxide (SiO) was alternately laminated by a vacuum deposition method₂) Layer and titanium oxide (TiO)₂) And an infrared-reflecting film (C) having a total number of layers of 30 and a thickness of about 3 μm.

On the surface of the obtained glass substrate (A) having the infrared reflective film (C) applied thereto, which was different from the surface of the infrared reflective film, heat-reactive compositions (coating liquids) Nos. 1 to 10 obtained in examples 1-1 to 1-10 were applied (film thickness: 10 μm) with a bar coater #30 and then dried at 100 ℃ for 10 minutes to prepare wavelength cut filters Nos. 1 to 10.

[ evaluation examples 2-1 to 2-10]

With respect to the wavelength cut filters nos. 1 to 10 of the present invention obtained in examples 2-1 to 2-10, absolute values of differences were obtained i) between the average value of the transmittances measured from the vertical direction of the wavelength cut filter in the wavelength range of 430 to 580nm, ii) between the average value of the transmittances measured from the vertical direction of the wavelength cut filter in the wavelength range of 800 to 1000nm, and iii) between the value (Ya) of the wavelength at which the transmittance reaches 80% when measured from the vertical direction of the wavelength cut filter in the wavelength range of 560 to 800nm and the value (Yb) of the wavelength at which the transmittance reaches 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 ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by Nippon spectral Co., Ltd.

TABLE 5

From the results of table 5, it is clear that the wavelength cut filter of the present invention has a high transmittance at a wavelength of 430 to 580nm, a low transmittance at a wavelength of 800 to 1000nm, and a low incident angle dependence.

From the above results, it is understood that the wavelength cut filter of the present invention, which is characterized in that the coating layer (B) containing the dye is formed on one surface of the glass substrate (a) and the infrared ray reflective film (C) is provided on the other surface of the glass substrate (a), has 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

1. A thermally reactive composition comprising: at least one (alpha) of cyanine compounds, a resin (beta) having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (gamma),

the resin (. beta.) having at least an ethylenically unsaturated bond and a hydrophilic group contains 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-3),

in the formula, X¹Represents a hydrogen atom or a methyl group, Y¹Is a divalent binding radical, R¹Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, the alkyl group, the aryl group and the aralkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, the methylene group in the alkyl group and the aralkyl group may be substituted with a bonding group of-O-, -S-, -CO-, -COO-, -OCO-or-NH-, or a combination thereof, and R is a halogen atom, a hydroxyl group or a nitro group²、R³And R⁴Each independently is a hydrogen atom or a methyl group,

the thermal polymerization initiator (γ) is a thermal azo polymerization initiator,

the content of the resin (beta) having at least an ethylenically unsaturated bond and a hydrophilic group is 30 to 99% by mass in the solid content of the heat reactive composition,

at least one (alpha) of the cyanine compounds is contained in an amount of 0.01 to 10.0 parts by mass in total per 100 parts by mass of a solid content of the resin (beta) having at least an ethylenically unsaturated bond and a hydrophilic group,

the content of the thermal polymerization initiator (γ) is 0.1 to 30% by mass in the solid content of the thermal reactive composition.

2. The thermally reactive composition of claim 1, wherein Y is¹Is a structure represented by the following general formula (1),

＊-Z¹-X²-Z²-＊ (1)

in the general formula (1), X²Represents an alkylene group having 1 to 15 carbon atoms, wherein hydrogen atoms in the alkylene group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and methylene groups in chain alkylene moieties in the alkylene group may be substituted with-O-, -S-, -CO-, -COO-, -OCO-or-NH-,

Z¹and Z²Independently represent a direct bond, -O-, -S-, -SO₂-、-SO-、-NR⁷-or-PR⁸-，R⁷And R⁸Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms,

the R is⁷And R⁸The alkyl group, the aryl group and the aralkyl group in (1) may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the R group⁷And R⁸The methylene group in the alkyl group and the aralkyl group in (1) may be replaced by an-O-, -S-, -CO-, -COO-, -OCO-or-NH-group, and the number of carbon atoms in the group represented by the general formula (1) is in the range of 1 to 35.

3. A wavelength cut filter characterized by having a coating layer (B) obtained from the heat-reactive composition according to claim 1 or 2 on one surface of a glass substrate (A) and having an infrared ray reflective film (C) on the other surface of the glass substrate (A).

4. The wavelength cut filter according to claim 3, wherein the transmittance of the wavelength cut filter satisfies the following (i) to (iii):

(i) an average value of transmittance measured from the direction perpendicular to the wavelength cut filter is 75% or more in the wavelength range of 430 to 580nm,

(ii) an average value of transmittance measured from the direction perpendicular to the wavelength cut filter is 5% or less at a wavelength of 800 to 1000nm,

(iii) in the wavelength range of 560-800 nm, the absolute value of the difference between the value (Ya) of the wavelength at which the transmittance of the wavelength cut filter is 80% when measured from the vertical direction and the value (Yb) of the wavelength at which the transmittance of the wavelength cut filter is 80% when measured from an angle of 35 DEG with respect to the vertical direction is 30nm or less.

5. A solid-state imaging device comprising the wavelength cut filter according to claim 3 or 4.

6. A camera module comprising the wavelength cut filter according to claim 3 or 4.