TWI738660B - Thermoreactive composition - Google Patents

Abstract

The thermoreactive composition of the present invention contains at least one cyanine compound (α), a resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (γ). Preferably, 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) . It is also preferable that the thermal polymerization initiator (γ) is an azo thermal polymerization initiator. In the following formulae, ^{the definitions of Y 1} , X ¹ , and R ¹ to R ⁴ refer to the specification.

Description

Thermoreactive composition

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

The sensitivity of solid-state imaging elements (CCD or C-MOS, etc.) used in digital still cameras, camcorders, mobile phone cameras, etc., ranges from the ultraviolet region to the infrared region of the wavelength of light. On the other hand, human visibility is only the visible region of light wavelength. 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 in a manner close to human visibility.

As infrared cut filters, there are known reflective filters that combine layers containing substances that do not have absorbing properties and are laminated into multiple layers and use the difference in refractive index, or transparent substrates containing or combined with light absorption The absorption filter of the agent.

Particularly, in the absorption filter, the deterioration of the light absorber due to heat treatment during manufacturing, etc., and the phenomenon that the infrared shielding ability is reduced is a problem.

Patent documents 1 and 2 describe a thermally reactive composition containing a thermal polymerization initiator. In addition, 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.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-256865

[Patent Document 2] US2010051883A1

[Patent Document 3] Japanese Patent Laid-Open No. 2013-173848

However, the compositions described in Patent Documents 1 to 3 are not sufficient in terms of heat resistance.

Therefore, the object of the present invention is to provide a heat-reactive composition having excellent heat resistance. In addition, another object of the present invention is to provide a wavelength cut filter using the above-mentioned thermally reactive composition.

The inventors have conducted intensive research repeatedly and found that the wavelength cut-off of a thermoreactive composition containing a cyanine compound, a resin having an ethylenic unsaturated bond and a hydrophilic group in one molecule, and a thermal polymerization initiator is not cut off. The heat resistance of the filter is reduced, and it is more suitable for a wavelength cut filter used in a solid-state imaging device, etc., thus achieving the invention.

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

In addition, the present invention provides a wavelength cut filter obtained by using the above-mentioned thermoreactive composition, and a solid-state imaging device and camera module using the wavelength cut filter.

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

1: Wavelength cut filter

2: Solid-state imaging element

3: Light receiving part

4: Adhesive

5: lens

6: Lens cover

7: Lens holder

7a: base part

7b: Lens barrel

8: Install the base plate

(A): Glass substrate

(B): Coating

(C): Infrared reflective film

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

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

3 is a cross-sectional view showing one form of the configuration of a camera module as one of the solid-state imaging devices of the present invention.

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

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

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

Hereinafter, the thermoreactive composition of the present invention will be described based on preferred embodiments.

The heat-reactive composition of the present invention contains at least one cyanine compound (α) (hereinafter also referred to as cyanine compound (α)), a resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group (hereinafter also referred to as cyanine compound (α)) It is called resin (β)), thermal polymerization initiator (γ), and optionally further contains 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 can be used without particular limitation, but from the viewpoint of ease of availability, it is preferably represented by the following general formula (II) By.

(In the formula, ring A and ring A'each independently represent a benzene ring, a naphthalene ring, a phenanthrene ring, or a pyridine ring, and R ¹¹ and R ^11' each independently represent a hydroxyl group, a halogen atom, a nitro group, a cyano group, and -SO ₃ H, carboxyl group, amino group, amide group, metallocene group, aryl group with 6 to 30 carbon atoms, aryl alkyl group with 7 to 30 carbon atoms or alkyl group with 1 to 8 carbon atoms, X ¹¹ And X ^11' each independently represent an oxygen atom, a sulfur atom, a selenium atom, -CR ²³ R ²⁴ -, a cycloalkane-1,1-diyl group with 3 to 6 carbon atoms or -NR ²⁵ -, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, a amide group, a metallocene group, and the number of carbon atoms 6-30 aryl, 7-30 arylalkyl or 1-8 alkyl, Y ¹¹ and Y ^11' each independently represent a hydrogen atom, or may be through a hydroxyl or halogen atom , Nitro, cyano, -SO ₃ H, carboxy, amine, amide or metallocene substituted aryl group with 6 to 30 carbon atoms, aryl alkyl with 7 to 30 carbon atoms or carbon Alkyl groups with 1-8 atoms, aryl, arylalkyl and alkyl in the above-mentioned R ¹¹ , R ^11' , Y ¹¹ , Y ^11' , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ There are also cases where it is substituted by a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amine group, a amide group or a metallocene group. The above-mentioned R ¹¹ , R ^11' , Y ¹¹ , Y ^11' , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ , the aryl alkyl group and the methylene group in the alkyl group are also substituted with -O-, -S-, -CO-, -COO-, In the case of -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N=CH- or carbon-carbon double bond, Q represents a methine chain with 1-9 carbon atoms and The chain may contain a linking group of a ring structure, and the hydrogen atom in the methine chain may also be substituted with a hydroxyl group, a halogen atom, a cyano group, -NRR', an aryl group, an arylalkyl group or an alkyl group, the -NRR ', aryl, arylalkyl and alkyl can be further substituted by hydroxyl, halogen atom, cyano or -NRR', and can also be substituted by -O-, -S-, -CO-, -COO-, -OCO -, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N=CH- or -CH=CH- interrupt, R and R'represent aryl, arylalkyl or alkyl, r and r'represents 0 or the number of substitutions in ring A and ring A', An ^q- represents an anion of q valence, q represents 1 or 2, and p represents a coefficient for keeping the charge neutral)

啉基羰基胺基、甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、正十八烷氧基羰基胺基、N-甲基-甲氧基羰基胺基、苯氧基羰基胺基、胺磺醯基胺基、N,N-二甲基胺基磺醯基胺基、甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯基胺基等；作為上述通式(II)中之R¹¹、R^11'及X¹¹及X^11'中之R²³、R²⁴及R²⁵所表示之醯胺基以及亦可對R¹¹、R^11'、R²³、R²⁴、R²⁵、Y¹¹、Y^11'所表示之芳基、芳基烷基、烷基進行取代之醯胺基，可列舉：甲醯胺基、乙醯胺基、乙基醯胺基、異丙基醯胺基、丁基醯胺基、辛基醯胺基、壬基醯胺基、癸基醯胺基、十一烷基醯胺基、十二烷基醯胺基、十六烷基醯胺基、十八烷基醯胺基、(2-乙基己基)醯胺基、苯甲醯胺基、三氟乙醯胺基、五氟苯甲醯胺基、二甲醯胺基、二乙醯胺基、二乙基醯胺基、二異丙基醯胺基、二丁基醯胺基、二辛基醯胺基、二壬基醯胺基、二癸基醯胺基、二-十一烷基醯胺基、二-十二烷基醯胺基、二(2- 乙基己基)醯胺基、二苯甲醯胺基、二-三氟乙醯胺基、二-五氟苯甲醯胺基等；作為上述通式(II)中之R¹¹、R^11'及X¹¹及X^11'中之R²³、R²⁴及R²⁵所表示之二茂金屬基以及亦可對R¹¹、R^11'、R²³、R²⁴、R²⁵、Y¹¹、Y^11'所表示之芳基、芳基烷基、烷基進行取代之二茂金屬基，可列舉：二茂鐵基、二茂鎳基、二茂鋯基、二茂鈦基、二茂鉿基等；作為上述通式(II)中之R¹¹、R^11'、Z¹¹、Z¹²、Z¹³、Y¹¹及Y^11'以及X¹¹及X^11'中之R²³、R²⁴及R²⁵所表示之碳原子數6~30之芳基，可列舉：苯基、萘基、2-甲基苯基、3-甲基苯基、4-甲基苯基、4-乙烯基苯基、3-異丙基苯基、4-異丙基苯基、4-丁基苯基、4-異丁基苯基、4-第三丁基苯基、4-己基苯基、4-環己基苯基、4-辛基苯基、4-(2-乙基己基)苯基、4-硬脂基苯基、2,3-二甲基苯基、2,4-二甲基苯基、2,5-二甲基苯基、2,6-二甲基苯基、3,4-二甲基苯基、3,5-二甲基苯基、2,4-二第三丁基苯基、2,5-二第三丁基苯基、2,6-二第三丁基苯基、2,4-二第三戊基苯基、2,5-二第三戊基苯基、2,5-二第三辛基苯基、2,4-二異丙苯基苯基、4-環己基苯基、(1,1'-聯苯)-4-基、2,4,5-三甲基苯基、二茂鐵基等；作為上述通式(II)中之R¹¹、R^11'、Y¹¹及Y^11'以及X¹¹及X^11'中之R²³、R²⁴及R²⁵所表示之碳原子數7~30之芳基烷基，可列舉：苄基、苯乙基、2-苯基丙烷-2-基、二苯基甲基、三苯基甲基、苯乙烯基、肉桂基、二茂鐵基甲基、二茂鐵基丙基等；作為上述通式(II)中之R¹¹、R^11'及Y¹¹、Y^11'以及X¹¹及X^11'中之R²³、R²⁴及R²⁵所表示之碳原子數1~8之烷基，可列舉：甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、第三戊基、己基、2-己基、3-己基、環己基、1-甲基環己基、庚基、2-庚基、3-庚基、異庚基、第三庚基、1-辛基、異辛基、第三辛 基等。 ^{As the halogen atom represented by R 11} , R ^{11 '} and ^{R 23} , R ²⁴ and R ^{25 in X 11} and X ^11' in the above-mentioned general formula (II), and can also be used for R ¹¹ , R ^{11 '} , R ²³ , R ²⁴ , R ²⁵ , Y ¹¹ , and Y ^11' represented by the halogen atom substituted by the aryl group, arylalkyl group, and alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as the above general formula (II) The amine groups represented ^{by R 11} , R ^11' and R ²³ , R ²⁴ and R ^{25 in X 11} and X ^{11 ' in R 11} , R ^11' , R ²³ , R ²⁴ , The aryl, arylalkyl, and alkyl substituted amino groups represented by R ²⁵ , Y ¹¹ , and Y ^11' include amino groups, ethylamino groups, dimethylamino groups, and diethylamino groups , Butylamino, Cyclopentylamino, 2-Ethylhexylamino, Dodecylamino, Anilino, Chlorophenylamino, Toluino, Methoxyanilin, N-methyl- Anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzylamino, methyl amide Amino, popenylamino, laurylamino, carbamate, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino,

Linylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tertiary butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino , Phenoxycarbonylamino group, sulfamoylamino group, N,N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group ^{R 11} , R ^{11 '} and ^{R 23} , R ²⁴ and R ^{25 in X 11} and X ^11' in the above general formula (II), etc.; and R ¹¹ , R ^11' , R ²³ , R ²⁴ , R ²⁵ , Y ¹¹ , and Y ^11' represent an aryl group, an arylalkyl group, and an amide group substituted with an alkyl group, and examples thereof include: methamido and acetamido Group, ethyl amide, isopropyl amide, butyl amide, octyl amide, nonyl amide, decyl amide, undecyl amide, dodecyl Amido, hexadecyl amido, octadecyl amido, (2-ethylhexyl) amido, benzyl amido, trifluoroacetamido, pentafluorobenzyl Amino, dimethylamino, diacetylamino, diethylamino, diisopropylamino, dibutylamino, dioctylamino, dinonylamino , Didecyl amide, di-undecyl amide, di-dodecyl amide, di(2-ethylhexyl) amide, dibenzyl amide, di-tris Fluoroacetamide group, di-pentafluorobenzamide group, etc.; as R ¹¹ , R ^11' and X ¹¹ and X ^11' in R ²³ , R ²⁴ and R ^{25 in} the above general formula (II) The metallocene group represented by R ¹¹ , R ^{11 '} , R ²³ , R ²⁴ , R ²⁵ , Y ¹¹ , Y ^11' represented by the aryl group, aryl alkyl group, and alkyl group can also be substituted Metallic bases include: ferrocene, nickelocene, zirconocene, titanocene, hafnium, etc.; as R ¹¹ , R ^11' , Z ^{11 in the above general formula (II)} , Z ¹² , Z ¹³ , Y ¹¹ and Y ^11', and R ²³ , R ²⁴ and R ^{25 in X 11} and X ^11' represent aryl groups with 6 to 30 carbon atoms, including: phenyl, naphthalene Group, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butyl Phenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)benzene Group, 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 Tributylphenyl, 2,4-Ditertiarypentylphenyl, 2,5-Ditertiarypentylphenyl, 2,5-Ditertiaryoctylphenyl, 2,4-Diisopropylbenzene Phenyl, 4- Cyclohexylphenyl, (1,1'-biphenyl)-4-yl, 2,4,5-trimethylphenyl, ferrocenyl, etc.; as R ¹¹ and R in the above general formula (II) The arylalkyl groups with 7 to 30 carbon atoms represented by R ²³ , R ²⁴ and R ^{25 in 11'} , Y ¹¹ and Y ^11' and X ¹¹ and X ^{11' include benzyl and phenethyl} , 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenyl methyl, ferrocenyl propyl, etc.; as the above general formula ( II) In R ¹¹ , R ^11' and Y ¹¹ , Y ^11' and R ²³ , R ²⁴ and R ^{25 in X 11} and X ^11' , the alkyl group with 1 to 8 carbon atoms, which can be enumerated: Methyl, ethyl, propyl, isopropyl, butyl, second butyl, tertiary butyl, isobutyl, pentyl, isopentyl, tertiary pentyl, hexyl, 2-hexyl, 3- Hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, 1-octyl, isooctyl, tertiary octyl, etc.

As the above-mentioned R ¹¹ , R ^11' and Y ¹¹ , Y ^{11 '} and X ¹¹ and X ^11' in R ²³ , R ²⁴ and R ²⁵ , it is also possible to pass a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H group, carboxyl group, amine group, amide group or metallocene group substituted aryl group with 6 to 30 carbon atoms, aryl alkyl group with 7 to 30 carbon atoms and alkyl group with 1 to 20 carbon atoms Examples include ^{aryl groups, arylalkyl groups, alkyl groups exemplified in the description of R 11} and the like, and hydrogen atoms in these groups are substituted with hydroxyl groups, halogen atoms, nitro groups, cyano groups, and -SO ₃ H groups. , Carboxyl group, amino group, amide group or metallocene group, the position and number of these substituents are not limited.

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

For example, as the group in which the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, and trifluoromethyl are listed. Group, nonafluorobutyl group, etc.; as the above-mentioned alkyl group having 1 to 8 carbon atoms interrupted by -O-, exemplified are: methoxy, ethoxy, isopropoxy, propoxy, butoxy , Pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and other alkoxy groups, or 2-methoxyethyl, 2-(2-methoxy Group) ethoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl, 3-methoxybutyl and other alkoxyalkyl groups, etc.; as the above-mentioned carbon A group in which an alkyl group having 1 to 8 atoms is substituted by a halogen atom and interrupted by -O- includes, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, and difluoromethyl Oxy, trifluoromethoxy, nonafluorobutoxy, etc.

In the above general formula (II), examples of the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by ^{X 11} and X ^{11' include cyclopropane-1,1-diyl group and cyclobutane} -1,1-diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1, 1-diyl, cyclohexane-1,1-diyl, etc.

As a linking group that constitutes a methine chain with 1 to 9 carbon atoms represented by Q in the above general formula (II) and may include a ring structure in the chain, the following (Q-1) to (Q-11) The base represented by any one is preferable because it is easy to manufacture. The number of carbon atoms in the methine chain with 1 to 9 carbon atoms means the number of carbon atoms in the methine chain and the linking group that can include a ring structure in the chain, and does not include the group that further substitutes the linking group (for example, the following The carbon atoms of R ¹⁴ to R ¹⁹ , Z') (for example, the carbon atoms at both ends of the linking group (Q-1)).

(In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z'each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, -NRR', an aryl group, an arylalkyl group Or alkyl, the -NRR', aryl, arylalkyl and alkyl can also be substituted by hydroxyl, halogen atom, cyano or -NRR', and can also be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N=CH- or -CH=CH- interrupt, R and R'represent aryl, arylalkyl Or alkyl)

Examples of the halogen atom, aryl group, arylalkyl group, or alkyl group represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z'can be exemplified in the description of ^{R 11, etc.} Examples of the aryl group, arylalkyl group, or alkyl group represented by R and R′ include those exemplified in ^{the description of R 11} and the like.

^{Examples of the q-valent anion represented by pAn q-} in the above general formula (II) include mesylate anion, dodecylsulfonate anion, benzenesulfonate anion, tosylate anion, trifluoromethanesulfonate anion , Naphthalenesulfonate anion, diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion, 2-amino-5-nitrobenzenesulfonate anion, naphthalene Disulfonate anion, naphtholsulfonate anion, bis(trifluoromethanesulfonyl) imidate anion, Japanese Patent Laid-Open No. 10-235999, Japanese Patent Laid-Open No. 10-337959, Japanese Patent Laid-open Hei 11-102088, Japanese Patent Laid-Open No. 2000-108510, Japanese Patent Laid-Open No. 2000-168223, Japanese Patent Laid-Open No. 2001-209969, Japanese Patent Laid-Open No. 2001-322354, Japanese Patent Laid-Open 2006-248180, Japanese Patent Laid-Open No. 2006-297907, Japanese Patent Laid-Open No. 8-253705, Japanese Patent Publication No. 2004-503379, Japanese Patent Publication No. 2005-336150, International Publication 2006/ Organic sulfonate anions such as sulfonate anions described in Bulletin No. 28006, etc., in addition to chloride ions, bromide ions, iodide ions, fluoride ions, chlorate ions, thiocyanate ions, and hexafluorophosphate ions. Ion, hexafluoroantimonate ion, tetrafluoroborate ion, octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonyl phenyl phosphate ion, 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphonate ion, tetrakis(pentafluorophenyl) borate ion, has the ability to de-excite (quench) the active molecules in the excited state ) Is a functional quencher anion or a metallocene compound anion such as ferrocene and ruthenium having anionic groups such as a carboxyl group, a phosphonic acid group, and a sulfonic acid group on the cyclopentadienyl ring.

As specific examples of the cyanine compound (α) used in the present invention, the following compound Nos. 1 to 104 can be cited. In addition, in the following examples, cyanine cations with anions omitted are shown.

[化4]

[化5]

[化6]

[化7]

[化8]

[化9]

[化10]

[化11]

[化12]

[化13]

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

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

r or r'is 0~2.

When r or r'is 1 or more, R ¹¹ and R ^11' are halogen atoms, nitro groups, carboxyl groups, ferrocene groups, unsubstituted carbon atoms of 1 to 8 (especially 1 to 4) An alkyl group or a halogen-substituted alkyl group with 1 to 8 carbon atoms (especially 1 to 4).

X ¹¹ and X ^11' are oxygen atoms, sulfur atoms, -CR ²³ R ²⁴ [especially when R ²³ and R ²⁴ are unsubstituted or substituted by halogen atoms and also substituted by carbon-carbon double bonds Alkyl groups with 1 to 8 carbon atoms (especially 1 to 4) may be unsubstituted or substituted by halogen atoms and may be substituted by carbon-carbon double bonds. The number of carbon atoms is 7-20 (especially 7-15) arylalkyl] or cycloalkane-1,1-diyl with 3-6 carbon atoms. More preferably, they are an oxygen atom, a sulfur atom, -CR ²³ R ^24- [especially R ²³ and R ²⁴ are unsubstituted alkyl groups with 1 to 4 carbon atoms].

Y ¹¹ and Y ^11' are substituted by halogen atoms, nitro groups, carboxyl groups or ferrocene groups, and also substituted by oxygen atoms or -CO-, with carbon atoms of 6 to 30 (especially 6 to 12). ), an aryl alkyl group with 7 to 30 carbon atoms (especially 7 to 15), or an alkyl group with 1 to 8 carbon atoms. More preferably, it is an arylalkyl group having 7 to 30 (especially 7 to 15) carbon atoms or an alkyl group having 1 to 8 carbon atoms in which there are cases where it is substituted with a halogen atom and there are cases where it is substituted with an oxygen atom.

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

The production method of the cyanine compound (α) used in the present invention is not particularly limited, and can be obtained by a method using a well-known general reaction, for example, as described in Japanese Patent Laid-Open No. 2010-209191 The described process is generally a synthesis method by reacting a compound with the structure and an imine derivative.

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 above 1200nm of the present invention, the effect of the present invention cannot be volatilized; if it does not reach 650nm, visible light will be absorbed, so it is not good.

In the heat-reactive composition of the present invention, the content of the above-mentioned cyanine compound (α) is singly or a total of plural kinds, relative to 100 parts by mass of the solid content of the resin (β) described later, the cyanine compound The total of at least one (α) is 0.01-10 parts by mass. If the content of the cyanine compound (α) is less than 0.01 parts by mass, the cured product of the present invention may not be able to obtain sufficient infrared shielding ability; if it is more than 10 parts by mass, the cyanine compound will be generated in the heat-reactive composition (α) The situation of precipitation.

<Resin (β)>

As the above-mentioned resin (β), as long as it is a resin having an ethylenically unsaturated bond and a hydrophilic group in one molecule, the previous ones can be used without particular limitation.

Examples of the hydrophilic group include a hydroxyl group, a mercapto group, a carboxyl group, a sulfo group, an amino group, an amido group, or a salt thereof. The hydroxyl group and the carboxyl group are preferred because the resin (β) has high solubility in alkali.

The preferred functional group equivalent of the hydrophilic group in the resin (β) (the mass of the resin containing 1 equivalent of the hydrophilic group) is 50 to 10,000.

The preferred mass average molecular weight of the resin (β) is 1,000 to 500,000.

In the above resin (β), those having a unit represented by the following general formula (I-1), a unit represented by the following general formula (I-2), and a unit represented by the following general formula (I-3) Since the developability or heat resistance is higher, it is preferable.

(In the formula, X ¹ represents a hydrogen atom or a methyl group, Y ¹ is a divalent bonding group, R ¹ represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or 7 ~30 Arylalkyl groups, the alkyl groups, aryl groups and arylalkyl groups may also be substituted by halogen atoms, hydroxyl groups or nitro groups, and the methylene groups in the alkyl groups and arylalkyl groups may also be substituted by When substituted with the bonding group of -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination of these, R ² , R ³ and R ⁴ are each independently hydrogen Atom or methyl)

^{As the divalent bonding group represented by Y 1} in the above general formula (I-2), a structure represented by the following general formula (1) can be cited.

[Chemical 15] *-Z ¹ -X ² -Z ² -* (1)

(In the formula, X ² represents -CR ⁵ R ⁶ -, -NR ⁷ -, divalent chain hydrocarbon group with 1 to 35 carbon atoms, divalent alicyclic hydrocarbon group with 3 to 35 carbon atoms, divalent The aromatic hydrocarbon group with 6 to 35 carbon atoms, the divalent heterocyclic group with 2 to 35 carbon atoms, or any one of the substituents represented by the following (1-1) to (1-3), R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an arylalkyl group with 7 to 30 carbon atoms. Z ¹ and Z ² each independently represent direct Bond, -O-, -S-, -SO ₂ -, -SO-, -NR ⁷ -or -PR ⁸ -, R ⁷ and R ⁸ represent a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, and a carbon atom An aryl group with 6 to 30 or an arylalkyl group with 7 to 30 carbon atoms. The alkyl, aryl and arylalkyl groups in ^{R 5} , R ⁶ , R ⁷ and R ^{8 may also be halogenated,} Substitution by hydroxy or nitro, the ^{alkyl group in the above R 5} , R ⁶ , R ⁷ and R ⁸ and the methylene group in the arylalkyl group are also substituted with -O-, -S-, -CO-,- In the case of COO-, -OCO- or -NH- groups. Among them, the number of carbon atoms of the group represented by the above general formula (1) is in the range of 1 to 35)

(In the above formula, R ⁷¹ represents a hydrogen atom, optionally substituted phenyl, or a cycloalkyl group with 3 to 10 ^{carbon atoms, and R 72} represents an alkyl group with 1 to 10 carbon atoms, and 1 to 10 carbon atoms. The alkoxy group, alkenyl group with 2-10 carbon atoms or halogen atom, the above-mentioned alkyl group, alkoxy group and alkenyl group may also have substituents, f is an integer of 0-5)

(In the above formula, R ⁷³ and R ⁷⁴ each independently represent an optionally substituted alkyl group with 1 to 10 carbon atoms, an optionally substituted aryl group with 6 to 30 carbon atoms, and an optionally substituted carbon atom Aryloxy groups with 6 to 30, arylthio groups with 6 to 30 carbon atoms that may have substituents, arylalkenyls with 6 to 30 carbon atoms that may have substituents, and carbon atoms that may have substituents An arylalkyl group of 7 to 30, a heterocyclic group containing 2 to 20 carbon atoms or a halogen atom that may have a substituent, the methylene group in the alkyl group and the arylalkyl group may also have an unsaturated bond, -O- or -S- interrupt, R ⁷³ can be adjacent to R ⁷³ to form a ring with each other, d represents the number from 0 to 4, f represents the number from 0 to 8, g represents the number from 0 to 4, and h represents the number from 0 to 4 Number, the total number of g and h is 2~4)

As the aryl group with 6 to 30 carbon atoms or the arylalkyl group with 7 to 30 (preferably 7 to 20) carbon atoms represented ^{by R 1} in the above general formula (I-3), the above-mentioned (α) The aryl group or arylalkyl group exemplified in the description of the cyanine compound of the component.

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

、哌啶、哌

、嘧啶、嗒

、三

、六氫三

、呋喃、四氫呋喃、苯并二氫哌喃、

、噻吩、硫雜環戊烷等經Z¹及Z²取代之基，該等基亦可組合複數種。又，該等鏈狀烴基、脂環式烴基及芳香族烴基亦可經鹵素原子、羥基或硝基取代。又，該等鏈狀烴基、脂環式烴基及芳香族烴基中之亞甲基亦存在被取代為-O-、-S-、-CO-、-COO-、-OCO-或-NH-基之情形。 In the above general formula (1), ^{the divalent chain hydrocarbon group with 1 to 35 carbon atoms represented by X 2} includes methane, ethane, propane, isopropane, butane, second butane, Tertiary butane, isobutane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, isoheptane, tertiary heptane Alkane, 1-methyloctane, isooctane, tertiary octane and other ^{groups substituted by Z 1} and Z ² , as the divalent alicyclic hydrocarbon group with 3 to 35 carbon atoms, examples include: Propane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane, etc. ^{substituted by Z 1} and Z ² , etc., Examples of divalent aromatic hydrocarbon groups with 6 to 35 carbon atoms include: phenylene, naphthyl, biphenyl and other groups substituted by Z ¹ and Z ² ; as a divalent carbon atom The number 3~35 contains heterocyclic group, including: pyridine, pyridine

, Piperidine, piper

, Pyrimidine, da

,three

Hexahydrosan

, Furan, tetrahydrofuran, chroman,

, Thiophene, thiolane, and other ^{groups substituted by Z 1} and Z ² , these groups can also be combined with plural kinds. In addition, these chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups may be substituted with halogen atoms, hydroxyl groups, or nitro groups. In addition, the methylene groups in these chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups also exist and are substituted with -O-, -S-, -CO-, -COO-, -OCO- or -NH- groups The situation.

As the alkyl group with 1 to 8 carbon atoms, the aryl group with 6 to 30 carbon atoms, or the one with 7 to 30 carbon atoms represented ^{by R 5} , R ⁶ , R ⁷ and R ⁸ in the above general formula (1) The arylalkyl group includes the alkyl group, aryl group, and arylalkyl group exemplified in the description of the cyanine compound (α); the alkyl group and aryl group in the above-mentioned R ⁵ , R ⁶ , R ⁷ and R ⁸ And arylalkyl groups can also be substituted by halogen atoms, hydroxy groups or nitro ^{groups. The alkyl groups in R 5} , R ⁶ and R ⁷ and the methylene groups in arylalkyl groups can also be substituted by -O-, -S- , -CO-, -COO-, -OCO-, -NH-, or a group composed of a plurality of these groups are interrupted, and the substitution position and interruption position of these groups are not particularly limited.

In the substituent represented by (1-1) above, the cycloalkyl group having 3 to 10 carbon atoms represented by ^{R 71 includes cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl,} Cyclooctyl, etc.; as the alkyl group having 1 to 10 carbon atoms represented by ^{R 72 , the alkyl group having 1 to 40 carbon atoms represented by R 1} can be exemplified by those that satisfy the specified number of carbon atoms. The alkoxy group having 1 to 10 carbon atoms represented by R ⁷² includes: methoxy, ethoxy, propoxy, isopropoxy, butoxy, second butoxy, Tertiary butoxy, isobutoxy, pentyloxy, isopentyloxy, tertiary pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, N-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, etc.

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

、哌啶、哌

、嘧啶、嗒

、三

、六氫三

、呋喃、四氫呋喃、苯并二氫哌喃、

、噻吩、硫雜環戊烷等。 Among the groups represented by (1-3) above, as the alkyl group having 1 to 10 carbon atoms represented by ^{R 73} and R ⁷⁴ and optionally having substituents, the number of carbon atoms represented by ^{R 1 is 1} Among the exemplified groups for the alkyl group of ~20, those satisfying the specified number of carbon atoms, etc.; as R ⁷³ and R ⁷⁴ , the aryl group having 6 to 30 carbon atoms that may have a substituent may be exemplified as R ¹¹ Groups such as aryl groups with 6 to 30 carbon atoms represented by R ⁷³ and R ⁷⁴ ; aryloxy groups with 6 to 30 carbon atoms that may have substituents represented by R 73 and R 74 include: phenoxy Group, naphthyloxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 4-vinylphenyldioxy, 3-isopropylphenoxy, 4 -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-di Methylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,4-di-tert-butylphenoxy, 2,5-di-tert-butyl Phenoxy, 2,6-di-tertiary butylphenoxy, 2,4-di-tertiary pentyl phenoxy, 2,5-tertiary pentyl phenoxy, 4-cyclohexyl phenoxy, Groups such as 2,4,5-trimethylphenoxy and ferrocenyloxy; as R ⁷³ and R ⁷⁴ , the arylthio group with 6 to 30 carbon atoms that may have a substituent may be Examples include the above-mentioned groups in which the oxygen atom of an aryloxy group having 6 to 30 carbon atoms that may have substituents is substituted with a sulfur atom; as the number of carbon atoms that may have substituents represented by ^{R 73} and R ⁷⁴ 8 to 30 arylalkenyl groups, including the above-mentioned optionally substituted aryloxy groups with 6 to 30 carbon atoms. Groups substituted with alkenyl groups such as butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, etc.; as R ⁷³ and R ⁷⁴ , the number of carbon atoms is 7 to 30 The arylalkyl group includes the groups exemplified as the arylalkyl group having 7 to 30 carbon atoms represented by ^{R 71} and R ^{72; as the carbon atom represented by R 73} and R ⁷⁴ that may have a substituent The number 2-20 contains heterocyclic group, including: pyridine, pyridine

, Piperidine, piper

, Pyrimidine, da

,three

Hexahydrosan

, Furan, tetrahydrofuran, chroman,

, Thiophene, thiolane, etc.

Examples of the substituents which may be possessed by the various groups represented by R ⁷³ and R ^{74 include a halogen atom, a hydroxyl group, and a nitro group.}

The composition ratio (mole ratio) of the units represented by the above general formulas (I-1)~(I-3) is (I-1): (I-2): (I-3)=0.1~0.65: 0.3 ~0.8: 0.001~2, any arrangement such as random copolymerization, block copolymerization, graft copolymerization, etc. can be used.

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

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 the ^{divalent bonding group of Y 1} is the structure represented by the above general formula (1), X ^{2 is} preferably an alkylene group having 1 to 15 carbon atoms, more preferably a cycloalkylene group An alkylene group with 7 to 15 carbon atoms. The hydrogen atoms in these alkylene groups can also be substituted with halogen atoms, hydroxyl groups or nitro atoms, and the methylene groups in the chain alkylene moieties in the alkylene groups can also be substituted with -O-,- In the case of S-, -CO-, -COO-, -OCO- or -NH-groups.

Z ¹ and Z ^{2 are} preferably direct bonds.

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 greater than 200 mg/KOH, the production of the resin (β) may become difficult.

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

In the thermally reactive composition of the present invention, the content of the resin (β) in the solid content of the thermally reactive composition of the present invention is 30 to 99% by mass, particularly preferably 60 to 95% by mass. If the content of the above-mentioned resin (β) is less than 30% by mass, the hardened product may have insufficient mechanical strength and cracks. If it is greater than 99% by mass, the hardening due to exposure may be insufficient and stickiness may occur. .

<Thermal polymerization initiator (γ)>

As the thermal polymerization initiator (γ), previously known compounds can be used, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate) , 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane) and other azo polymerization start Agents; Peroxides such as benzoyl peroxide, di-tert-butyl benzoyl peroxide, tert-butyl peroxy pivalate, and bis(4-tertiary butylcyclohexyl) peroxydicarbonate Polymerization initiator, persulfate such as ammonium persulfate, sodium persulfate, potassium persulfate, etc. These can be used singly or in combination of two or more.

Among the above-mentioned thermal polymerization initiators (γ), in terms of heat resistance, an azo-based polymerization initiator is preferred, and an azobis-based compound is more preferred. As the azobis-based compound, in terms of easy industrial availability, a compound represented by the following general formula (A) can be preferably cited.

[化18A]

(In the formula, R ₁₀₁ also has a branched or linear alkyl group with 1 to 10 carbon atoms _{when it has a substituent, and R 102} also has a branched or linear carbon atom with a substituent. An alkyl group of 1 to 10 or a group represented by the following general formula (B). The methylene group in the alkyl group may be substituted with -O-, -CO-O-, -O-CO-,- CO-NH-, -NH-CO- or carbon-carbon double bond, R ₁₀₁ and R ₁₀₂ bonded to the same carbon atom can also be connected to each other to form a ring. X ₁₀₁ is a cyano group, -CONR ₁₀₃ R ₁₀₄ ,- COOR ₁₀₅ , -C=NR ₁₀₆ or a branched or straight chain alkyl group with 1 to 10 carbon atoms where there are substituents, R ₁₀₃ , R ₁₀₄ , R ₁₀₅ and R ₁₀₆ are each independently a hydrogen atom or (Alkyl group with 1 to 4 carbon atoms)

(In the formula, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ are each independently a hydrogen atom or an alkyl group with 1 to 4 carbon atoms may also have substituents. R ₁₁₁ and R ₁₁₂ may also be connected to each other to form a ring, * (Represents the bonding part)

Examples of 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 include the alkyl groups represented by the above-mentioned R ¹¹ and the like Among the bases, those satisfying the above-mentioned specific number of carbon atoms.

Examples of the ring formed by connecting R ₁₀₁ and R _{102 to} each other include a cycloalkyl ring, and a cycloalkyl ring having 3 to 8 carbon atoms is preferred.

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, the substituent includes an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, or a hydroxyl group.

In the thermally reactive composition of the present invention, the content of the thermal polymerization initiator (γ) in the solid content of the thermally reactive composition of the present invention is 0.1-30% by mass, particularly preferably 0.5-10% by mass %. If the content of the above-mentioned thermal polymerization initiator (γ) is less than 0.1% by mass, sufficient heat resistance may not be obtained; if it is greater than 30% by mass, the thermal polymerization initiator ( γ) The situation.

<Monomers with unsaturated bonds (ω)>

It is also possible to further add a monomer (ω) having an unsaturated bond to the thermoreactive 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, acrylic acid Stearyl ester, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate Ester, 2-hydroxypropyl methacrylate, butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth)acrylate, bisphenol F diglycidyl ether (meth)acrylate, bisphenol Z diglycidol Ether (meth)acrylate, tripropylene glycol di(meth)acrylate, etc. Among the above, monomers having a plurality of unsaturated bonds can improve infrared shielding ability and heat resistance, and are therefore preferred.

<Solvent (σ)>

烷、四氫呋喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、二丙二醇二甲醚等醚系溶劑；乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸環己酯、乳酸乙酯、琥珀酸二甲酯、TEXANOL等酯系溶劑；乙二醇單甲醚、乙二醇單乙醚等溶纖劑系溶劑；甲醇、乙醇、異或正丙醇、異或正丁醇、戊醇、二丙酮醇等醇系溶劑；乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、丙二醇-1-單甲醚-2-乙酸酯(PGMEA)、二丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯、丙酸乙氧基乙酯、1-第三丁氧基-2-丙醇、乙酸3-甲氧基丁酯、環己醇乙酸酯等醚酯系溶劑；苯、甲苯、二甲苯等BTX系溶劑；己烷、庚烷、辛烷、環己烷等脂肪族烴系溶劑；松節油、D-檸檬烯、蒎烯等萜烯系烴油；礦油精、Swazol # 310(科斯莫松山石油股份有限公司)、Solvesso # 100(Exxon Chemical股份有限公司)等鏈烷系溶劑；四氯化碳、氯仿、三氯乙烯、二氯甲烷、1,2-二氯乙烷等鹵化脂肪族烴系溶劑；氯苯等鹵化芳香族烴系溶劑；卡必醇系溶劑、苯胺、三乙基胺、吡啶、乙酸、乙腈、二硫化碳、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、二甲基亞碸、水等，該等溶劑可使用1種或以2種以上之混合溶劑之形式使用。該等中，酮類、醚酯系溶劑等、特別是丙二醇-1-單甲醚-2-乙酸酯、環己酮等於熱反應性組合物中與樹脂(β)及熱聚合起始劑(γ)之相溶性良好，因此較佳。 A solvent (σ) can be further added to the heat-reactive composition of the present invention. As the solvent, usually, solvents that can dissolve or disperse the above-mentioned components (cyanine compound (α) etc.) can be mentioned as needed, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, Methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketones; diethyl ether, two

Ether solvents such as alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Ester solvents such as isopropyl ester, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and TEXANOL; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol , Ethanol, iso-or n-propanol, iso-or n-butanol, pentanol, diacetone alcohol and other alcoholic solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-mono Methyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-tertiary butoxy-2-propanol , 3-methoxybutyl acetate, cyclohexanol acetate and other ether ester solvents; benzene, toluene, xylene and other BTX solvents; hexane, heptane, octane, cyclohexane and other aliphatic hydrocarbons Solvents; terpene-based hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, Swazol # 310 (Kosmo Songshan Petroleum Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.) and other paraffinic solvents; Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, three Ethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfide, water, etc. , These solvents can be used in the form of one or more than two mixed solvents. Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate and cyclohexanone are equivalent to the resin (β) and the thermal polymerization initiator in the thermally reactive composition. The compatibility of (γ) is good, so it is preferable.

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) becomes 5-30% by mass. When the concentration of the composition other than the solvent (σ) is less than 5 mass%, it may become difficult to thicken the film thickness, and the light of the desired wavelength cannot be fully absorbed; when it exceeds 30 mass%, there may be A situation in which the storability of the composition is reduced due to the precipitation of the composition, or the viscosity is increased, resulting in a decrease in operation.

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 dioxide, and aluminum oxide; layered clay minerals, Milo Milori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, silicic acid Calcium, aluminum hydroxide, platinum, gold, silver, copper, etc., of which titanium oxide, silicon dioxide, layered clay minerals, silver, etc. are preferred. In the thermally reactive composition of the present invention, the content of the above-mentioned inorganic compound relative to 100 parts by mass of the above-mentioned resin (β) is preferably 0.1-50 parts by mass, more preferably 0.5-20 parts by mass, and the inorganic compounds can be Use 1 type or 2 or more types.

These inorganic compounds can be used as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, etc., for example.

When pigments and/or inorganic compounds are used in the heat-reactive composition of the present invention, a dispersant may be added. The dispersant is not particularly limited as long as it can disperse or stabilize pigments and/or inorganic compounds. Commercially available dispersants, such as BYK series manufactured by BYK-Chemie, etc., can be used. , Polymer dispersants containing polyester, polyether, polyurethane having basic functional groups can be suitably used, the functional groups having nitrogen atoms as basic functional groups are amines, and/ Or its quaternary salt, and the amine value is 1-100mgKOH/g.

等熱聚合抑制劑；塑化劑；接著促進劑；填充劑；消泡劑；調平劑；表面調整劑；抗氧化劑；紫外線吸收劑；分散助劑；凝聚抑制劑；觸媒；硬化促進劑；交聯劑；增黏劑等慣用之添加物。 In addition, in the heat-reactive composition of the present invention, p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol, and phenothiol may be added as needed.

Thermal polymerization inhibitors; plasticizers; then accelerators; fillers; defoamers; leveling agents; surface modifiers; antioxidants; ultraviolet absorbers; dispersing aids; aggregation inhibitors; catalysts; hardening accelerators ; Crosslinking agent; Tackifier and other commonly used additives.

In the thermoreactive composition of the present invention, optional components other than the above-mentioned cyanine compound (α), resin (β) and thermal polymerization initiator (γ) (among them, the monomer having an unsaturated bond (ω) and Melt The content of the agent (except σ) can be appropriately selected according to the purpose of use and is not particularly limited, but it 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, by using other organic polymers together with the above-mentioned resin (β), the properties of the cured product containing the heat-reactive composition of the present invention can also be improved. Examples of the above-mentioned organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (Meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane Ester resin, polycarbonate, polyvinyl butyral, cellulose ester, polypropylene amide, saturated polyester, phenol resin, phenoxy resin, polyamide resin, polyamide resin, epoxy resin Among them, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred.

In the case of using other organic polymers, the amount used is preferably 10 to 500 parts by mass relative to 100 parts by mass of the above-mentioned resin (β).

In the heat-reactive composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, etc. can be further used in combination.

As the above-mentioned chain transfer agent or sensitizer, a compound containing a sulfur atom is generally used. Examples include: thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycamine Acid, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)aminomethanyl]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, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole , 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate) and other mercapto compounds, right The disulfide compound obtained by oxidation of the mercapto compound Alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, trimethylolpropane tris(3-mercaptoisobutyrate), Butanediol bis(3-mercaptoisobutyrate), hexamethylene dithiol, decane dithiol, 1,4-dimethyl mercaptobenzene, butanediol dithiopropionate, butanediol dithio Acetate, ethylene glycol dithioacetate, trimethylolpropane trithioacetate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trihydroxymethyl Methyl propane trithioacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioacetate, trihydroxyethyl trithiopropionate, the following compound C1, trimercaptopropionate tris(2-hydroxyl Aliphatic polyfunctional thiol compounds such as ethyl) ester isocyanurate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko Corporation.

As the above-mentioned surfactants, fluorosurfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, and anionic surfactants such as alkali salts of higher fatty acids, alkyl sulfonates, and alkyl sulfates can be used. , Higher amine halide, quaternary ammonium salt and other cationic surfactants, polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride and other non-ionic interface Surfactants, amphoteric surfactants, silicone surfactants and other surfactants can also be used in combination.

As the above-mentioned silane coupling agent, for example, the silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among these, KBE-9007, KBM-502, KBE-403, etc. having isocyanate groups, methacrylic groups, and epoxy groups can be suitably used. The silane coupling agent.

Examples of the above-mentioned melamine compounds include: (poly)methylolmelamine, (poly)methylol glycoluril, (poly)methylol benzoguanamine, (poly)methylolurea, and other nitrogen compounds, which are active methylol A compound in which all or part (at least 2) of the group (CH _{2 OH group) is etherified with an alkyl group.} Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, or a butyl group, which may be the same or different from each other. In addition, the methylol group that is not alkyl etherified may undergo self-condensation within one molecule, or may undergo condensation between two molecules, resulting in the formation of an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. can be used. Among these, preferred are melamine etherified with alkyl groups such as hexamethoxymethyl melamine and hexabutoxymethyl melamine.

The heat-reactive composition of the present invention can be dissolved or dispersed in a solvent in the case of a solvent-free solid state, and then coated by a spin coater, a roll coater, a bar coater, or a die nozzle. It can be applied to support substrates such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc., by known methods such as machine, curtain coater, slit coater, dip coater, various printing, dipping, etc. . In addition, it can also be temporarily applied to a supporting substrate such as a film, and then transferred to another supporting substrate. The application method is not limited.

The heating conditions for curing the heat-reactive composition of the present invention are 1-100 minutes at 70-250°C. It can be pressurized after pre-baking, post-baking, or baking at different temperatures in several stages.

The heating conditions vary depending on the types and blending ratios of the ingredients. For example, at 70~180°C, 5~15 minutes for an oven, and 1~5 minutes for a hot plate. After that, in order to harden the coating film, heat treatment is performed at 100 to 250°C, preferably 180 to 250°C, more preferably 200 to 250°C, if it is an oven, heat treatment is performed for 30 to 90 minutes, and if it is a hot plate, it is heated Heat treatment for 5-30 minutes to obtain a cured film.

The heat-reactive composition (or its hardened product) of the present invention can be used in heat-reactive coatings or varnishes, heat-reactive adhesives, printed substrates, or color televisions, PC monitors, personal digital assistants, digital cameras, etc. Color filters in liquid crystal display panels, color filters in CCD image sensors, electrode materials for plasma display panels, powder coating Cloth, printing ink, printing plate, adhesive, dental composition, three-dimensional molding resin, gel coat, photoresist for electronic engineering, plating resist, etching resist, both liquid and dry film , Solder resists, used to manufacture color filters for various display purposes or used to form structures in the manufacturing steps of plasma display panels, electroluminescent display devices, and LCDs, used to seal electrical and electronic parts The composition, solder resist, magnetic recording material, micro mechanical parts, waveguide, optical switch, plating mask, etching mask, color test system, glass fiber cable coating, screen printing template, for borrowing Materials for producing three-dimensional objects from stereo lithography, materials for holographic recording, image recording materials, micro electronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, printed wiring It is used in various applications such as photoresist materials for boards, photoresist materials for UV and visible laser direct imaging, photoresist materials or protective films used in the formation of the dielectric layer in the successive build-up of printed circuit boards. There are no special restrictions.

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

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

The wavelength cut filter of the present invention has a coating (B) obtained from the thermoreactive composition of the present invention on one side of a glass substrate (A), and an infrared reflective film (A) on the other side of the glass substrate (A) C) person. The coating (B) and the infrared reflective film (C) are respectively laminated on each surface of the glass substrate (A). As shown in Figure 1, the side having the coating (B) obtained from the thermoreactive composition of the present invention can be used as the incident side of light, or as shown in Figure 2, an infrared reflective film (C) can be provided. The side is the incident side of light. Hereinafter, each layer will be described in order.

<Glass substrate (A)>

As the glass substrate (A) used in the wavelength cut filter of the present invention, it can be appropriately selected and used from transparent glass materials in the visible region. Soda-lime glass, white board glass, borosilicate glass, and reinforced glass can be used. Glass, quartz glass, phosphate-based glass, etc., among which soda-lime glass is cheap and easy to obtain, so preferred, white board glass, borosilicate glass and strong Chemical glass is easily available, has high hardness, and is excellent in workability, so it is preferred.

Furthermore, if the glass substrate (A) is pretreated with a silane coupling agent, etc., and then the coating solution containing the thermoreactive composition of the present invention is applied to form the coating layer (B), the coating solution after drying contains The dye coating (B) has improved adhesion to the glass substrate.

Examples of the silane coupling agent include: γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl) Epoxy functional alkoxysilanes such as ethyl trimethoxysilane, N-β (aminoethyl)-γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, N -Phenyl-γ-aminopropyl trimethoxysilane and other amino functional alkoxysilanes, γ-mercaptopropyl trimethoxysilane and other mercapto functional alkoxysilanes, etc.

In addition, there may be a base layer between the glass substrate (A) and the coating layer (B). The base layer is obtained by applying the following coating liquid by the coating method shown below, and the thickness is 30~1000nm. The above coating liquid is formed by agglomerating primary particles with an average primary particle size of 5~100nm The aggregates of metal oxide fine particles with an average secondary particle size of 20 to 250 nm are dispersed in the solvent shown below. The aggregate of the metal oxide fine particles is preferably 0.1 to 50% by mass relative 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 in terms of weight reduction and strength, it is more preferably 0.05 to 1 mm.

In the present invention, the substrate is a glass plate, so it can be directly coated on the substrate and dried and then cut and processed, and the structure or manufacturing process becomes simpler. In addition, since the substrate is a glass plate, it has higher heat resistance (resistance to reflow at 260°C) compared to the case of plastic.

<Coating (B)>

The coating layer (B) obtained by the thermoreactive composition of the present invention used in the wavelength cut filter of the present invention can be applied to the glass substrate (A) by applying the thermoreactive composition of the present invention as described above Formed from above. The obtained coating film may be heated as necessary to harden it.

When the thickness of the dye-containing coating (B) is 1 to 200 μm, a uniform film can be obtained, which is advantageous for thinning, so it is preferable. If it is less than 1 μm, the function may not be sufficiently exhibited; 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 the function of blocking light in the wavelength region of 700 to 1200 nm, and can be formed by alternately laminating low refractive index layers and high refractive index layers The dielectric multilayer film is formed.

As the material constituting the low refractive index layer, a material having a refractive index of 1.2 to 1.6 can be used, for example, silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride, etc. can be used.

As the material constituting the high refractive index layer, a material with a refractive index of 1.7 to 2.5 can be used, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, sulfide Zinc, indium oxide, etc., in addition to these, those containing these as main components and containing a small amount of titanium oxide, tin oxide, cerium oxide, and the like can be mentioned.

Regarding the method of laminating the above-mentioned low-refractive index layer and high-refractive index layer, there is no particular limitation as long as a dielectric multilayer film formed by laminating these layers can be formed. For example, it can be exemplified on a glass substrate by a CVD method , Sputtering method, vacuum evaporation method, etc. to form a dielectric multilayer film formed by alternately laminating low-refractive index layers and high-refractive index layers. In addition, a dielectric multilayer film may be formed in advance, and it may be bonded to the glass substrate with an adhesive.

The number of layers is 10 to 80, and it is preferably 25 to 50 in terms of manufacturing process and strength.

The thickness of the low refractive index layer and the high refractive index layer are usually 1/10 to 1/2 of the thickness of the wavelength λ (mm) of the light to be blocked. If the thickness is less than 0.1λ or greater than 0.5λ, the optical film thickness represented by the product (nd) of the refractive index (n) and the physical film thickness (d) and the multiple of λ/4 will have a large difference, and the specificity cannot be achieved. Interruption or transmission of wavelength.

As the above-mentioned infrared reflective film (C), in addition to the above-mentioned dielectric multilayer film, it may be Use an organic material such as a film containing a dye with a maximum absorption wavelength of 700 to 1100 nm, a polymer laminate, or a film formed by coating a cholesteric liquid crystal.

The wavelength cut filter of the present invention preferably has a transmittance satisfying the following (i) to (iii). Furthermore, the transmittance was measured by the UV-Vis-NIR Spectrophotometer V-570 manufactured by JASCO Corporation.

(i) In the wavelength range of 430~580nm, the average transmittance when measured from the vertical direction of the wavelength cut filter (the direction perpendicular to the surface of the glass substrate, the same below) is 75% or more .

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

(iii) In the wavelength range of 560~800nm, when the transmittance is measured from the vertical direction of the wavelength cut filter, the value of the wavelength (Ya) at which 80% of the wavelength is perpendicular to the wavelength cut filter When measuring at an angle of 35°, the absolute value of the difference in the value (Yb) of the wavelength at which the transmittance becomes 80% is 30 nm or less.

In the wavelength cut filter, if the average value of the transmittance in the wavelength range of 430~580nm in the above (i) is less than 75%, it will basically not transmit the light in the visible light region. (i) The average transmittance in the wavelength range of 430~580nm is more preferably 80% or more. If the average value of the transmittance in the wavelength of 800~1000nm of the above (ii) exceeds 5%, there is a risk that since the light in the infrared region is hardly cut off, it is not easy to correct the sensitivity in a way close to human visibility. (ii) The average transmittance in the wavelength of 800~1000nm is more preferably 1% or less.

In addition, if the absolute value of the difference between Ya and Yb in (iii) exceeds 30 nm, there is a possibility that the dependence of the incident angle of light will increase, and the characteristics of the wavelength cut filter will change due to the incident angle of light. , So there are disadvantages such as changes in the color tones in the center and the periphery of the screen. (iii) The absolute value of the difference between Ya and Yb is more preferably 5 nm or less, and still more preferably 3 nm or less.

As the specific application of the wavelength cut filter of the present invention, an automobile or a building can be cited Heat ray cut filter installed on the window glass of objects; CCD or CMOS in solid-state imaging devices such as digital still cameras, digital video cameras, surveillance cameras, vehicle cameras, network cameras, mobile phone cameras, etc. Visibility correction applications for solid-state imaging elements; automatic exposure meters; display devices such as plasma displays, etc.

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

The solid-state imaging device of the present invention has the same structure 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 can be fixed on the light incident side of the solid-state image sensor 2 to a part other than the solid-state image sensor as shown in FIGS. 5 and 6, or as shown in FIGS. 3 and 4. It is directly fixed to the front surface of the solid-state imaging element 2.

The solid-state imaging device of the present invention may be equipped with optical low-pass filters, anti-reflection filters, color filters, etc., as required, and the order of stacking these is not particularly limited.

As shown in FIGS. 3 and 4, regarding the camera module of one of the solid-state imaging devices of the present invention, the wavelength cut filter 1 of the present invention is laminated on the solid-state imaging device on the light incident side of the solid-state imaging device 2. Give specific instructions.

3 and 4 are cross-sectional views showing a configuration of a camera module, which is one of the solid-state imaging devices of the present invention. Regarding the camera module, the solid-state imaging element 2 and the wavelength-cutting filter 1 are formed on one surface of the solid-state imaging element 2 except for the light-receiving portion 3, and the solid-state imaging element 2 and the wavelength-cutting filter 1 are combined by the adhesive 4 The solid-state imaging element 2 is formed in a rectangular shape in plan view on a semiconductor substrate, and the wavelength cut filter 1 is on the opposite side of the light-receiving portion 3 of the solid-state imaging element 2. Coating (B)/glass substrate (A)/infrared reflective film (C) wavelength cut filter 1 (Figure 3), or laminated with infrared reflective film (C)/glass substrate (A)/containing dye The coating (B) wavelength cut filter 1 (Figure 4). The camera module, which is a solid-state imaging device, captures light from the outside through the wavelength cut filter 1 and receives the light through a light-receiving element arranged in the light-receiving section 3 of the solid-state imaging element 2.

As shown in FIGS. 5 and 6, regarding the camera module, which is one of the solid-state imaging devices of the present invention, the wavelength cut filter 1 of the present invention is fixed on the light-incident side of the solid-state imaging device 2 to a part other than the solid-state imaging device. The situation will be explained in detail.

5 and 6 are cross-sectional views showing a configuration of a camera module, which is one of the solid-state imaging devices of the present invention. In the camera module, a solid-state imaging element 2 is formed on one surface of the solid-state imaging element 2 except for the light-receiving portion 3, and the solid-state imaging element 2 is formed in a rectangular shape in plan view on a semiconductor substrate. 2 is on the opposite side of the light-receiving part 3 of the solid-state imaging element 2. From the light incident side, it is laminated with a dye-containing coating (B), a glass substrate (A), and an infrared reflective film (C). The wavelength cut filter Sheet 1 (Figure 5), or a wavelength cut filter 1 (Figure 6) with an infrared reflective film (C), a glass substrate (A), and a dye-containing coating (B) laminated in sequence. A camera module as a solid-state imaging device captures light from the outside through the wavelength cut filter 1, and receives the light through a light-receiving element arranged in the light-receiving portion 3 of the solid-state imaging element 2.

As the adhesive 4, UV curable adhesives such as acrylic resins and epoxy resins, or thermosetting resins can be used. After the adhesive 4 is uniformly coated, a well-known photolithography technique can be used to apply the adhesive 4 if necessary. Patterning is performed, and bonding is performed by thermal hardening. When bonding, it can also be vacuum pressurized after bonding in a vacuum environment.

The mounting substrate 8 uses a hard substrate such as a glass epoxy substrate or a ceramic substrate, and is provided with a control circuit for controlling the solid-state imaging element 2.

The solid-state imaging element 2 is arranged on the mounting substrate 8, and then the adhesive 4 is pre-coated on the position of the mounting substrate 8 where the lens holder 7 is fixed.

The lens cover 6 protects the lens 5. In addition, the lens holder 7 holds the lens 5 and includes a box-shaped base portion 7 a that is mounted on the mounting substrate 8 and covers the solid-state imaging element 2, and a cylindrical lens barrel portion 7 b that holds the lens 5.

Then, the lens holder 7 is arranged on the mounting substrate 8 in such a way that it is in contact with the adhesive 4 applied on the lower end surface of the lens holder 7, and then the light receiving portion 3 of the solid-state imaging element 2 and the lens holder Adjust the position of the lens holder 7 in such a way that the distance of the lens 5 in 7 is the same as the focal length of the lens 5.

After adjusting the position of the lens holder 7, ultraviolet rays are irradiated to the adhesive 4 to harden the adhesive 4, so that the camera module can be manufactured.

It is also possible to heat the entire mounting substrate 8 to which the lens holder 7 is fixed at about 85° C., and to cure the adhesive 4 sufficiently by thermal curing.

Furthermore, in the manufacturing method of the camera module, since the step of irradiating ultraviolet rays includes the step of heating the entire mounting substrate 8, the lens holder 7, the lens 5, and the wavelength cut filter 1 all need to be more heat-resistant. High material. Specifically, in addition to the heating for thermally hardening the adhesive 4 as described above, it is ideal to heat and melt a plurality of solders arranged on the lower surface of the mounting substrate 8 at about 260°C to be soldered to other substrates. It is formed by a material with reflow resistance.

Example

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

[Manufacturing Example 1] Preparation of resin (β) 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), and a radical polymerization initiator was added to the solution. 4 parts by mass of azobisisobutyronitrile were stirred at 80°C 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 and stirred at 120° C. for 3 hours to obtain resin (β) No. 1.

The resin (β) No.1 is 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 The group represented by the formula (n), Z ¹ and Z ² are direct bonds), R ¹ is an alkyl group with 1 to 8 carbon atoms, R ² to R ³ are hydrogen atoms, and R ⁴ is a methyl group. (β).

[化20]

[Manufacturing Example 2] Preparation of resin (β) No.2

Dissolve 20 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate, and 50 parts by mass of benzyl methacrylate in 500 parts by mass of cyclohexanone, and add azobisisobutyl as a radical polymerization initiator 4 parts by mass of nitrile was stirred at 80°C for 3 hours. Then, 20 parts by mass of acrylic acid was added and stirred at 120°C for 3 hours to obtain resin (β) No. 2.

[Manufacturing Example 3] Preparation of resin (β) No.3

Dissolve 50 parts by mass of glycidyl methacrylate, 5 parts by benzyl methacrylate, and 40 parts by mass of styrene in 500 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA), and add as free 1 part by mass of 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, which is a base polymerization initiator, was stirred at 140°C for 2 hours. Next, 20 parts by mass of acrylic acid was added and stirred at 120°C for 3 hours to obtain resin (β) No. 3.

[Manufacturing Example 4] Preparation of resin (β) No. 4

Dissolve 40 parts by mass of glycidyl methacrylate, 5 parts by benzyl methacrylate, and 40 parts by mass of styrene in 500 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA), and use as free 10 parts by mass of azobisisobutyronitrile as a base polymerization initiator was stirred at 80°C for 3 hours. Next, 20 parts by mass of acrylic acid was added and stirred at 120°C for 3 hours to obtain resin (β) No. 4.

[Manufacturing Example 5] Preparation of resin (β) No.5

Dissolve 40 parts by mass of glycidyl methacrylate, 5 parts by benzyl methacrylate, and 40 parts by mass of styrene in 500 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA), and add as free 5 parts by mass of azobisisobutyronitrile as a base polymerization initiator was stirred at 80°C for 3 hours. Next, 20 parts by mass of acrylic acid was added and stirred at 120°C for 3 hours. Then, 5 parts by mass of tetrahydrophthalic anhydride was added, and after stirring at 120°C for 3 hours, a resin was obtained (β)No.5.

[Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-5] Preparation of thermoreactive composition No.1 to No.11 and comparative composition No.1 to No.5

<Step 1> Preparation of dye solution No.1~No.10 and comparison dye solution No.1~No.5

The solvent (σ) is added to the cyanine compound (α) shown in [Table 1] to [Table 3] as the component (A), stirred and dissolved to obtain dye liquid No.1 to No.10 And compare the dye solution No.1~No.5.

<Step 2> Preparation of thermoreactive composition No.1~No.10 and comparative composition No.1~No.5

According to the formulation of [Table 1] ~ [Table 3], add resin (β) and polymerization initiator (γ) ( Or (γ ' )), monomers with unsaturated bonds (ω) and solvent (σ) and stirred to prepare thermoreactive compositions No.1 to No.10 and comparative compositions No.1 to No.5 .

A-1: Hexafluorophosphate of compound No.76

A-2: Compound No.100 of hexafluorophosphate

A-3: Bis(trifluoromethanesulfonyl)imidate of compound No.100

A-4: Bis(trifluoromethanesulfonyl)imidate of compound No.102

A-5: Bis(trifluoromethanesulfonyl)imidate of compound No.103

B-1: Resin (β) No. 1 obtained by Production Example 1

B-2: ACA Z251 (propenylated acrylate manufactured by Daicel Allnex)

B-3: ACA Z250 (propenylated acrylate manufactured by Daicel Allnex)

B-4: ACA 200M (propenylated acrylate manufactured by Daicel Allnex)

B-5: SPC-1000 (Acrylic resin manufactured by Showa Denko Corporation)

B-6: SPC-3000 (Acrylic resin manufactured by Showa Denko Corporation)

B-7: Resin (β) No. 2 obtained in Production Example 2

B-8: Resin (β) No. 3 obtained in Production Example 3

B-9: Resin (β) No. 4 obtained in Production Example 4

B-10: Resin (β) 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 (an oil-soluble azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.)

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

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

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

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

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

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

E-1: Cyclohexanone

E-2: Diacetone alcohol

E-3: Methyl ethyl ketone

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

The thermoreactive composition No. 1 to No. 10 obtained in Examples 1-1 to 1-10 and the comparative composition No. 1 to No. 5 obtained in Comparative Examples 1-1 to 1-5 were respectively Coated on a glass substrate under the conditions of 410 rpm×7 seconds, and dried on a hot plate (90°C, 10 minutes). After drying, the coating film was cured by heating at 150°C for 10 minutes on a hot plate. After hardening The coating film was heated under the conditions of 150°C×1 hour to evaluate the heat resistance. The evaluation was performed by calculating the transmittance change of the maximum absorption wavelength before and after heating. The transmittance change amount is calculated by the following formula.

Transmittance change (%)=(X-Y)/X×100 (X is the transmittance of the maximum absorption wavelength before heating, and Y is the transmittance of the wavelength measured after heating)

The results are shown in [Table 4].

(In Table 4, "-" means that the film cannot be formed uniformly, so it cannot be evaluated)

According to the results of the above [Table 4], it can be seen that the heat-reactive composition of the present invention has less color difference change and higher heat resistance.

[Examples 2-1~2-10] Manufacturing of wavelength cut filter No.1~No.10

On one side of a glass substrate (A) with a thickness of 100μm, alternately laminate silicon _{dioxide (SiO 2} ) and titanium oxide (TiO ₂ ) layers by vacuum evaporation to form a thickness of approximately 3μm with a total of 30 layers The infrared reflective film (C).

On the obtained glass substrate (A) with infrared reflecting film (C) applied and infrared reflecting film On a different surface, the heat-reactive composition (coating liquid) No. 1 to No. 10 obtained in Examples 1-1 to 1-10 was applied by bar coater #30 (film thickness 10μm). After that, it was dried at 100°C for 10 minutes to produce wavelength cut filters No.1 to No.10.

[Evaluation examples 2-1~2-10]

Regarding the wavelength cut filter No. 1 to No. 10 of the present invention obtained in Examples 2-1 to 2-10, find i) in the wavelength range of 430 to 580 nm, from the vertical of the wavelength cut filter The average value of the transmittance when measured in the direction, ii) the average value of the transmittance when measured from the vertical direction of the wavelength cut filter in the wavelength of 800~1000nm, and iii) the average value of the transmittance in the wavelength of 560~800nm In the range, the value of the wavelength (Ya) at which the transmittance becomes 80% when measured from the vertical direction of the wavelength cut-off filter and measured from an angle of 35° relative to the vertical direction of the wavelength cut-off filter In this case, the transmittance becomes the absolute value of the difference between the wavelength value (Yb) of 80%. The results are shown in [Table 5]. In addition, the above-mentioned transmittance was measured by the UV-Vis-NIR Spectrophotometer V-570 manufactured by JASCO Corporation.

According to the results of the above [Table 5], it can be seen that the wavelength cut filter of the present invention has a higher transmittance in the wavelength range of 430~580nm, and a lower transmittance in the wavelength of 800~1000nm. And the incidence angle dependence is low.

Based on the above results, it can be seen that the wavelength cutoff of the present invention is characterized by forming a coating layer (B) containing a dye on one side of the glass substrate (A) and having an infrared reflective film (C) on the other side of the glass substrate (A) The incident angle dependence of the filter is relatively low. Therefore, the wavelength cut filter of the present invention is useful in solid-state imaging devices and camera modules.

Claims (8)

A thermoreactive composition containing at least one cyanine compound (α), a resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (γ), relative to the above resin ( β) 100 parts by mass, the content of at least one (α) of the above-mentioned cyanine compound is 0.01 parts by mass to 10 parts by mass, and the content of the above-mentioned resin (β) is 30-99 parts by mass in the solid content of the thermoreactive composition % By mass, the content of the thermal polymerization initiator (γ) in the solid content of the thermoreactive composition is 0.1-30% by mass, and at least one of the cyanine compounds (α) includes the following general formula The compound represented by (II); and the above-mentioned resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group has a unit represented by the following general formula (I-1), and the following general formula (I-2) ) And the unit represented by the following general formula (I-3);

(In the formula, ring A and ring A'each independently represent a benzene ring, a naphthalene ring, a phenanthrene ring, or a pyridine ring, and R ¹¹ and R ^11' each independently represent a hydroxyl group, a halogen atom, a nitro group, a cyano group, and -SO ₃ H, carboxyl group, amino group, amide group, metallocene group, aryl group with 6 to 30 carbon atoms, aryl alkyl group with 7 to 30 carbon atoms or alkyl group with 1 to 8 carbon atoms, X ¹¹ And X ^11' each independently represent an oxygen atom, a sulfur atom, a selenium atom, -CR ²³ R ²⁴ -, a cycloalkane-1,1-diyl group with 3 to 6 carbon atoms or -NR ²⁵ -, R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, a amide group, a metallocene group, and an aryl group with 6 to 30 carbon atoms , C7-30 arylalkyl group or C1-C8 alkyl group, Y ¹¹ and Y ^11' each independently represent a hydrogen atom, or can also be passed through a hydroxyl group, a halogen atom, a nitro group, or a cyano group , -SO ₃ H, carboxyl, amino, amide or metallocene substituted aryl group with 6 to 30 carbon atoms, aryl alkyl with 7 to 30 carbon atoms or one with 1 to 8 carbon atoms Alkyl groups, the aryl groups, arylalkyl groups and alkyl groups in the above-mentioned R ¹¹ , R ^11' , Y ¹¹ , Y ^11' , R ²³ , R ²⁴ and R ²⁵ also exist through hydroxyl, halogen atom, nitro, cyanide the substituent groups, -SO ₃ H, carboxyl, amino, acyl group or a metallocene-based case, the above-described ^{R 11, R 11 ', Y} 11, Y 11', R 23, R 24 and R ²⁵ are the aryl The methylene group in the alkyl group and the alkyl group also exists and is substituted with -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-,- In the case of NHCO-, -N=CH- or carbon-carbon double bond, Q represents a methine chain with 7 or 9 carbon atoms and a linking group that may include a ring structure in the chain. The hydrogen in the methine chain Atoms can also be substituted with hydroxyl, halogen, cyano, or aryl. r and r'represent 0 or the number of substitutions in ring A and ring A', An ^q- represents an anion of q valence, and q represents 1 or 2, 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 represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or 7 ~30 Arylalkyl groups, the alkyl groups, aryl groups and arylalkyl groups may also be substituted by halogen atoms, hydroxyl groups or nitro groups, and the methylene groups in the alkyl groups and arylalkyl groups may also be substituted by When substituted with a bonding group of -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination thereof, R ² , R ³ and R ⁴ are each independently a hydrogen atom Or methyl). A thermoreactive composition, characterized in that it contains at least one cyanine compound (α), a resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (γ) relative to The resin (β) is 100 parts by mass, the content of at least one (α) of the cyanine compound is 0.01 parts by mass to 10 parts by mass, and the content of the resin (β) in the solid content of the thermoreactive composition is 30~99% by mass, the content of the thermal polymerization initiator (γ) in the solid content of the thermally reactive composition is 0.1-30% by mass, and the thermally reactive composition is used to form a glass substrate ( A) The above-mentioned coating (B) of a wavelength cut filter with a coating (B) on one side and an infrared reflective film (C) on the other side of the glass substrate (A), and at least an ethylenically unsaturated bond and hydrophilic The resin (β) of the sex group 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) ；

(In the formula, X ¹ represents a hydrogen atom or a methyl group, Y ¹ is a divalent bonding group, R ¹ represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or 7 ~30 Arylalkyl groups, the alkyl groups, aryl groups and arylalkyl groups may also be substituted by halogen atoms, hydroxyl groups or nitro groups, and the methylene groups in the alkyl groups and arylalkyl groups may also be substituted by When substituted with a bonding group of -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination thereof, R ² , R ³ and R ⁴ are each independently a hydrogen atom Or methyl). The thermally reactive composition according to claim 1 or 2, wherein the thermal polymerization initiator (γ) is an azo thermal polymerization initiator. A thermoreactive composition, characterized in that it contains at least one cyanine compound (α), a resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group, and a thermal polymerization initiator (γ) relative to 100 parts by mass of the resin (β), the content of at least one (α) of the cyanine compound is 0.01 parts by mass to 10 parts by mass, and the content of the resin (β) in the solid content of the thermoreactive composition is 30~99% by mass, the content of the thermal polymerization initiator (γ) is 0.1-30% by mass in the solid content of the thermally reactive composition, and the thermal polymerization initiator (γ) is azo thermal polymerization The initiator, and the resin (β) having at least an ethylenically unsaturated bond and a hydrophilic group has a unit represented by the following general formula (I-1), a unit represented by the following general formula (I-2), and The unit represented by the following general formula (I-3);

(In the formula, X ¹ represents a hydrogen atom or a methyl group, Y ¹ is a divalent bonding group, R ¹ represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or 7 ~30 Arylalkyl groups, the alkyl groups, aryl groups and arylalkyl groups may also be substituted by halogen atoms, hydroxyl groups or nitro groups, and the methylene groups in the alkyl groups and arylalkyl groups may also be substituted by When substituted with a bonding group of -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination thereof, R ² , R ³ and R ⁴ are each independently a hydrogen atom Or methyl). A wavelength cut filter, characterized in that: on one side of a glass substrate (A) there is a coating (B) obtained from the thermally reactive composition as claimed in any one of claims 1 to 4, and the coating (B) is on the glass substrate (A) The other side of (A) has an infrared reflective film (C). For example, the wavelength cut-off filter of claim 5, in which the transmittance satisfies the following (i)~(iii): (i) In the range of wavelength 430~580nm, it is measured from the vertical direction of the wavelength cut-off filter The average value of the transmittance is 75% or more; (ii) The average value of the transmittance when measured from the vertical direction of the wavelength cut filter at a wavelength of 800 to 1000 nm is less than 5%; (iii) In the wavelength range of 560~800nm, when the transmittance is measured from the vertical direction of the wavelength cut filter, the value of the wavelength (Ya) at which the transmittance becomes 80% and the vertical direction relative to the wavelength cut filter is 35° The absolute value of the difference of the wavelength (Yb) at which the transmittance becomes 80% when the angle is measured is 30nm or less. A solid-state imaging device, characterized by being provided with a wavelength cut-off filter as claimed in claim 5 or 6. A camera module, characterized in that it is provided with a wavelength cut-off filter as in claim 5 or 6.

Images