JP6908522B2 - Thermoreactive composition - Google Patents

Description

The present invention comprises 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. Regarding.

The sensitivity of a solid-state image sensor (CCD, C-MOS, etc.) used in a digital still camera, a video camera, a camera for a mobile phone, or the like ranges from the ultraviolet region to the infrared region of the wavelength of light. On the other hand, human luminosity factor is only in the visible region of the wavelength of light. Therefore, by providing an infrared cut filter between the image pickup lens and the solid-state image sensor, the sensitivity of the solid-state image sensor is corrected so as to approach the human visual sensitivity.

The infrared cut filter is a reflective filter in which layers containing substances having no absorption characteristics are combined and laminated in multiple layers to utilize the difference in refractive index, or a light absorber is contained in a transparent substrate or combined. Absorption type filters are known.

In particular, in the absorption type filter, there is a problem that the light absorber deteriorates due to heat treatment at the time of manufacture and the infrared ray blocking ability is lowered.
Patent Documents 1 and 2 describe thermoreactive compositions containing a thermal polymerization initiator. Further, 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.

Japanese Unexamined Patent Publication No. 2007-256865 US20100051883A1 Japanese Unexamined Patent Publication No. 2013-173848

However, the compositions described in Patent Documents 1 to 3 have not been sufficient in terms of heat resistance.
Therefore, an object of the present invention is to provide a heat-reactive composition having excellent heat resistance. Another object of the present invention is to provide a wavelength cut filter using the above heat reactive composition.

As a result of diligent studies, the present inventor has made a wavelength cut filter 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. It was found that it is suitable for a wavelength cut filter used in a solid-state imaging device or the like without lowering the heat resistance of ethylene, and the present invention has been reached.

The present invention provides a heat-reactive composition containing at least one of cyanine compounds (α), at least a resin having an ethylenically unsaturated bond and a hydrophilic group (β), and a thermal polymerization initiator (γ). be.

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

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 thermopolymerization initiator has excellent heat resistance. Further, the cured product is suitable for a wavelength cut filter.

It is a schematic cross-sectional view which shows an example of the layer structure of the wavelength cut filter of this invention. It is a schematic cross-sectional view which shows another example of the layer structure of the wavelength cut filter of this invention. It is sectional drawing which shows one form of the structure of the camera module which is one of the solid-state image pickup apparatus of this invention. It is sectional drawing which shows another form of the structure of a camera module. It is sectional drawing which shows still another form of the structure of a camera module. It is sectional drawing which shows still another form of the structure of a camera module.

Hereinafter, the heat-reactive composition of the present invention will be described based on a preferred embodiment.

The thermally reactive composition of the present invention is a resin (β) having at least one kind of cyanine compound (α) (hereinafter, also referred to as a cyanine compound (α)), at least an ethylenically unsaturated bond and a hydrophilic group (hereinafter, a resin). (Also referred to as (β)), a thermal polymerization initiator (γ), and if necessary, a monomer (ω) having an unsaturated bond and a solvent (σ). Hereinafter, each component will be described in order.

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

（式中、環Ａ及び環Ａ’は、それぞれ独立に、ベンゼン環、ナフタレン環、フェナントレン環又はピリジン環を表し、
Ｒ¹¹及びＲ¹¹’は、それぞれ独立に、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、アミノ基、アミド基、メタロセニル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数１〜８のアルキル基を表し、
Ｘ¹¹及びＸ^11'は、それぞれ独立に、酸素原子、硫黄原子、セレン原子、−ＣＲ²³Ｒ²⁴−、炭素原子数３〜６のシクロアルカン−１，１−ジイル基又は−ＮＲ²⁵−を表し、
Ｒ ²³、Ｒ²⁴及びＲ²⁵は、それぞれ独立に、水素原子、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、アミノ基、アミド基、メタロセニル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数１〜８のアルキル基を表し、
Ｙ¹¹及びＹ^11'は、それぞれ独立に、水素原子、又は水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、アミノ基、アミド基若しくはメタロセニル基で置換されてもよい炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基若しくは炭素原子数１〜８のアルキル基を表し、
上記Ｒ¹¹、Ｒ¹¹’、Ｙ¹¹、Ｙ^11'、Ｒ ²³、Ｒ²⁴及びＲ²⁵におけるアリール基、アリールアルキル基及びアルキル基は、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、アミノ基、アミド基又はメタロセニル基で置換されている場合もあり、上記Ｒ¹¹、Ｒ¹¹’、Ｙ¹¹、Ｙ^11'、Ｒ ²³、Ｒ²⁴及びＲ²⁵におけるアリールアルキル基及びアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は炭素−炭素二重結合で置き換えられている場合もあり、
Ｑは、炭素原子数１〜９のメチン鎖を構成し、鎖中に環構造を含んでもよい連結基を表し、該メチン鎖中の水素原子は水酸基、ハロゲン原子、シアノ基、−ＮＲＲ’、アリール基、アリールアルキル基又はアルキル基で置換されていてもよく、該−ＮＲＲ’、アリール基、アリールアルキル基及びアルキル基は更に水酸基、ハロゲン原子、シアノ基又は−ＮＲＲ’で置換されていてもよく、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で中断されてもよく、
Ｒ及びＲ’は、アリール基、アリールアルキル基又はアルキル基を表し、
ｒ及びｒ’は、０又は環Ａ及び環Ａ’において置換可能な数を表し、
Ａｎ^q-はｑ価のアニオンを表し、ｑは１又は２を表し、ｐは電荷を中性に保つ係数を表す。）

(In the formula, ring A and ring A'independently represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring, respectively.
R ¹¹ and R ¹¹ 'are each independently, a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, carboxyl group, amino group, amido group, metallocenyl group, an aryl group having 6 to 30 carbon atoms, Represents 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 -, cycloalkane-1,1-diyl group or -NR ²⁵ 3 to 6 carbon atoms - a Represent,
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, carboxyl group, amino group, amido group, metallocenyl group, 6 carbon atoms Represents an aryl group of 30, 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 hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, carboxyl group, an amino group, carbon atoms which may be substituted by an amide group or a metallocenyl group Represents an aryl group having 6 to 30 atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.
The ^{aryl groups, arylalkyl groups and alkyl groups in R 11} , R ¹¹ ', Y ¹¹ , Y ^11' , R ²³ , R ²⁴ and R ²⁵ are hydroxyl groups, halogen atoms, nitro groups, cyano groups and -SO ₃ H. , carboxyl group, sometimes amino group is substituted with an amide group or metalocenyl group, the ^{R 11, R 11 ', Y} 11, Y 11', arylalkyl group and an alkyl in R ^23, R ²⁴ and R ²⁵ The methylene group in the group is -O-, -S-, -CO- _{, -COO-, -OCO-, -SO 2-} , -NH-, -CONH-, -NHCO-, -N = CH- or It may have been replaced with a carbon-carbon double bond,
Q represents a linking group that constitutes 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 is a hydroxyl group, a halogen atom, a cyano group, -NRR', It may be substituted with an aryl group, an arylalkyl group or an alkyl group, and the -NRR', an aryl group, an arylalkyl group and an alkyl group may be further substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR'. Often, -O-, -S-, -CO-, _{-COO-, -OCO-, -SO 2-} , -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH- May be interrupted by
R and R'represent an aryl group, an arylalkyl group or an alkyl group.
r and r'represent 0 or a substitutable number in ring A and ring A'
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents the coefficient that keeps the charge neutral. )

The general formula R ¹¹ in (II), R ¹¹ 'and X ¹¹ and X ^11' in R ^23, R ²⁴ and halogen atoms and R ¹¹ represented by ^{R 25, R 11 'R 23} , R 24, R ^{Examples of the aryl group represented by 25} , Y ¹¹ , and Y ^11' , the arylalkyl group, and the halogen atom in which the alkyl group may be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The general formula R ¹¹ in (II), R ¹¹ 'and X ¹¹ and X ^11' R ²³ in, R ²⁴ and amino groups and R ¹¹ represented by ^{R 25, R 11 'R 23} , R 24, R ^The aryl group represented by 25, Y ¹¹ , Y ^11' , the arylalkyl group, and the amino group in which the alkyl group may be substituted include amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-. Ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, Lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N- Examples thereof include methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino and the like.
The general formula R ¹¹ in (II), R ¹¹ 'and X ¹¹ and X ^11' in R ^23, R ²⁴ and amide groups and R ¹¹ represented by ^{R 25, R 11 'R 23} , R 24, R ^25, Y ^11, Y ¹¹ represented by an aryl group ^', the aryl alkyl group, an amido group optionally substituted alkyl group, formamide, acetamide, ethylamide, isopropylamide, butylamide, octyl amide, nonylamide, decyl amide, Undecylamide, dodecylamide, hexadecylamide, octadecylamide, (2-ethylhexyl) amide, benzamide, trifluoroacetamide, pentafluorobenzamide, diformamide, diacetamide, diethylamide, diisopropylamide, dibutylamide, dioctylamide, dinonylamide, Examples thereof include didecylamide, diundecylamide, didodecylamide, di (2-ethylhexyl) amide, dibenzamide, ditrifluoroacetamide, dipentafluorobenzamide and the like.
The general formula R ¹¹ in (II), R ¹¹ 'and X ¹¹ and X ^11' in R ^23, R ²⁴ and metallocenyl groups and R ¹¹ represented by ^{R 25, R 11 'R 23} , R 24, R ^{Examples of the aryl group represented by 25} , Y ¹¹ , and Y ^11' , the arylalkyl group, and the metallocenyl group in which the alkyl group may be substituted include ferrosenyl, nickerosenyl, zirconosenyl, titanosenyl, hafnosenyl, and the like.
Represented by ^{R 11, R 11 ', Z} 11, Z 12, Z 13 and Y ¹¹ and Y ^11' and X ¹¹ and X ¹¹ 'in R ^23, R ²⁴ and R ²⁵ in the general formula (II) Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, and the like. 4-Butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 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, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di Examples thereof include −tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrosenyl and the like.
R ¹¹ in the general formula (II), R ¹¹ 'and Y ¹¹ and Y ^11' and X ¹¹ and X ¹¹ 'R ^23, aryl alkyl R ²⁴ and having 7 to 30 carbon atoms represented by R ²⁵ in Examples of the group include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrosenylmethyl, ferrosenylpropyl and the like.
As the alkyl group having 1 to 8 carbon atoms represented by R ^11, R ¹¹ and Y ^11, Y ^{11 'and} X ¹¹ and X ^11' in R ^23, R ²⁴ and R ²⁵ in the general formula (II) Methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1- Examples thereof include methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl and the like.
In the R ^11, R ¹¹ 'and Y ^11, Y ^11' and X ¹¹ and X ¹¹ 'R ^23, R ²⁴ and R ²⁵ in a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H group, Examples of the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms and the alkyl group having 1 to 20 carbon atoms which may be substituted with a carboxyl group, an amino group, an amide group or a metallocenyl group include aryl groups exemplified in the description, such as the R ^11, an aryl group, a hydrogen atom of the alkyl group and in these groups, a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H group, a carboxyl group, an amino group , Which are substituted with an amide group or a metallocenyl group, and the position and number of these substituents are not limited.
Further, a methylene group of said R ^11, R ¹¹ 'and Y ^11, Y ^11' and X ¹¹ and X ¹¹ arylalkyl group, and the alkyl group in R ^23, R ²⁴ and R ²⁵ 'in the, -O-, Replaced by -S-, -CO-, _{-COO-, -OCO-, -SO 2-} , -NH-, -CONH-, -NHCO-, -N = CH- or carbon-carbon double bonds If so, the number and position of these substitutions is arbitrary.
For example, examples of the group in which the alkyl group having 1 to 8 carbon atoms is replaced with a halogen atom include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, nonafluorobutyl and the like. Be,
Examples of the group in which the alkyl group having 1 to 8 carbon atoms is interrupted by −O− include methyloxy, ethyloxy, iso-propyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, and heptyl. Alkoxy groups such as oxy, octyloxy and 2-ethylhexyloxy, 2-methoxyethyl, 2- (2-methoxy) ethoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl, 3-methoxybutyl and the like. Alkoxyalkyl groups, etc.
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 chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, and difluoromethyloxy. , Trifluoromethyloxy, nonafluorobutyloxy and the like.

In the general formula (II), as cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X ¹¹ and X ¹¹ ', cyclopropane-1,1-diyl, cyclobutane-1, Examples thereof include 1-diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl, cyclohexane-1,1-diyl and the like. ..

The following (Q-1) to (Q-11) are examples of a linking group that constitutes a methine chain having 1 to 9 carbon atoms and may contain a ring structure in the chain, which is represented by Q in the general formula (II). ) Is preferable because it is easy to manufacture. The number of carbon atoms in a methine chain having 1 to 9 carbon atoms represents a linking group that may contain a ring structure in the methine chain and the chain, and a group that further substitutes the linking group (for example, R ^{14 to} R ¹⁹ below, It does not contain carbon atoms of Z') (for example, carbon atoms at both ends of the linking group (Q-1)).

（式中、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹及びＺ’は、各々独立に、水素原子、水酸基、ハロゲン原子、シアノ基、−ＮＲＲ’、アリール基、アリールアルキル基又はアルキル基を表し、該−ＮＲＲ’、アリール基、アリールアルキル基及びアルキル基は、水酸基、ハロゲン原子、シアノ基又は−ＮＲＲ’で置換されていてもよく、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で中断されていてもよく、
Ｒ及びＲ’は、アリール基、アリールアルキル基又はアルキル基を表す。）

(In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z'are independent of hydrogen atom, hydroxyl group, halogen atom, cyano group, -NRR', aryl group and aryl alkyl. Representing a group or alkyl group, the -NRR', aryl group, arylalkyl group and alkyl group may be substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR', and -O-, -S-,. It may be interrupted at -CO-, _{-COO-, -OCO-, -SO 2-} , -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH-.
R and R'represent an aryl group, an arylalkyl group or an alkyl group. )

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

^{Examples of the q-valent anion represented by pAn q-} in the general formula (II) include methanesulfonic anion, dodecylsulfonic acid anion, benzenesulfonic anion, toluenesulfonic anion, trifluoromethanesulfonic anion, and naphthalenesulfone. Acid anion, diphenylamine-4-sulfonic acid anion, 2-amino-4-methyl-5-chlorobenzene sulfonic acid anion, 2-amino-5-nitrobenzene sulfonic acid anion, naphthalenedisulfonic acid anion, naphthol sulfonic acid anion, bis (trifluo) Lomethanesulfonyl) imidate anion, JP-A-10-235999, JP-A-10-337959, JP-A-11-102088, JP-A-2000-108510, JP-A-2000-168223, JP-A-2001 -2099969, 2001-322354, 2006-248180, 2006-297907, 8-253705, 2004-503379, 2005-336150 In addition to organic sulfonate anions such as sulfonate anions described in Japanese Patent Publication No. 2006/28006, chloride ion, bromide ion, iodide ion, fluoride ion, chlorate ion, thiocitanoate ion, Hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion, octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis ( 4,6-di-t-butylphenyl) phosphonate ion, tetrakis (pentafluorophenyl) borate ion, quencher anion or cyclopenter having the function of deexciting (quenching) the active molecule in the excited state. Examples thereof include ferrocene having an anionic group such as a carboxyl group, a phosphonic acid group, and a sulfonic acid group in the dienyl ring, and a metallocene compound anion such as luteosen.

Specific examples of the cyanine compound (α) used in the present invention include the following compound No. 1 to 104 can be mentioned. In the following examples, the cyanine cation without the anion is shown.

Among the compounds represented by the general formula (II), the following compounds are preferable.
Ring A or ring A'is a benzene ring or a naphthalene ring.
Those in which r or r'is 0 to 2.
'If one or more, R ¹¹ and R ^11' r or r is a halogen atom, an alkyl group or carbon nitro group, a carboxyl group, ferrocenyl group, an unsubstituted 1-8 carbon atoms (especially 1 to 4) A halogen-substituted alkyl group having 1 to 8 atoms (particularly 1 to 4).
X ¹¹ and X ^{11 'are} an oxygen atom, a sulfur atom, -CR ²³ R ²⁴ [particularly, sometimes R ²³ and R ²⁴ are unsubstituted or substituted with a halogen atom, a carbon - carbon double bond It may be replaced by an alkyl group with 1 to 8 carbon atoms (particularly 1 to 4), unsubstituted or halogen atom, or it may be replaced by a carbon-carbon double bond. An arylalkyl group having 7 to 20 carbon atoms (particularly 7 to 15)] or a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms. Further, an oxygen atom, a sulfur atom, and −CR ²³ R ^24- [in particular, an alkyl group having 1 to 4 carbon atoms in which ^{R 23} and R ^{24 are unsubstituted] are more preferable.}
Y ¹¹ and Y ^{11 'is} a halogen atom, a nitro group, may have been substituted with a carboxyl group or a ferrocenyl group, carbon number 6 to 30 which sometimes has been replaced by an oxygen atom or -CO- (especially An aryl group of 6 to 12), an arylalkyl group having 7 to 30 carbon atoms (particularly 7 to 15), or an alkyl group having 1 to 8 carbon atoms. Further, an arylalkyl group having 7 to 30 carbon atoms (particularly 7 to 15) or an alkyl group having 1 to 8 carbon atoms may be substituted with a halogen atom or an oxygen atom. , More preferred.
Q constitutes a methine chain having 7 or 9 carbon atoms. Further, a methine chain having 7 or 9 carbon atoms is formed, and 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 methine chain having 7 or 9 carbon atoms and having a ring structure in the chain.

The production method of the cyanine compound (α) used in the present invention is not particularly limited, and it can be obtained by a method utilizing a well-known general reaction. For example, the route described in JP-A-2010-209191. As described above, a method of synthesizing by reacting a compound having a corresponding structure with an imine derivative can be mentioned.

The cyanine compound (α) used in the present invention preferably has a maximum absorption wavelength (λmax) of the coating film of 650 to 1200 nm, more preferably 650 to 900 nm. If the maximum absorption wavelength (λmax) of the coating film is 1200 nm or more of the present invention, the effect of the present invention is not exhibited, and if it is less than 650 nm, visible light is absorbed, which is not preferable.

In the heat-reactive composition of the present invention, the content of the cyanine compound (α) is at least one kind of cyanine compound (α) with respect to 100 parts by mass of the solid content of the resin (β) described later, either alone or in total. The total of α) is 0.01 to 10 parts by mass. If the content of the cyanine compound (α) is less than 0.01 parts by mass, sufficient infrared shielding ability may not be obtained in the cured product of the present invention, and if it is more than 10 parts by mass, the heat-reactive composition may not have sufficient infrared shielding ability. In some cases, precipitation of cyanine compound (α) may occur.

<Resin (β)>
The resin (β) is not particularly limited as long as it is a resin having an ethylenically unsaturated bond and a hydrophilic group in one molecule, and conventionally used resins 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 the hydroxyl group and the carboxyl group are preferable because the resin (β) has high solubility in alkali. ..
The preferred functional group equivalent of the hydrophilic group in the resin (β) (mass of the resin containing 1 equivalent of the hydrophilic group) is 50 to 10,000.
The preferable mass average molecular weight of the resin (β) is 1000 to 500,000.

Among the resins (β), the resin (β) has 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 one is preferable because it has high developability and heat resistance.

(式中、Ｘ¹は水素原子又はメチル基を表し、Ｙ¹は、二価の結合基であり、Ｒ¹は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、該アルキル基、アリール基及びアリールアルキル基は、ハロゲン原子、水酸基又はニトロ基で置換されている場合もあり、該アルキル基及びアリールアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨ−、あるいはこれらの組み合わせの結合基で置き換えられている場合もあり、Ｒ²、Ｒ³及びＲ⁴は、それぞれ独立に、水素原子又はメチル基である。)

(In the formula, X ¹ represents a hydrogen atom or a methyl group, Y ¹ is a divalent bonding group, R ¹ is an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. Alternatively, it represents an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and among the alkyl group and the arylalkyl group. Methylene groups in may be replaced with -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination of these binding groups, R ² , R ³ And R ⁴ are independently hydrogen atoms or methyl groups.)

^{Examples of the divalent bonding group represented by Y 1} in the general formula (I-2) include a structure represented by the following general formula (1).

（式中、Ｘ²は、−ＣＲ⁵Ｒ⁶−、−ＮＲ⁷−、二価の炭素原子数１〜３５の鎖状炭化水素基、二価の炭素原子数３〜３５の脂環式炭化水素基、二価の炭素原子数６〜３５の芳香族炭化水素基、二価の炭素原子数２〜３５の複素環含有基、又は下記（１−１）〜（１−３）で表されるいずれかの置換基を表し、Ｒ⁵及びＲ⁶は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、Ｚ¹及びＺ²は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＯ−、−ＮＲ⁷−又は−ＰＲ⁸−を表し、Ｒ⁷及びＲ⁸は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、
上記Ｒ⁵、Ｒ⁶、Ｒ⁷及びＲ⁸におけるアルキル基、アリール基及びアリールアルキル基は、ハロゲン原子、水酸基又はニトロ基で置換されていてもよく、上記Ｒ⁵、Ｒ⁶、Ｒ⁷及びＲ⁸におけるアルキル基及びアリールアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨ−基で置き換えられている場合もある。但し、上記一般式（１）で表される基の炭素原子数は１〜３５の範囲内である。）

(Wherein, X ^{2 is, -CR 5 R 6 -, -} NR 7 -, a divalent chain hydrocarbon group having a carbon number of 1 to 35, a divalent alicyclic carbon atoms from 3 to 35 carbon It is represented by a hydrogen group, an aromatic hydrocarbon group having 6 to 35 divalent carbon atoms, a heterocyclic group containing 2 to 35 divalent carbon atoms, or (1-1) to (1-3) below. R ⁵ and R ⁶ represent 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. represents, Z ¹ and Z ² are independently a direct bond, -O -, - S -, - SO 2 -, - SO -, - NR 7 - or -PR ⁸ - represents, R ⁷ and R ⁸ Represents a hydrogen atom, 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.
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 above R ⁵ , R ⁶ , R ⁷ and R may be substituted. ^{The methylene group in the alkyl group and the arylalkyl group in 8} may be replaced with the -O-, -S-, -CO-, -COO-, -OCO- or -NH- group. However, the number of carbon atoms of the group represented by the general formula (1) is in the range of 1 to 35. )

（上記式中、Ｒ⁷¹は水素原子、置換基を有していてもよいフェニル基、又は炭素原子数３〜１０のシクロアルキル基を表し、
Ｒ⁷²は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基は置換基を有していてもよく、
ｆは０〜５の整数である。）

(In the above formula, R ⁷¹ represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms.
R ⁷² represents 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, and the alkyl group, the alkoxy group and the alkenyl group are substituents. May have
f is an integer from 0 to 5. )

（上記式中、Ｒ⁷³及びＲ⁷⁴は、それぞれ独立に、置換基を有していてもよい炭素原子数１〜１０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリール基、置換基を有していてもよい炭素原子数６〜３０のアリールオキシ基、置換基を有していてもよい炭素原子数６〜３０のアリールチオ基、置換基を有していてもよい炭素原子数６〜３０のアリールアルケニル基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基、置換基を有していてもよい炭素原子数２〜２０の複素環含有基又はハロゲン原子を表し、
該アルキル基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、
Ｒ⁷³は、隣接するＲ⁷³同士で環を形成していてもよく、
ｄは０〜４の数を表し、
ｆは０〜８の数を表し、ｇは０〜４の数を表し、
ｈは０〜４の数を表し、
ｇとｈの数の合計は２〜４である。）

(In the above formula, R ⁷³ and R ⁷⁴ independently have an alkyl group having 1 to 10 carbon atoms which may have a substituent and 6 to 30 carbon atoms which may have a substituent. It has an aryl group, 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 substituent, and a substituent. It may have an arylalkenyl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, and a complex having 2 to 20 carbon atoms which may have a substituent. Represents a ring-containing group or 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 between adjacent R ^73s.
d represents a number from 0 to 4
f represents a number from 0 to 8, g represents a number from 0 to 4, and
h represents a number from 0 to 4
The total number of g and h is 2-4. )

The aryl group having 6 to 30 carbon atoms or the arylalkyl group having 7 to 30 carbon atoms (preferably 7 to 20) represented by ^{R 1} in the general formula (I-3) includes the component (α). Examples thereof include the aryl group or the arylalkyl group exemplified in the description of the cyanine compound.
Examples of the alkyl group having 1 to 20 carbon atoms include nonyl, decyl, undecylic, dodecyl, tridecylic, isotridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl and the like, in addition to the alkyl group exemplified in the above description of the cyanine compound (α). Be done.

In the above general formula (1), ^{the chain hydrocarbon groups having divalent carbon atoms 1 to 35 represented by X 2} include methane, ethane, propane, iso-propane, butane, sec-butane, and tert-. Butane, iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane, tert-octane Etc., including groups substituted with ^{Z 1} and Z ^2,
Examples of the divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like, Z ¹ and Z. Examples include groups substituted with ^2.
Examples of the divalent aromatic hydrocarbon group having 6 to 35 carbon atoms include a group in which a group such ^{as phenylene, naphthylene, and biphenyl is substituted with Z 1} and Z ^2.
Examples of the divalent heterocyclic group having 3 to 35 carbon atoms include pyridine, pyrazine, piperazine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chromane, xanthene, thiophene, and thiolane. ^{Examples include groups substituted with 1} and Z ² , and a plurality of these groups may be combined. Further, these chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups may be substituted with halogen atoms, hydroxyl groups or nitro groups. The methylene groups in these chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups are -O-, -S-, -CO-, -COO-, -OCO- or -NH- groups. It may have been replaced.

^{Alkyl groups having 1 to 8 carbon atoms represented by R 5} , R ⁶ , R ⁷ and R ⁸ in the above general formula (1), aryl groups having 6 to 30 carbon atoms or aryls having 7 to 30 carbon atoms. Examples of the alkyl group include an alkyl group, an aryl group, and an arylalkyl group exemplified in the above description of the cyanine compound (α).
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 in R ⁵ , R ⁶ and R ^{7 may be substituted.} The methylene group in the group and the arylalkyl group may be interrupted by -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a group in which a plurality of these groups are combined. Often, these replacement positions and interruption positions are not particularly limited.

Among the substituents represented by (1-1) above, ^{examples of the cycloalkyl group represented by R 71} having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohebutyl, cyclooctyl and the like. ,
As the alkyl group having 1 to 10 carbon atoms represented by ^{R 72} , among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by ^{R 1, a group satisfying a predetermined carbon atom number and the like are used.} Listed,
Alkoxy groups having 1 to 10 carbon atoms represented by R ⁷² include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, second butyloxy, tertiary butyloxy, isobutyloxy, amyloxy, isoamyloxy, and tertiary amyloxy. , Hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and the like.
Examples of the substituent which the alkyl group represented by R ⁷² , the alkoxy group and the alkenyl group may have include a halogen atom, a hydroxyl group and a nitro group.

Among the groups represented by (1-3) above, the alkyl group having 1 to 10 carbon atoms which may have a substituent represented by ^{R 73} and R ⁷⁴ is a carbon represented by ^{R 1.} Among the groups exemplified as alkyl groups having 1 to 20 atoms, a group satisfying a predetermined number of carbon atoms and the like can be mentioned.
The aryl group having 6 to 30 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ is a group exemplified as an aryl group having 6 to 30 carbon atoms represented by ^{R 11 or the like.} Etc.,
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, and 4} -Methylphenyloxy, 4-vinylphenyldioxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4 -Cyclohexylphenyloxy, 4-octylphenyloxy, 4- (2-ethylhexyl) phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6-dimethyl Phenyloxy, 3.4-Dimethylphenyloxy, 3.5-Dimethylphenyloxy, 2,4-G-tert-butylphenyloxy, 2,5-G-tert-butylphenyloxy, 2,6-G-tert-butylphenyl Oxygen, 2.4-di tert-pentylphenyloxy, 2,5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrosenyloxy and other groups are listed. Be,
As ^{the arylthio group having 6 to 30 carbon atoms which may have a substituent represented by R 73} and R ⁷⁴ , the aryloxy group having 6 to 30 carbon atoms which may have the above-mentioned substituent may be used. Examples include groups in which the oxygen atom of the above is replaced with a sulfur atom.
As the ^{arylalkenyl group having 8 to 30 carbon atoms which may have a substituent represented by R 73} and R ⁷⁴ , the aryloxy group having 6 to 30 carbon atoms which may have the above-mentioned substituent may be used. Examples thereof include a group in which the oxygen atom of the group is replaced with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like.
Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ⁷³ and R ⁷⁴ include the groups exemplified as the arylalkyl group having 7 to 30 carbon atoms represented by ^{R 71} and R ^72.
Examples of the heterocyclic group having 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, and the like. Examples include furan, tetrahydrofuran, chroman, xanthene, thiophene, thiolan and the like.
Examples of the above-mentioned substituent which the above-mentioned various groups represented by R ⁷³ and R ^{74 may have include a halogen atom, a hydroxyl group, and a nitro group.}

The composition ratio (molar ratio) of the units represented by the general formulas (I-1) to (I-3) is (I-1) :( I-2) :( I-3) = 0.1 to 1. The ratio is 0.65: 0.3 to 0.8: 0.001 to 2, and any sequence such as random copolymerization, block copolymerization, and graft copolymerization may be taken.

Among the resins (β) having the 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, and more preferably an alkyl group having 1 to 4 carbon atoms.
When Y ¹ has a divalent bonding group having a structure represented by the above general formula (1), X ² is preferably an alkylene group having 1 to 15 carbon atoms, and has a cycloalkylene group and 7 carbon atoms. ~ 15 alkylene groups are more preferred. 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 moiety in the alkylene group is -O-, -S-, -CO-. , -COO-, -OCO- or -NH- groups may be replaced.
Z ¹ and Z ² are preferably directly bonded.

The acid value of the resin (β) is preferably 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, sufficient alkali developability may not be obtained, and if it is larger than 200 mg / KOH, it may be difficult to produce the resin (β).
Here, the acid value is based on JIS K0050 and JISK0211.

In the heat-reactive composition of the present invention, the content of the resin (β) is preferably 30 to 99% by mass, particularly 60 to 95% by mass, based on 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 mechanical strength of the cured product may be insufficient and cracks may occur, and if it is more than 99% by mass, curing by exposure becomes insufficient and tack occurs. May be done.

<Thermal polymerization initiator (γ)>
Conventionally known compounds can be used as the thermal polymerization initiator (γ), and for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2 , 2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane) and other azo-based polymerization initiators; benzoyl peroxide, di-t-butylbenzoyl peroxide , T-butylperoxypivalate, peroxide-based polymerization initiators such as di (4-t-butylcyclohexyl) peroxydicarbonate, persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate, etc. Be done. These can be used alone or in admixture of two or more.

Among the above-mentioned thermal polymerization initiators (γ), azo-based polymerization initiators are preferable, and azobis-based compounds are more preferable, from the viewpoint of heat resistance. As the azobis-based compound, a compound represented by the following general formula (A) is preferably mentioned because it is industrially easily available.

（式中、Ｒ₁₀₁は置換基を有している場合もある分岐又は直鎖の炭素原子数１〜１０のアルキル基であり、Ｒ₁₀₂は置換基を有している場合もある分岐又は直鎖の炭素原子数１〜１０のアルキル基あるいは下記一般式（Ｂ）で表される基であり、前記アルキル基におけるメチレン基は−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−又は炭素−炭素二重結合で置き換えられていてもよく、同じ炭素原子と結合するＲ₁₀₁とＲ₁₀₂とは互いに連結して環を形成してもよい。Ｘ₁₀₁はシアノ基、−ＣＯＮＲ₁₀₃Ｒ₁₀₄、−ＣＯＯＲ₁₀₅、−Ｃ＝Ｎ−Ｒ₁₀₆又は置換基を有している場合もある分岐又は直鎖の炭素原子数１〜１０のアルキル基であり、Ｒ₁₀₃、Ｒ₁₀₄、Ｒ₁₀₅及びＲ₁₀₆はそれぞれ独立に水素原子又は炭素原子数１〜４のアルキル基である。）

(In the formula, R ₁₀₁ is a branched or linear alkyl group having 1 to 10 carbon atoms _{which may have a substituent, and R 102} may have a substituent or a branched or direct group. An alkyl group having 1 to 10 carbon atoms in the chain or a group represented by the following general formula (B), and the methylene group in the alkyl group is -O-, -CO-O-, -O-CO-,-. It may be replaced with CO-NH-, -NH-CO- or a carbon-carbon double bond, and R ₁₀₁ and R ₁₀₂ bonded to the same carbon atom may be linked to each other to form a ring. X ₁₀₁ is a branched or linear alkyl group with 1-10 carbon atoms that may have a cyano group, -CONR ₁₀₃ R ₁₀₄ , -COOR ₁₀₅ , -C = N-R _{106 or a substituent.} , R ₁₀₃ , R ₁₀₄ , R ₁₀₅ and R ₁₀₆ are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.)

（式中、Ｒ₁₁₁、Ｒ₁₁₂及びＲ₁₁₃はそれぞれ独立に水素原子又は置換基を有している場合もある炭素原子数１〜４のアルキル基であり、Ｒ₁₁₁、Ｒ₁₁₂は互いに連結して環を形成していてもよく、＊は結合部分を表す。）

(In the formula, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ are alkyl groups having 1 to 4 carbon atoms, which may independently have hydrogen atoms or substituents, respectively, and R ₁₁₁ and R ₁₁₂ are linked to each other. It may form a ring, and * represents a bonding portion.)

The alkyl groups represented by _{R 101} , R ₁₀₂ , X ₁₀₁ , R ₁₀₃ , R ₁₀₄ , R ₁₀₅ , R ₁₀₆ , R ₁₁₁ , R ₁₁₂ and R ₁₁₃ are exemplified as the alkyl groups represented by ^{R 11 and the like.} Among the groups, those satisfying the above-mentioned predetermined number of carbon atoms can be mentioned.
Examples of _{the ring formed by connecting R 101} and R ₁₀₂ to each other include a cycloalkyl ring, preferably a cycloalkyl ring having 3 to 8 carbon atoms.
Examples of the ring formed by connecting R ₁₁₁ and R ₁₁₂ to each other include an imidazole ring.
When the _{alkyl group represented by R 101} , R ₁₀₂ , X ₁₀₁ , R ₁₁₁ , R ₁₁₂ and R ₁₁₃ has a substituent, examples of the substituent include an alkoxy group having 1 to 4 carbon atoms, a carboxyl group or a hydroxyl group. Be done.

In the heat-reactive composition of the present invention, the content of the heat-polymerization initiator (γ) is 0.1 to 30% by mass, particularly 0.5 to 10% by mass, based on the solid content of the heat-reactive composition of the present invention. Mass% is preferred. 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 is larger than 30% by mass, thermal polymerization is initiated in the heat-reactive composition. The agent (γ) may precipitate.

<Monomer with unsaturated bond (ω)>
A monomer (ω) having an unsaturated bond can be further added to the heat-reactive composition of the present invention. 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, and acrylate. Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylpropantriacrylate, -2-hydroxyethyl methacrylate, -2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tershally butyl, cyclohexyl methacrylate, trimethyl propantrimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl Examples thereof include ether (meth) acrylate, bisphenol Z diglycidyl ether (meth) acrylate, and tripropylene glycol di (meth) acrylate. Among the above, a monomer having a plurality of unsaturated bonds is preferable because it can improve infrared shielding ability and heat resistance.

<Solvent (σ)>
A solvent (σ) can be further added to the heat-reactive composition of the present invention. The solvent is usually a solvent capable of dissolving or dispersing each of the above components (cyanine compound (α), etc.) as needed, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl. Ketones such as ketones, cyclohexanone, 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, etc. Ester solvents such as -n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol , Iso- or n-propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol and other alcohol solvents; 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-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate and other ether ester solvents; benzene, BTX-based solvents such as toluene and xylene; aliphatic hydrocarbon-based solvents such as hexane, heptane, octane and cyclohexane; terpene-based hydrocarbon oils such as terepine oil, D-lymonen and pinen; mineral spirit, swazole # 310 (Cosmo Matsuyama) Paraffin-based solvent such as Petroleum Co., Ltd., Solbesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvent such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; chlorobenzene Halogenated aromatic hydrocarbon solvents such as carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl. Examples thereof include sulfoxide, water and the like, and these solvents can be used as one kind or a mixed solvent of two or more kinds. Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like are used in the heat-reactive composition with the resin (β) and the thermal polymerization initiator (γ). It is preferable because it has good compatibility.

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

The heat-reactive composition of the present invention can 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; layered clay minerals, miloli blue and calcium carbonate. Magnesium carbonate, cobalt-based, manganese-based, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, serenes, aluminum silicates, calcium silicates, aluminum hydroxide, platinum, gold, silver, copper Among these, 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 with respect to 100 parts by mass of the resin (β). Therefore, one kind or two or more kinds of these inorganic compounds can be used.

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

When a pigment and / or an inorganic compound is used in the heat-reactive composition of the present invention, a dispersant can be added. The dispersant is not particularly limited as long as it can disperse or stabilize the pigment and / or the inorganic compound, and commercially available dispersants such as those manufactured by Big Chemie, BYK series and the like can be used. A polymer dispersant composed of polyester, polyether, and polyurethane having a basic functional group, a functional group having a nitrogen atom as a basic functional group and having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine. Those having a value of 1 to 100 mgKOH / g are preferably used.

Further, in the heat-reactive composition of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion accelerator; a filler; Conventional additives such as defoaming agent; leveling agent; surface conditioner; antioxidant; ultraviolet absorber; dispersion aid; anti-aggregation agent; catalyst; curing accelerator; cross-linking agent; thickener can be added. ..

In the heat-reactive composition of the present invention, any component other than the above-mentioned cyanine compound (α), resin (β) and thermal polymerization initiator (γ) (provided that the monomer (ω) having an unsaturated bond and the solvent (σ) are used. ) Is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total 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 made of 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, polymethylmethacrylate, methylmethacrylate-ethylacrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methylmethacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Examples thereof include polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin. Among these, polystyrene, (meth) acrylic acid-methylmethacrylate copolymer, and epoxy resin are preferable.
When another organic polymer is used, the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the resin (β).

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

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thioapple acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric 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-mercaptobutansulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-Mercaptoethylamine, 2-Mercaptoimidazole, 2-Mercaptobenzoimidazole, 2-Mercapto-3-pyridinol, 2-Mercaptobenzothiazole, Mercaptoacetic acid, Trimethylolpropanthris (3-mercaptopropionate), Pentaerythritoltetrakis Mercapto compounds such as (3-mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid. Alkyliodated compounds such as, trimethylolpropanetris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthio. Propionate, Butanediol Bisthioglycolate, Ethethylene Glycol Bisthioglycolate, Trimethylol Propanetristhioglycolate, Butanediol Bisthiopropionate, Trimethylol Propanetristhiopropionate, Trimethylol Propanetristhioglycolate , Pentaerythritol tetraxthiopropionate, pentaerythritol tetraxthioglycolate, trishydroxyethyl tristhiopropionate, compound C1, trimercaptopropionate tris (2-hydroxyethyl) isocyanurate and other aliphatic polyfunctional thiol compounds. , Showa Denko Co., Ltd. Karenz MT BD1, PE1, NR1 and the like.

Examples of the surfactant include fluorosurfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, and higher amines. Cationic surfactants such as halides and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among these, it has an isocyanate group such as KBE-9007, KBM-502, KBE-403, a methacryloyl group, and an epoxy group. Silane coupling agents are preferably used.

Examples of the melamine compound include all or a part _{of active methylol groups (CH 2} OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycol uryl, (poly) methylolbenzoguanamine, and (poly) methylol urea. Compounds in which (at least two) are alkyl etherified can be mentioned. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, which may be the same or different from each other. Further, the methylol group which has not been alkyl etherized may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluryl, tetrabutoxymethylglycoluryl and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

In the case of a solid state without a solvent, the heat-reactive composition of the present invention is dissolved or dispersed in a solvent, and then a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, a slit coater, a dip coater, and various types. It can be applied on a supporting substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, or plastic by a known means such as printing or dipping. Further, once applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on the application method.

The heating conditions for curing the heat-reactive composition of the present invention are 70 to 250 ° C. for 1 to 100 minutes. After pre-baking, it may be pressurized and post-baked, or it may be baked at several different temperatures.
The heating conditions vary depending on the type and blending ratio of each component, but are, for example, 70 to 180 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, the coating film is cured by 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. A membrane can be obtained.

The heat-reactive composition (or a cured product thereof) of the present invention is a heat-reactive paint or varnish, a heat-reactive adhesive, a printed circuit board, or a color display for a color television, a PC monitor, a mobile information terminal, a digital camera, or the like. Color filters for liquid crystal display panels, color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, three-dimensional modeling resins, gel coats, for electronic engineering Structures for manufacturing photo resists, electroplated resists, etching resists, both liquid and dry films, solder resists, color filters for various display applications, or in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs. Resists for forming, compositions for encapsulating electrical and electronic parts, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cables Uses coatings, screen printing stencil, materials for manufacturing three-dimensional objects by stereolithography, holography recording materials, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, microcapsules. Decolorizing material for image recording material, photoresist material for printed wiring board, photoresist material for UV and visible laser direct imaging system, photoresist material or protective film used for forming a dielectric layer in sequential lamination of printed circuit boards. It can be used for various purposes such as, and there is no particular limitation on the use.

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.

Subsequently, 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 heat-reactive composition of the present invention on one surface of the glass substrate (A), and is on the other surface of the glass substrate (A). It has an infrared reflective film (C). The coating layer (B) and the infrared reflective film (C) are laminated on each surface of the glass substrate (A), respectively. 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 incident side of light, and as shown in FIG. 2, it has an infrared reflective film (C). The side may be the incident side of light. Hereinafter, each layer will be described in order.

<Glass substrate (A)>
As the glass substrate (A) used for the wavelength cut filter of the present invention, a glass material transparent in the visible region can be appropriately selected and used, but soda lime glass, white plate glass, borosilicate glass, tempered glass, etc. Quartz glass, phosphate glass, etc. can be used. Among them, soda lime glass is preferable because it is inexpensive and easily available, and white plate glass, borosilicate glass, and tempered glass are easily available, have high hardness, and are excellent in workability. Therefore, it is preferable.

Further, after the glass substrate (A) is pretreated with a silane coupling agent or the like, a coating liquid made of the heat-reactive composition of the present invention is applied to form the coating layer (B). The adhesion of the coating layer (B) containing the dye after drying to the glass substrate is enhanced.

Examples of the silane coupling agent include epoxy-functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and other aminofunctional alkoxysilanes, γ-mercaptopropyltrimethoxy Examples thereof include mercaptofunctional alkoxysilane such as silane.

Further, a base layer may be provided between the glass substrate (A) and the coating layer (B). The base layer is a coating solution in which aggregates of metal oxide fine particles having an average secondary particle size of 20 to 250 nm, in which primary particles having an average primary particle size of 5 to 100 nm are aggregated, are dispersed in the solvent shown below. , Obtained by coating by the coating method shown below, and has a thickness of 30 to 1000 nm. The aggregate of the metal oxide fine particles is preferably 0.1 to 50% by 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, and more preferably 0.05 to 1 mm from the viewpoint of weight reduction and strength.

In the present invention, since the base material is a glass plate, it is possible to directly coat the base material, dry it, and then cut it, which simplifies the structure and process. Further, since the substrate is a glass plate, it has higher heat resistance (260 ° C. reflow resistance) than when it is made of plastic.

<Coating layer (B)>
In the coating layer (B) obtained from the heat-reactive composition of the present invention used for the wavelength cut filter of the present invention, the heat-reactive composition of the present invention is applied onto the glass substrate (A) as described above. It can be formed by The obtained coating film is heated and cured as necessary.

The thickness of the coating layer (B) containing the dye is preferably 1 to 200 μm because a uniform film can be obtained and it is advantageous for thinning. If it is less than 1 μm, the function cannot be fully exhibited, and if it exceeds 200 μm, the solvent may remain at the time of coating.

<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 the wavelength range of 700 to 1200 nm, and low refractive index layers and high refractive index layers are alternately laminated. It is formed by a dielectric multilayer film.

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 for example, silica, alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoride, and the like can be used. Can be mentioned.

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, and oxidation. In addition to yttrium, zinc oxide, zinc sulfide, indium oxide and the like, those containing these as main components and containing a small amount of titanium oxide, tin oxide, cerium oxide and the like can be mentioned.

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 CVD method or a sputtering method is performed on a glass substrate. , A method of forming a dielectric multilayer film in which low refractive index layers and high refractive index layers are alternately laminated by a vacuum vapor deposition method or the like can be mentioned. It is also possible to form a dielectric multilayer film in advance and attach it to a glass substrate with an adhesive.
The number of layers is 10 to 80, preferably 25 to 50, from the viewpoint of process and strength.

The thickness of the low refractive index layer and the high refractive index layer is usually 1/10 to 1/2 of the wavelength λ (nm) of the light beam to be blocked. When the thickness is less than 0.1λ or larger than 0.5λ, the product (nd) of the refractive index (n) and the physical film thickness (d) is specified as being significantly different from the optical film thickness represented by a multiple of λ / 4. There is a risk that wavelengths cannot be blocked or transmitted.

The infrared reflective film (C) includes, in addition to the above-mentioned dielectric multilayer film, a film containing a dye having a maximum absorption wavelength of 700 to 1100 nm, a laminated film of a polymer, and a film formed by applying a cholesteric liquid crystal. It is also possible to use a material using an organic material such as.

The wavelength cut filter of the present invention preferably has a transmittance of the following (i) to (iii). The transmittance was measured with an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation.
(I) In the wavelength range of 430 to 580 nm, the average value of the transmittance measured from the vertical direction of the wavelength cut filter (the direction perpendicular to the plate surface of the glass substrate, the same applies hereinafter) is 75% or more.
(Ii) At a wavelength of 800 to 1000 nm, the average value of the transmittance measured from the vertical direction of the wavelength cut filter is 5% or less.
(Iii) A wavelength value (Ya) 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 ° with respect to the vertical direction of the wavelength cut filter. The absolute value of the difference between the wavelength values (Yb) at which the transmittance is 80% when measured from is 30 nm or less.
In the wavelength cut filter, if the average value of the transmittance in the wavelength range of 430 to 580 nm of (i) is less than 75%, light in the visible light region is hardly transmitted. The average value of the transmittance in the wavelength range of 430 to 580 nm in (i) is more preferably 80% or more. If the average value of the transmittance at the wavelength of 800 to 1000 nm in (ii) exceeds 5%, the light in the infrared region is hardly cut, so that it may be difficult to correct the sensitivity so as to approach the human visual sensitivity. be. It is more preferable that the average value of the transmittance of (ii) at a wavelength of 800 to 1000 nm is 1% or less.
Further, when the absolute value of the difference between Ya and Yb in (iii) above exceeds 30 nm, the dependence on the incident angle of light becomes high, and the characteristics of the wavelength cut filter change depending on the incident angle of light, so that the center of the screen. There is a risk of adverse effects such as changes in color in the surrounding area. The absolute value of the difference between Ya and Yb in (iii) is more preferably 5 nm or less, and even more preferably 3 nm or less.

Specific applications of the wavelength cut filter of the present invention include a heat ray cut filter mounted on a window glass of an automobile or a building; a digital still camera, a digital video camera, a surveillance camera, an in-vehicle camera, a webcam, and a mobile phone. For visual sensitivity correction for solid-state image sensors such as CCD and CMOS in solid-state image sensors such as cameras; automatic exposure meters; display devices such as plasma displays can be mentioned.

Next, the solid-state image sensor and the camera module of the present invention will be described.
The solid-state image pickup device of the present invention is configured in the same manner as 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 FIGS. 5 and 6, the wavelength cut filter 1 of the present invention may be fixed to a portion other than the solid-state image sensor on the light incident side of the solid-state image sensor 2, or as shown in FIGS. 3 and 4. In addition, it may be fixed directly to the front surface of the solid-state image sensor 2.

An optical low-pass filter, an antireflection filter, a color filter, and the like can be arranged in the solid-state image sensor of the present invention, if necessary, and the order in which these are laminated is not particularly limited.

As shown in FIGS. 3 and 4, regarding the camera module which is one of the solid-state image sensors of the present invention, the wavelength cut filter 1 of the present invention is laminated on the solid-state image sensor on the light incident side of the solid-state image sensor 2. A specific case will be described.
3 and 4 are cross-sectional views showing a configuration of a camera module which is one of the solid-state image sensors of the present invention. The camera module is a coating layer (B) / glass substrate containing a dye from the light incident side on the opposite side of the solid-state image sensor 2 formed on the semiconductor substrate in a rectangular shape in a plan view and the light receiving portion 3 of the solid-state image sensor 2. Wavelength cut filter 1 (FIG. 3) laminated in the order of (A) and infrared reflective film (C) / or infrared reflective film (C), glass substrate (A), and coating layer (B) containing a dye are laminated in this order. The wavelength cut filter 1 (FIG. 4) is formed in a region excluding the light receiving portion 3 on one surface of the solid-state image sensor 2, and the solid-state image sensor 2 and the wavelength cut filter 1 are joined by an adhesive 4. The camera module, which is a solid-state image sensor, takes in light from the outside through the wavelength cut filter 1 and receives it by a light-receiving element arranged in the light-receiving unit 3 of the solid-state image sensor 2.

As shown in FIGS. 5 and 6, with respect to the camera module which is one of the solid-state image pickup devices of the present invention, the wavelength cut filter 1 of the present invention is applied to a portion other than the solid-state image sensor on the light incident side of the solid-state image sensor 2. The case where it is fixed will be specifically described.
5 and 6 are cross-sectional views showing a configuration of a camera module which is one of the solid-state image sensors of the present invention. The camera module is a coating layer (B) / glass substrate containing a dye from the light incident side on the opposite side of the solid-state image sensor 2 formed on the semiconductor substrate in a rectangular shape in a plan view and the light receiving portion 3 of the solid-state image sensor 2. Wavelength cut filter 1 (FIG. 5) laminated in the order of (A) and infrared reflective film (C) / or infrared reflective film (C), glass substrate (A), and coating layer (B) containing a dye are laminated in this order. It is formed in a region excluding the light receiving portion 3 on one surface of the wavelength cut filter 1 (FIG. 6) and the solid-state image sensor 2. The camera module, which is a solid-state image sensor, takes in light from the outside through the wavelength cut filter 1 and receives it by a light-receiving element arranged in the light-receiving unit 3 of the solid-state image sensor 2.

As the adhesive 4, a UV curable adhesive such as an acrylic resin or an epoxy resin or a thermosetting resin can be used, and after the adhesive 4 is uniformly applied, well-known photolithography is required. Adhesive 4 is patterned using technology and joined by thermosetting. When joining, vacuum pressurization may be performed after bonding 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 sensor 2.
The solid-state image sensor 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. Further, the lens holder 7 holds the lens 5, and includes a box-shaped base portion 7a that is attached to the mounting substrate 8 and covers the solid-state image sensor 2, and a cylindrical lens barrel portion 7b that holds the lens 5. It has.

Subsequently, the lens holder 7 is arranged on the mounting substrate 8 so that the lower end surface of the lens holder 7 is in contact with the coated adhesive 4, and the light receiving portion 3 of the solid-state image sensor 2 and the lens 5 in the lens holder 7 are further arranged. The position of the lens holder 7 is adjusted so that the distance of the lens 5 matches the focal length of the lens 5.

After adjusting the position of the lens holder 7, the adhesive 4 is irradiated with ultraviolet rays to cure the adhesive 4, and a camera module can be manufactured.
The entire mounting substrate 8 to which the lens holder 7 is fixed may be heated at about 85 ° C., and the adhesive 4 may be sufficiently cured by thermosetting.

Since the camera module manufacturing method includes a step of heating the entire mounting substrate 8 after the step of irradiating ultraviolet rays, the lens holder 7, the lens 5, and the wavelength cut filter 1 are all materials having high heat resistance. Is required to be used. Specifically, in addition to heating the adhesive 4 for thermosetting as described above, a plurality of solders arranged on the lower surface of the mounting substrate 8 are heat-melted at about 260 ° C. and soldered to other substrates. Therefore, it is desirable that the material is made of a material having reflow resistance.

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.

[Production Example 1] Resin (β) No. Preparation of 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), and azobisisobuty was added to this solution as a radical polymerization initiator. 4 parts by mass of ronitrile was added, and the mixture was stirred at 80 ° C. for 3 hours. Subsequently, 10 parts by mass of celloxide 2021P (alicyclic epoxy resin manufactured by Daicel Chemical Co., Ltd.) modified with acrylic acid was added, and the mixture was stirred at 120 ° C. for 3 hours to obtain a resin (β) No. I got 1.
This resin (β) No. In the above general formula (I), X ¹ is a hydrogen atom or a methyl group, and Y ¹ is a divalent bonding group represented by the above general formula (1) (X ² is the following formula (n). ), Z ¹ and Z ² are direct bonds), R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ^{2 to} R ³ are hydrogen atoms. , R ⁴ is a resin (β) which is a methyl group.

（ｎ）

(N)

[Production Example 2] Resin (β) No. Preparation of 2 20 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate and 50 parts by mass of benzyl methacrylate are dissolved in 500 parts by mass of cyclohexanone, 4 parts by mass of azobisisobutyronitrile is added as a radical polymerization initiator, and the temperature is 80 ° C. The mixture was stirred for 3 hours. Subsequently, 20 parts by mass of acrylic acid was added, and the mixture was stirred at 120 ° C. for 3 hours to obtain resin (β) No. I got 2.

[Production Example 3] Resin (β) No. Preparation of 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), and 1-di (t) was used as a radical polymerization initiator. -Butylperoxy) -3,3,5-trimethylcyclohexane 1 part by mass was added, and the mixture was stirred at 140 ° C. for 2 hours. Next, 20 parts by mass of acrylic acid was added, and the mixture was stirred at 120 ° C. for 3 hours to obtain resin (β) No. I got 3.

[Production Example 4] Resin (β) No. Preparation of 4 Azobisisobutyro as a radical polymerization initiator by dissolving 40 parts by mass of glycidyl methacrylate, 5 parts by mass of benzyl methacrylate, and 40 parts by mass of styrene in 500 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA). The mixture was stirred at 80 ° C. for 3 hours using 10 parts by mass of nitrile. Next, 20 parts by mass of acrylic acid was added, and the mixture was stirred at 120 ° C. for 3 hours to obtain resin (β) No. I got 4.

[Production Example 5] Resin (β) No. Preparation of 5 Azobisisobutyro as a radical polymerization initiator by dissolving 40 parts by mass of glycidyl methacrylate, 5 parts by mass of benzyl methacrylate, and 40 parts by mass of styrene in 500 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA). 5 parts by mass of nitrile was added, and the mixture was stirred at 80 ° C. for 3 hours. Then, 20 parts by mass of acrylic acid was added, and the mixture was stirred at 120 ° C. for 3 hours. Next, 5 parts by mass of tetrahydropyran anhydride was added, and the mixture was stirred at 120 ° C. for 3 hours, and then the resin (β) No. I got 5.

[Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-5] Thermally reactive composition No. 1-No. 11. And Comparative Composition No. 1-No. Preparation of <Step 1> Dye solution No. 1-No. No. 10 and Comparative Dye Liquid No. 1-No. Preparation of No. 5 Preparation (A) A solvent (σ) was added to the cyanine compound (α) shown in [Table 1] to [Table 3] as a component, and the mixture was stirred and dissolved to dissolve the dye solution No. 1-No. No. 10 and Comparative Dye Liquid No. 1-No. I got 5.

<Step 2> Thermally reactive composition No. 1-No. 10 and Comparative Composition No. 1-No. Preparation of 5
According to the formulation of [Table 1] to [Table 3], the above dye solution No. 1-No. No. 10 and Comparative Dye Liquid No. 1-No. A resin (β), a polymerization initiator (γ) (or (γ')), a monomer (ω) having an unsaturated bond, and a solvent (σ) were added to No. 5 and stirred to obtain the heat-reactive composition No. 5. 1-No. 10 and Comparative Composition No. 1-No. 5 was prepared.

A-1: Compound No. Hexafluorophosphate of 76 A-2: Compound No. Hexafluorophosphate A-3: Compound No. 100 bis (trifluoromethanesulfonyl) imidate A-4: Compound No. 102 bis (trifluoromethanesulfonyl) imidate A-5: Compound No. 103 bis (trifluoromethanesulfonyl) imidate B-1: Resin (β) No. obtained in Production Example 1. 1
B-2: ACA Z251 (Acrylate acrylate manufactured by Daicel Ornex)
B-3: ACA Z250 (acrylic acrylate manufactured by Daicel Ornex)
B-4: ACA 200M (Acrylate acrylate manufactured by Daicel Ornex)
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 (β) No. obtained in Production Example 2. 2
B-8: Resin (β) No. obtained in Production Example 3 3
B-9: Resin (β) No. obtained in Production Example 4. 4
B-10: Resin (β) No. obtained in Production Example 5 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 (BASF Photopolymerization Initiator)
C'-2: SP-246 (ADEKA photopolymerization initiator)
C'-3: OXE-01 (BASF photopolymerization initiator)
C'-4: OXE-02 (BASF photopolymerization initiator)
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 1-1-1-10 and Comparative Evaluation Examples 1-1-1-5]
The heat-reactive composition No. 1 to 1-10 obtained in Examples 1-1 to 1-10. 1-No. Comparative Composition No. 10 and Comparative Composition Nos. 1-1 to 1-5 obtained in Comparative Examples 1-1 to 1-5. 1-No. Each of 5 was applied to a glass substrate under the condition of 410 rpm × 7 seconds, and dried on a hot plate (90 ° C. for 10 minutes). 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 its heat resistance. The evaluation was performed by calculating the change in the transmittance of the maximum absorption wavelength before and after heating. The amount of change in transmittance was calculated by the following formula.
Amount of change in transmittance (%) = (XY) / X × 100 (X is the transmittance of the maximum absorption wavelength before heating, Y is the transmittance at the wavelength measured after heating)
These results are shown in [Table 4].

（表４中、「−」は均一に成膜できないため評価できないことを示す。）

(In Table 4, "-" indicates that the film cannot be evaluated because the film cannot be formed uniformly.)

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

[Examples 2-1 to 2-10] Wavelength cut filter No. 1-No. _{Manufacturing of No. 10 Silica (SiO 2} ) layers and titanium oxide (TiO ₂ ) layers are alternately laminated on one surface of a glass substrate (A) having a thickness of 100 μm by a vacuum vapor deposition method, and the total number of layers is 30. An infrared reflective film (C) having a thickness of about 3 μm was formed.
The heat-reactive composition (coating) obtained in Examples 1-1 to 1-10 is formed on a surface of the glass substrate (A) to which the obtained infrared reflective film (C) is applied, which is different from the infrared reflective film. Liquid) No. 1-No. No. 10 was applied with a bar coater # 30 (thickness 10 μm) and then dried at 100 ° C. for 10 minutes to obtain a wavelength cut filter No. 10. 1-No. 10 was made.

[Evaluation Examples 2-1 to 2-10]
The wavelength cut filter No. 1 of the present invention obtained in Examples 2-1 to 2-10. 1-No. Regarding 10, i) the average value of the transmittance when measured from the vertical direction of the wavelength cut filter in the wavelength range of 430 to 580 nm, and ii) the transmission when measured from the vertical direction of the wavelength cut filter at the wavelength of 800 to 1000 nm. Average value of rate and iii) In the wavelength range of 560 to 800 nm, with respect to the wavelength value (Ya) at which the transmittance is 80% when measured from the vertical direction of the wavelength cut filter, and the vertical direction of the wavelength cut filter. The absolute value of the difference between the wavelength values (Yb) at which the transmittance is 80% when measured from an angle of 35 ° was determined. The results are shown in [Table 5]. The upper transmittance was measured with an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation.

From the results shown in [Table 5] above, the wavelength cut filter of the present invention has a high transmittance in the wavelength range of 430 to 580 nm, a low transmittance in the wavelength range of 800 to 1000 nm, and a low incident angle dependence.

From the above results, it is characterized that the coating layer (B) containing a dye is formed on one surface of the glass substrate (A) and the infrared reflective film (C) is provided on the other surface of the glass substrate (A). The wavelength cut filter of the present invention is less dependent on the incident angle. Therefore, the wavelength cut filter of the present invention is useful for a solid-state image sensor and a camera module.

Claims (8)

A heat-reactive composition containing at least one of the cyanine compounds (α), at least a resin having an ethylenically unsaturated bond and a hydrophilic group (β), and a thermal polymerization initiator (γ).
The content of at least one (α) of the cyanine compound is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin (β).
The content of the resin (β) is 30 to 99% by mass in the solid content of the heat-reactive composition.
The content of the thermal polymerization initiator (γ) is 0.1 to 30% by mass in the solid content of the heat-reactive composition.
As at least one kind (α) of the cyanine compound, a compound represented by the following general formula (II) is included.
The resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group is represented by the following general formula (I-1), the unit represented by the following general formula (I-2), and the following general formula. A heat-reactive composition having a unit represented by (I-3).

(In the formula, ring A and ring A'independently represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring, respectively.
R ¹¹ and R ¹¹ 'are each independently, a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, carboxyl group, amino group, amido group, metallocenyl group, an aryl group having 6 to 30 carbon atoms, Represents 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 -, cycloalkane-1,1-diyl group or -NR ²⁵ 3 to 6 carbon atoms - a Represent,
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, carboxyl group, amino group, amido group, metallocenyl group, 6 carbon atoms Represents an aryl group of 30, 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 hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, carboxyl group, an amino group, carbon atoms which may be substituted by an amide group or a metallocenyl group Represents an aryl group having 6 to 30 atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.
The ^{aryl groups, arylalkyl groups and alkyl groups in R 11} , R ¹¹ ', Y ¹¹ , Y ^11' , R ²³ , R ²⁴ and R ²⁵ are hydroxyl groups, halogen atoms, nitro groups, cyano groups and -SO ₃ H. , Carboxyl group, amino group, amide group or metallocenyl group, and arylalkyl group and alkyl in ^{R 11} , R ¹¹ ', Y ¹¹ , Y ^11' , R ²³ , R ²⁴ and R ^{25 above.} The methylene group in the group is -O-, -S-, -CO- _{, -COO-, -OCO-, -SO 2-} , -NH-, -CONH-, -NHCO-, -N = CH- or It may have been replaced with a carbon-carbon double bond,
Q represents a linking group that constitutes a methine chain having 7 or 9 carbon atoms and may contain a ring structure in the chain, and the hydrogen atom in the methine chain is substituted with a hydroxyl group, a halogen atom, a cyano group or an aryl group. May have been
r and r'represent 0 or a substitutable number in ring A and ring A'
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents the coefficient that keeps the charge neutral. )

(In the formula, X ¹ represents a hydrogen atom or a methyl group, Y ¹ is a divalent bonding group, R ¹ is an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. Alternatively, it represents an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and among the alkyl group and the arylalkyl group. Methylene groups in may be replaced with -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination of these binding groups, R ² , R ³ And R ⁴ are independently hydrogen atoms or methyl groups.) A heat-reactive composition containing at least one of the cyanine compounds (α), at least a resin having an ethylenically unsaturated bond and a hydrophilic group (β), and a thermal polymerization initiator (γ).
The content of at least one (α) of the cyanine compound is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin (β).
The content of the resin (β) is 30 to 99% by mass in the solid content of the heat-reactive composition.
The content of the thermal polymerization initiator (γ) is 0.1 to 30% by mass in the solid content of the heat-reactive composition.
Forming the coating layer (B) of a wavelength cut filter having a coating layer (B) on one surface of the glass substrate (A) and an infrared reflective film (C) on the other surface of the glass substrate (A). Ri use der,
The resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group is represented by the following general formula (I-1), the unit represented by the following general formula (I-2), and the following general formula ( A heat-reactive composition comprising the unit represented by I-3).

(In the formula, X ¹ represents a hydrogen atom or a methyl group, Y ¹ is a divalent bonding group, R ¹ is an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. Alternatively, it represents an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and among the alkyl group and the arylalkyl group. Methylene groups in may be replaced with -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination of these binding groups, R ² , R ³ And R ⁴ are independently hydrogen atoms or methyl groups.) The heat-reactive composition according to claim 1 or 2, wherein the thermal polymerization initiator (γ) is an azo thermal polymerization initiator. A heat-reactive composition containing at least one of the cyanine compounds (α), at least a resin having an ethylenically unsaturated bond and a hydrophilic group (β), and a thermal polymerization initiator (γ).
The content of at least one (α) of the cyanine compound is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin (β).
The content of the resin (β) is 30 to 99% by mass in the solid content of the heat-reactive composition.
The content of the thermal polymerization initiator (γ) is 0.1 to 30% by mass in the solid content of the heat-reactive composition.
The thermal polymerization initiator (γ) is an azo thermal polymerization initiator.
The resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group is represented by the following general formula (I-1), the unit represented by the following general formula (I-2), and the following general formula ( A heat-reactive composition comprising the unit represented by I-3).

(In the formula, X ¹ represents a hydrogen atom or a methyl group, Y ¹ is a divalent bonding group, R ¹ is an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. Alternatively, it represents an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and among the alkyl group and the arylalkyl group. Methylene groups in may be replaced with -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination of these binding groups, R ² , R ³ And R ⁴ are independently hydrogen atoms or methyl groups.) The coating layer (B) obtained from the heat-reactive composition according to any one of claims 1 to 4 is provided on one surface of the glass substrate (A), and the other surface of the glass substrate (A). A wavelength cut filter characterized by having an infrared reflective film (C). The wavelength cut filter according to claim 5 , wherein the transmittance satisfies the following (i) to (iii).
(I) The average value of the transmittance when measured from the vertical direction of the wavelength cut filter in the wavelength range of 430 to 580 nm is 75% or more. (Ii) When measured from the vertical direction of the wavelength cut filter in the wavelength range of 800 to 1000 nm. The wavelength value (Ya) 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 when the average value of the transmittance is 5% or less (iii), and the wavelength cut filter. The absolute value of the difference between the wavelength values (Yb) at which the transmittance is 80% when measured from an angle of 35 ° with respect to the vertical direction of is 30 nm or less. A solid-state image pickup 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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