CN107531857A - Heat reactivity composition - Google Patents

Abstract

The heat reactivity composition of the present invention contains：At least one of cyanine compound (α), the resin (β) and thermal polymerization (γ) at least with ethylenic unsaturated bond and hydrophilic radical.The unit that resin (β) preferably comprises the unit of following formulas (I 1) expression, the unit that following formulas (I 2) represent and following formulas (I 3) represent.Thermal polymerization (γ) is preferably azo thermal polymerization.In following formula, X¹、Y¹、R¹~R⁴Definition with reference to specification.

Description

Heat reactivity composition

Technical field

The present invention relates to the resin containing cyanine compound, an intramolecular with ethylenic unsaturated bond and hydrophilic radical With the heat reactivity composition of thermal polymerization and the wavelength cut-off filter of the heat reactivity composition is used.

Background technology

Digital camera, video camera, mobile phone are with the sense of the solid-state imager (CCD and C-MOS etc.) used in camera etc. The ultraviolet region from the wavelength of light is spent until region of ultra-red.On the other hand, the visibility of people is only the visibility region of the wavelength of light. Therefore, by setting infrared cut off filter between pick-up lens and solid-state imager, approached with the visibility with people Mode correct the sensitivity of solid-state imager.

As infrared cut off filter, it is known that combine the layer containing the material without absorption characteristic and be laminated into more Layer simultaneously make use of the Reflection Filter of their specific refractivity or transparency carrier is contained or combine the suction of light absorber Receipts type filter.

For absorption-type filter, heating when manufacture etc. being present and causing the bad of light absorber Change, cause infrared ray breaking capacity decline the problem of.

The heat reactivity composition containing thermal polymerization has been recorded in patent document 1 and 2.In addition, in patent document 3 Describe the resin that there is ethylenic unsaturated bond and hydrophilic radical containing cyanine compound, an intramolecular and photopolymerization triggers The composition of agent.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2007-256865 publications

Patent document 2：US2010051883A1

Patent document 3：Japanese Unexamined Patent Publication 2013-173848 publications

The content of the invention

Invent problem to be solved

But the composition described in patent document 1~3 is in terms of heat resistance and insufficient.

It is therefore an object of the present invention to provide a kind of heat reactivity composition of excellent heat resistance.In addition, the present invention's is another One purpose is to provide a kind of wavelength cut-off filter for having used above-mentioned heat reactivity composition.

Means for solving the problems

Further investigation has been repeated in the present inventor, as a result finds, has alkene using containing cyanine compound, an intramolecular Wavelength obtained from the heat reactivity composition of the resin and thermal polymerization of keyed unsaturated bond and hydrophilic radical is cut Only the heat resistance of filter will not decline, and be suitable for the wavelength cut-off filter used in solid camera head etc., so as to complete The present invention.

The present invention provides a kind of heat reactivity composition, and it contains：At least one of cyanine compound (α), at least have There are the resin of ethylenic unsaturated bond and hydrophilic radical (β) and thermal polymerization (γ).

In addition, the present invention provide it is a kind of using wavelength cut-off filter obtained from above-mentioned heat reactivity composition and Its solid camera head and camera module are used.

Invention effect

There is resin and the thermal polymerization of ethylenic unsaturated bond and hydrophilic radical containing cyanine compound, an intramolecular The heat reactivity composition of the invention of initiator has excellent heat resistance.In addition, its solidfied material is suitable for wavelength cut-off filter Light device.

Brief description of the drawings

Fig. 1 is the schematic section of one of the layer construction for representing the wavelength cut-off filter of the present invention.

Fig. 2 is the schematic section of another of the layer construction for representing the wavelength cut-off filter of the present invention.

Fig. 3 is cutting for a form of the composition of the camera module of one of the solid camera head for being denoted as the present invention Face figure.

Fig. 4 is the sectional view of another form of the composition for representing camera module.

Fig. 5 is the sectional view of another form of the composition for representing camera module.

Fig. 6 is the sectional view of another form of the composition for representing camera module.

Embodiment

Hereinafter, the heat reactivity composition of the present invention is illustrated based on preferable embodiment.

The heat reactivity composition of the present invention contains：At least one of cyanine compound (α) is (also referred to as cyanine below Compound (α)), at least there is resin (β) (being also referred to as resin (β) below), the hot polymerization of ethylenic unsaturated bond and hydrophilic radical Close initiator (γ) and the monomer (ω) and solvent (σ) with unsaturated bond further added as needed.Below to each Composition illustrates successively.

<Cyanine compound (α)>

The cyanine compound (α) used in the heat reactivity composition of the present invention is not particularly limited, and can use conventional Known cyanine compound, but from the viewpoint of easiness is obtained, preferably by the compound of following logical formula (II)s expressions.

[changing 1]

(in formula, ring A and ring A ' separately represent phenyl ring, naphthalene nucleus, phenanthrene ring or pyridine ring,

R¹¹And R^11’Separately represent hydroxyl, halogen atom, nitro, cyano group ,-SO₃H, carboxyl, amino, amide groups, cyclopentadienyl The aralkyl or carbon number that aryl that Metal Substrate (metallocenyl), carbon number are 6~30, carbon number are 7~30 For 1~8 alkyl,

X¹¹And X¹¹' separately represent oxygen atom, sulphur atom, selenium atom ,-CR²³R²⁴-, carbon number be 3~6 ring Alkane -1,1- diyl or-NR²⁵-,

R²¹、R²²、R²³、R²⁴And R²⁵Separately represent hydrogen atom, hydroxyl, halogen atom, nitro, cyano group ,-SO₃H, carboxylic The aralkyl or carbon atom that aryl that base, amino, amide groups, Metallocenyl, carbon number are 6~30, carbon number are 7~30 Number is 1~8 alkyl,

Y¹¹And Y¹¹' separately represent hydrogen atom or can be by hydroxyl, halogen atom, nitro, cyano group ,-SO₃H, carboxyl, Amino, amide groups or Metallocenyl substitution carbon number be 6~30 aryl, carbon number be 7~30 aralkyl or carbon Atomicity is 1~8 alkyl,

Above-mentioned R¹¹、R^11’、Y¹¹、Y¹¹'、R²¹、R²²、R²³、R²⁴And R²⁵In aryl, aralkyl and alkyl sometimes also by hydroxyl Base, halogen atom, nitro, cyano group ,-SO₃H, carboxyl, amino, amide groups or Metallocenyl substitution, above-mentioned R¹¹、R^11’、Y¹¹、Y¹¹'、 R²¹、R²²、R²³、R²⁴And R²⁵In aralkyl and alkyl in methylene sometimes also by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,- SO₂- ,-NH- ,-CONH- ,-NHCO- ,-N=CH- or carbon-to-carbon double bond displacement,

Q represents to form carbon number as that can contain the linker of circular structure, this time in 1~9 methine chain and chain Hydrogen atom in methyl chain can also be substituted by hydroxyl, halogen atom, cyano group ,-NRR ', aryl, aralkyl or alkyl ,-the NRR ', Aryl, aralkyl and alkyl can also further by hydroxyl, halogen atom, cyano group or-NRR ' substitute, can also by-O- ,-S- ,- CO-、-COO-、-OCO-、-SO₂- ,-NH- ,-CONH- ,-NHCO- ,-N=CH- or-CH=CH- interrupt,

R and R ' represents aryl, aralkyl or alkyl,

R and r ' represents 0 or the commutable quantity on ring A and ring A ',

An^q-The anion of q valencys is represented, q expressions 1 or 2, p represent to remain electric charge into the coefficient of neutrality.)

As the R in above-mentioned logical formula (II)¹¹、R^11’And X¹¹And X^11’In R²³、R²⁴And R²⁵Represented halogen atom, with And can be to R¹¹、R^11’、R²³、R²⁴、R²⁵、Y¹¹、Y¹¹' the halogen atom that is substituted of represented aryl, aralkyl, alkyl, can be with Include fluorine atom, chlorine atom, bromine atoms, iodine atom.

As the R in above-mentioned logical formula (II)¹¹、R^11’And X¹¹And X^11’In R²³、R²⁴And R²⁵Represented amino and Can be to R¹¹、R^11’、R²³、R²⁴、R²⁵、Y¹¹、Y¹¹' the amino that is substituted of represented aryl, aralkyl, alkyl, it can enumerate Go out amino, ethylamino, dimethylamino, diethylamino, butylamino, clopentylamino, 2- ethylhexylaminos, 12 Alkyl amino, anilino-, chlorphenylamino, toluidino, anisidino, N- metlyl-phenylamines base, diphenyl amino, naphthyl Amino, 2- pyridinylaminos, methyloxycarbonylamino, phenoxycarbonylamino, acetyl-amino, benzoyl-amido, formyl Base amino, pivaloyl group amino, lauroyl amino, carbamoylamino, N, N- Dimethylaminocarbonyls amino, N, N- diethylaminocarbonyls amino, morpholino carbonyl amino, methyloxycarbonylamino, ethoxycarbonylamino group, tert-butoxy carbonyl Base amino, n-octadecane Epoxide carbonyl amino, N- methyl methoxycarbonylaminos, phenoxycarbonylamino, sulfamoyl ammonia Base, N, N- dimethylaminosulfonylaminos, Methylsulfonylamino, butyl sulfuryl amino, phenyl sulfonyl amino etc..

As the R in above-mentioned logical formula (II)¹¹、R^11’And X¹¹And X^11’In R²³、R²⁴And R²⁵Represented amide groups, with And can be to R¹¹、R^11’、R²³、R²⁴、R²⁵、Y¹¹、Y¹¹' the amide groups that is substituted of represented aryl, aralkyl, alkyl, can be with Include formamido, acetamido, ethyl acylamino, Isopropyl amide base, butyl amide base, octyl group amide groups, nonyl acyl Amido, decyl amide groups, undecyl amide groups, laurylamide base, hexadecyl amide base, octadecyl amide base, (2- ethylhexyls) amide groups, benzamido, trifluoroacetyl amido, phenyl-pentafluoride formamido, diformamide base, diacetayl amide Base, diethyl acylamino, diisopropylamide base, dibutylamide base, dioctyl amide groups, dinonyl amide groups, didecyl Amide groups, two (undecyl) amide groups, two (dodecyl) amide groups, two (2- ethylhexyls) amide groups, dibenzamide Base, two (trifluoroacetyl) amidos, two (phenyl-pentafluoride formyl) amidos etc..

As the R in above-mentioned logical formula (II)¹¹、R^11’And X¹¹And X^11’In R²³、R²⁴And R²⁵Represented Metallocenyl, And can be to R¹¹、R^11’、R²³、R²⁴、R²⁵、Y¹¹、Y¹¹' the Metallocenyl that is substituted of represented aryl, aralkyl, alkyl, Ferrocenyl, dicyclopentadienyl nickel base, zirconocene base, titanocenes base, hafnocene base etc. can be included.

As the R in above-mentioned logical formula (II)¹¹、R^11’、Z¹¹、Z¹²、Z¹³And Y¹¹、Y¹¹' and X¹¹And X^11’In R²³、R²⁴With R²⁵Represented carbon number is 6~30 aryl, can include phenyl, naphthyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- Aminomethyl phenyl, 4- ethenylphenyls, 3- isopropyl phenyls, 4- isopropyl phenyls, 4- butyl phenyls, 4- isobutyl phenenyls, uncle 4- Butyl phenyl, 4- hexyls phenyl, 4- cyclohexyl phenyls, 4- octyl phenyls, 4- (2- ethylhexyls) phenyl, 4- stearyl benzene Base, 2,3- 3,5-dimethylphenyls, 2,4- 3,5-dimethylphenyls, 2,5- 3,5-dimethylphenyls, 2,6- 3,5-dimethylphenyls, 3,4- dimethyl benzenes Base, 3,5- 3,5-dimethylphenyls, 2,4- di-tert-butyl-phenyls, 2,5- di-tert-butyl-phenyls, 2,6- di-tert-butyl-phenyls, the uncles of 2,4- bis- Amyl group phenyl, 2,5- di-tert-pentyl-phenyls, the t-octyl phenyl of 2,5- bis-, 2,4- dicumylphenyls, 4- cyclohexyl phenyls, (1,1 '- Xenyl) -4- bases, 2,4,5- trimethylphenyls, ferrocenyl etc..

As the R in above-mentioned logical formula (II)¹¹、R^11’And Y¹¹、Y¹¹' and X¹¹And X^11’In R²³、R²⁴And R²⁵Represented Carbon number is 7~30 aralkyl, can include benzyl, phenethyl, 2- phenyl-propane -2- bases, diphenyl methyl, triphen Ylmethyl, styryl, cinnamyl, ferrocenyl methyl, ferrocenyl propyl group etc..

As the R in above-mentioned logical formula (II)¹¹、R^11’And Y¹¹、Y¹¹' and X¹¹And X¹¹' in R²³、R²⁴And R²⁵Represented Carbon number is 1~8 alkyl, can include methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, isobutyl Base, amyl group, isopentyl, tertiary pentyl, hexyl, 2- hexyls, 3- hexyls, cyclohexyl, 1- methylcyclohexyls, heptyl, 2- heptyl, 3- heptan Base, different heptyl, tertiary heptyl, 1- octyl groups, iso-octyl, t-octyl etc..

As above-mentioned R¹¹、R^11’And Y¹¹、Y¹¹' and X¹¹And X¹¹' in R²³、R²⁴And R²⁵In, can be former by hydroxyl, halogen Son, nitro, cyano group ,-SO₃Aryl, the carbon that H bases, carboxyl, amino, amide groups or the carbon number of Metallocenyl substitution are 6~30 The alkyl that the aralkyl and carbon number that atomicity is 7~30 are 1~20, can be included in above-mentioned R¹¹Deng explanation in it is listed Hydrogen atom in the aryl of act, aralkyl, alkyl and these groups is by hydroxyl, halogen atom, nitro, cyano group ,-SO₃H bases, carboxyl, Group after amino, amide groups or Metallocenyl substitution, the position of these substituents and quantity do not limit.

In addition, work as above-mentioned R¹¹、R^11’And Y¹¹、Y¹¹' and X¹¹And X¹¹' in R²³、R²⁴And R²⁵In aralkyl and alkyl In methylene by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-SO₂- ,-NH- ,-CONH- ,-NHCO- ,-N=CH- or carbon-to-carbon When double bond is replaced, the quantity of these displacements and position are arbitrary.

For example, the group substituted as the alkyl that above-mentioned carbon number is 1~8 by halogen atom, can include such as chlorine Methyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, nine fluorine butyl etc..

As above-mentioned carbon number be 1~8 alkyl by-O- interrupt group, can include methoxyl group, ethyoxyl, The alkane such as isopropoxy, propoxyl group, butoxy, amoxy, isoamoxy, hexyloxy, epoxide in heptan, octyloxy, 2- ethyl hexyl oxies Epoxide and 2- methoxy ethyls, 2- (2- methoxyl groups) ethoxyethyl group, 2- ethoxyethyl groups, 2- butoxyethyl groups, 4- methoxies Alkoxyalkyls such as base butyl, 3- methoxybutyls etc..

The group for being substituted and being interrupted by-O- by halogen atom as the alkyl that above-mentioned carbon number is 1~8, can be enumerated Go out such as chloromethoxy, dichloro methoxyl group, trichloromethoxy, fluoro-methoxy, difluoro-methoxy, trifluoromethoxy, nine fluorine Butoxy etc..

In above-mentioned logical formula (II), as X¹¹And X^11’Represented carbon number is 3~6 loop chain alkane -1,1- diyl, can To include cyclopropane -1,1- diyl, cyclobutane -1,1- diyl, 2,4- dimethylcyclobutanes -1,1- diyl, 3,3- dimethyl Cyclobutane -1,1- diyl, pentamethylene 1,1- diyls, hexamethylene -1,1- diyl etc..

Can in the methine chain and chain that are 1~9 as represented by the Q in above-mentioned logical formula (II), composition carbon number With the linker containing circular structure, any one group represented in following (Q-1)~(Q-11) is due to easy to manufacture Preferably.The carbon number in methine chain for being 1~9 on carbon number, does not include in methine chain or methine chain The carbon atom for the group that the ring structure contained is further substituted with is (for example, the carbon atom of two ends in linker (Q-1), following R¹⁴~R¹⁹, Z ' carbon atom).

[changing 2]

(in formula, R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And Z ' separately represent hydrogen atom, hydroxyl, halogen atom, cyano group ,- NRR ', aryl, aralkyl or alkyl, should-NRR ', aryl, aralkyl and alkyl can also by hydroxyl, halogen atom, cyano group or- NRR ' substitutes, can also be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-SO₂- ,-NH- ,-CONH- ,-NHCO- ,-N=CH- or- CH=CH- is interrupted, and R and R ' represent aryl, aralkyl or alkyl.)

As above-mentioned R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And halogen atom, aryl, aralkyl or the alkyl that Z ' is represented, Ke Yilie Enumerate in R¹¹Deng explanation in cited group, as R and R ' aryl, aralkyl or the alkyl that represent, can include R¹¹Deng explanation in cited group.

As the pAn in above-mentioned logical formula (II)^q-The anion of represented q valencys, can include methanesulfonic acid anion, ten Dialkyl group sulfonic acid anion, benzene sulfonate anion, toluenesulfonate anion, trifluoromethanesulfonic acid anion, naphthalene sulfonic acids anion, two Phenyl amine -4- sulfonic acid anions, 2- amino -4- methyl-5-chloros benzene sulfonate anion, 2- amino -5- nitrobenzene-sulfonic acids anion, Naphthalenedisulfonic acid anion, naphtholsulfonic acid anion, double (trifluoro methylsulfonyl) imines acid anions, Japanese Unexamined Patent Publication 10-235999 Number publication, Japanese Unexamined Patent Publication 10-337959 publications, Japanese Unexamined Patent Publication 11-102088 publications, Japanese Unexamined Patent Publication 2000- No. 108510 publications, Japanese Unexamined Patent Publication 2000-168223 publications, Japanese Unexamined Patent Publication 2001-209969 publications, Japanese Unexamined Patent Publication 2001-322354 publications, Japanese Unexamined Patent Publication 2006-248180 publications, Japanese Unexamined Patent Publication 2006-297907 publications, Japan are special Open flat 8-253705 publications, Japanese Unexamined Patent Application Publication 2004-503379 publications, Japanese Unexamined Patent Publication 2005-336150 publications, international public affairs The organic sulfonic acid anions such as the sulfonic acid anion described in No. 2006/28006 publication etc. are opened, can additionally include chloride Ion, bromide ion, iodide ion, fluoride ion, chlorate ions, thiocyanate ion, hexafluorophosphate ion, hexafluoro antimony Acid ion, tetrafluoro boric acid ion, octylphosphonic acid ion, dodecylphosphoric acid ion, octadecyl phosphate ion, phosphenylic acid from Son, nonyl phenyl phosphate ion, 2,2 '-di-2-ethylhexylphosphine oxide (4,6- di-tert-butyl-phenyl) phosphonic acids ion, four (pentafluorophenyl group) boric acid Ion, have make in excited state bioactive molecule deexcitation (being quenched) function quencher anion, in cyclopentadiene The metallocene compound anion such as the ferrocene with the anionic property group such as carboxyl or phosphonate group, sulfonic group, ruthenocene on ring Deng.

As the concrete example of the cyanine compound (α) used in the present invention, can include following compound Ns o.1~ 104.In addition, in following example, represented with the cyanine cation for eliminating anion.[changing 3]

[changing 4]

[changing 5]

[changing 6]

[changing 7]

[changing 8]

[changing 9]

[changing 10]

[changing 11]

[changing 12]

[changing 13]

In the compound that above-mentioned logical formula (II) represents, preferably following compound.

Ring A or ring A ' is the compound of phenyl ring or naphthalene nucleus.

R or r ' is 0~2 compound.

When r or r ' is more than 1, R¹¹And R^11’For halogen atom, nitro, carboxyl, ferrocenyl, unsubstituted carbon number Alkyl or carbon number for 1~8 (particularly 1~4) are the compound of the haloalkyl of 1~8 (particularly 1~4).

X¹¹And X^11'For oxygen atom, sulphur atom ,-CR²³R²⁴(particularly, R²³And R²⁴To be unsubstituted or taken sometimes by halogen atom Generation, also sometimes by the carbon number of carbon-to-carbon double bond displacement for 1~8 the alkyl of (particularly 1~4), unsubstituted or sometimes former by halogen Son substitution, the carbon number also replaced sometimes by carbon-to-carbon double bond are the aralkyl of 7~20 (particularly 7~15)) or carbon number For the compound of 3~6 loop chain alkane -1,1- diyl.And then more preferably oxygen atom, sulphur atom ,-CR²³R²⁴- (particularly, R²³With R²⁴The alkyl for being 1~4 for unsubstituted carbon number).

Y¹¹And Y^11'To be substituted sometimes by halogen atom, nitro, carboxyl or ferrocenyl, also put sometimes by oxygen atom or-CO- The carbon number changed be 6~30 (particularly 6~12) aryl, carbon number be 7~30 (being particularly 7~15) aralkyl or Carbon number is the compound of 1~8 alkyl.And then the carbon atom for being substituted sometimes by halogen atom, also being replaced sometimes by oxygen atom The alkyl that number is the aralkyl of 7~30 (particularly 7~15) or carbon number is 1~8 is preferred.

Q forms the compound for the methine chain that carbon number is 7 or 9.In addition, form the methine that carbon number is 7 or 9 The compound that hydrogen atom in chain and the methine chain is substituted by hydroxyl, halogen atom, cyano group or aryl.In addition, it is former to form carbon Subnumber is the compound for having in 7 or 9 methine chain and chain ring structure.

The manufacture method of the cyanine compound (α) used in the present invention is not particularly limited, can be by using many institutes The method of known in general reaction obtains, such as can include as described in Japanese Unexamined Patent Publication 2010-209191 publications Path it is such, the method for passing through the reaction of the compound with corresponding structure and imine derivative to synthesize.

The maximum absorption wavelength (λ max) of the film of the cyanine compound (α) used in the present invention is preferably 650~ 1200nm, more preferably 650~900nm.The maximum absorption wavelength (λ max) of film if the present invention more than 1200nm, then The effect of the present invention can not be played, if being less than 650nm, visible ray can be absorbed, thus it is not preferred.

In the heat reactivity composition of the present invention, the content of above-mentioned cyanine compound (α) adds up to according to independent or a variety of, 0.01 is added up to relative at least one of the mass parts of solid constituent 100, cyanine compound (α) of resin described later (β) ~10 mass parts.The content of cyanine compound (α) is if less than 0.01 mass parts, then in the solidfied material of the present invention, sometimes without Method obtains sufficient infrared ray shielding function, if greater than 10 mass parts, then cyanine occurs in heat reactivity composition sometimes The precipitation of compound (α).

<Resin (β)>

As above-mentioned resin (β), as long as soon as intramolecular has the resin of ethylenic unsaturated bond and hydrophilic radical, Can be without particular limitation using the resin used in the past.

As hydrophilic radical, hydroxyl, mercapto, carboxyl, sulfo group, amino, amide groups or its salt etc., hydroxyl can be included Base and carboxyl are preferable due to dissolubility of the resin (β) in alkali can be made high.

Preferable functional equivalent (the matter of the resin containing the equivalent of hydrophilic radical 1 of hydrophilic radical in resin (β) Amount) it is 50~10000.

The preferable matter average molecular weight of resin (β) is 1000~500000.

In above-mentioned resin (β), there is the unit that the unit of following formulas (I-1) expression, following formulas (I-2) represent with The resin of the unit of formula (I-3) expression is stated because developability and heat resistance are high, thus is preferable.

[changing 14]

(in formula, X¹Represent hydrogen atom or methyl, Y¹For the combination base of divalence, R¹Represent carbon number be 1~20 alkyl, The aralkyl that the aryl or carbon number that carbon number is 6~30 are 7~30, the alkyl, aryl and aralkyl are sometimes also by halogen Atom, hydroxyl or nitro substitute, and the methylene in the alkyl and aralkyl is sometimes also by-O- ,-S- ,-CO- ,-COO- ,-OCO- Or-NH- or the displacement of the combination base of combinations thereof, R²、R³And R⁴It is separately hydrogen atom or methyl.)

As the Y in above-mentioned formula (I-2)¹The combination base of represented divalence, following formulas (1) expression can be included Structure.

[changing 15]

*-Z¹-X²-Z²- * (1)

(in formula, X²Expression-CR⁵R⁶-、-NR⁷-, the chain alkyl that the carbon number of divalence is 1~35, the carbon atom of divalence Number is 2~35 for 3~35 alicyclic type hydrocarbon, the aromatic hydrocarbyl that the carbon number of divalence is 6~35, the carbon number of divalence Group containing heterocycle or any one substituent for representing of following (1-1)~(1-3), R⁵And R⁶Represent hydrogen atom, carbon number The aralkyl that the aryl or carbon number for being 6~20 for 1~8 alkyl, carbon number are 7~30, Z¹And Z²Independently earth's surface Show Direct Bonding ,-O- ,-S- ,-SO₂-、-SO-、-NR⁷- or-PR⁸-, R⁷And R⁸Represent hydrogen atom, the alkane that carbon number is 1~8 The aralkyl that the aryl or carbon number that base, carbon number are 6~30 are 7~30.

Above-mentioned R⁵、R⁶、R⁷And R⁸In alkyl, aryl and aralkyl can also be substituted by halogen atom, hydroxyl or nitro, on State R⁵、R⁶、R⁷And R⁸In alkyl and aralkyl in methylene sometimes also by-O- ,-S- ,-CO- ,-COO- ,-OCO- or-NH- Base is replaced.But, in the range of the carbon number for the group that above-mentioned formula (1) represents is 1~35.)

[changing 16]

(in above-mentioned formula, R⁷¹Represent hydrogen atom, can have substituent phenyl or carbon number be 3~10 cycloalkanes Base, R⁷²Represent the alkene that alkoxy, carbon number that alkyl, carbon number that carbon number is 1~10 are 1~10 are 2~10 Base or halogen atom, abovementioned alkyl, alkoxy and alkenyl can also have substituent, and f is 0~5 integer.)

[changing 17]

[changing 18]

(in above-mentioned formula, R⁷³And R⁷⁴Separately represent can have substituent carbon number be 1~10 alkyl, The aryl that can be 6~30 with the carbon number of substituent, the fragrant oxygen that can be 6~30 with the carbon number of substituent Base, the arylthio that can be 6~30 with the carbon number of substituent, can be 6~30 with the carbon number of substituent Aromatic yl alkenyl, the aralkyl that can be 7~30 with the carbon number of substituent, can be with the carbon number of substituent 2~20 group or halogen atom containing heterocycle, the methylene in the alkyl and aralkyl can also be by unsaturated bond ,-O- or-S- Interrupt, on R⁷³, adjacent R can be passed through⁷³Ring is formed each other, and d represents 0~4 number, and f represents 0~8 number, and g represents 0 ~4 number, the number of h expressions 0~4, g and h number add up to 2~4.)

As the R in above-mentioned formula (I-3)¹The aryl or carbon number that the carbon number of expression is 6~30 are 7~30 The aralkyl of (being preferably 7~20), can include cited aryl in the explanation of the cyanine compound of above-mentioned (α) composition Or aralkyl.

As the alkyl that carbon number is 1~20, except cited alkyl in above-mentioned cyanine compound (α) explanation In addition, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, ten can also be included Six alkyl, heptadecyl, octadecyl etc..

In above-mentioned formula (1), as X²The carbon number of the divalence of expression is 1~35 chain alkyl, can be included Methane, ethane, propane, isopropyl alkane, butane, secondary butane, tertiary butane, iso-butane, hexane, 2- methyl hexanes, 3- methyl hexanes, heptan Alkane, 2- methyl heptanes, 3- methyl heptanes, isoheptane, tertiary heptane, 1- methyloctanes, isooctane, tertiary octane etc. are by Z¹And Z²Substitution Group afterwards.

As divalence carbon number be 3~35 alicyclic type hydrocarbon, can include cyclopropane, cyclobutane, pentamethylene, Hexamethylene, cycloheptane, 2,4- dimethylcyclobutanes, 4- hexahydrotoluenes etc. are by Z¹And Z²Group after substitution etc..

The aromatic hydrocarbyl that carbon number as divalence is 6~35, can include phenylene, naphthylene, xenyl Deng group by Z¹And Z²Group after substitution etc..

The group containing heterocycle that carbon number as divalence is 3~35, can include pyridine, pyrazine, piperidines, piperazine Piperazine, pyrimidine, pyridazine, triazine, Hexahydrotriazine, furans, tetrahydrofuran, chroman, xanthene, thiophene, thiophane etc. are by Z¹And Z²Take Group after generation, above-mentioned group can also multiple combinations.In addition, above-mentioned chain alkyl, alicyclic type hydrocarbon and aromatic hydrocarbyl It can also be substituted by halogen atom, hydroxyl or nitro.In addition, in above-mentioned chain alkyl, alicyclic type hydrocarbon and aromatic hydrocarbyl Methylene is also replaced by-O- ,-S- ,-CO- ,-COO- ,-OCO- or-NH- bases sometimes.

As the R in above-mentioned formula (1)⁵、R⁶、R⁷And R⁸Alkyl that the carbon number of expression is 1~8, carbon number 6 ~30 aryl or carbon number is 7~30 aralkyl, can be included listed in above-mentioned cyanine compound (α) explanation Alkyl, aryl, the aralkyl of act.

Above-mentioned R⁵、R⁶、R⁷And R⁸In alkyl, aryl and aralkyl can also be substituted by halogen atom, hydroxyl or nitro, on State R⁵、R⁶And R⁷In alkyl and aralkyl in methylene can also by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-NH- or this The group that a little group multiple combinations form interrupts, and their the position of substitution and interruption position is not particularly limited.

In the substituent that above-mentioned (1-1) is represented, as R⁷¹The carbon number of expression is 3~10 cycloalkyl, can be enumerated Go out cyclopropyl, cyclobutyl, cyclopenta, suberyl, cyclooctyl etc..

As R⁷²The carbon number of expression is 1~10 alkyl, can be included as R¹The carbon number of expression be 1~ Group of carbon number etc. as defined in meeting in group cited by 40 alkyl.

As R⁷²The carbon number of expression is 1~10 alkoxy, can include methoxyl group, ethyoxyl, propoxyl group, different Propoxyl group, butoxy, sec-butoxy, tert-butoxy, isobutoxy, amoxy, isoamoxy, tertiary amoxy, hexyloxy, hexamethylene Epoxide, epoxide in heptan, different epoxide in heptan, tertiary epoxide in heptan, n-octyloxy, different octyloxy, tertiary octyloxy, 2- ethyl hexyl oxies, nonyl epoxide, Decyloxy etc..

As R⁷²The substituent that alkyl, alkoxy and the alkenyl of expression can have, can include halogen atom, hydroxyl Base, nitro.

In the group that above-mentioned (1-3) is represented, as R⁷³And R⁷⁴Represent can have the carbon number of substituent for 1~ 10 alkyl, it can include as R¹The carbon number of expression is as defined in satisfaction in the group cited by 1~20 alkyl Group of carbon number etc..

As R⁷³And R⁷⁴What is represented can have the aryl that the carbon number of substituent is 6~30, can include conduct R¹¹Carbon number Deng expression is group cited by 6~30 aryl etc..

As R⁷³And R⁷⁴What is represented can have the aryloxy group that the carbon number of substituent is 6~30, can include benzene Epoxide, naphthoxy, 2- methylphenoxies, 3- methylphenoxies, 4- methylphenoxies, 4- vinyl benzenes epoxide, 3- cumenes Epoxide, 4- cumenes epoxide, 4- butyl phenoxies, 4- tert-butyl benzenes epoxide, 4- hexyls phenoxy group, 4- cyclohexyl benzenes epoxide, 4- Octylphenoxies, 4- (2- ethylhexyls) phenoxy group, 2,3- dimethyl phenoxies, 2,4- dimethyl phenoxies, 2,5- diformazans Phenoxyl, 2,6- dimethyl phenoxies, 3,4- dimethyl phenoxies, 3,5- dimethyl phenoxies, 2,4- di-tert-butyl oxygen Base, 2,5- di-t-butyls phenoxy group, 2,6- di-t-butyls phenoxy group, the tert-amyl benzene epoxides of 2,4- bis-, 2,5- tert-amyl benzenes epoxide, The groups such as 4- cyclohexyl benzenes epoxide, 2,4,5- trimethylbenzene epoxides, ferrocene epoxide.

As R⁷³And R⁷⁴What is represented can have the arylthio that the carbon number of substituent is 6~30, can include The oxygen atom for stating the aryloxy group that can have that the carbon number of substituent is 6~30 is replaced as group after sulphur atom etc..

As R⁷³And R⁷⁴What is represented can have the aromatic yl alkenyl that the carbon number of substituent is 8~30, can enumerate Go out it is above-mentioned can have substituent carbon number be 6~30 aryloxy group oxygen atom vinyl, pi-allyl, 1- propylene Group after the displacement of the alkenyls such as base, isopropenyl, 2- cyclobutenyls, 1,3-butadiene base, 2- pentenyls, 2- octenyls etc..

As R⁷³And R⁷⁴The carbon number of expression is 7~30 aralkyl, can be included as R⁷¹And R⁷²The carbon of expression Atomicity is group cited by 7~30 aralkyl etc..

As R⁷³And R⁷⁴What is represented can have the group containing heterocycle that the carbon number of substituent is 2~20, Ke Yilie Enumerate pyridine, pyrazine, piperidines, piperazine, pyrimidine, pyridazine, triazine, Hexahydrotriazine, furans, tetrahydrofuran, chroman, xanthene, thiophene Fen, thiophane etc..

As R⁷³And R⁷⁴The above-mentioned substituent that can have of above-mentioned various groups represented, can include halogen atom, Hydroxyl, nitro.

The composition for the unit that above-mentioned formula (I-1)~(I-3) is represented is (I-1) than (mol ratio)：(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 can be taken.

In the resin (β) of the unit represented with above-mentioned formula (I-1), (I-2) and (I-3), preferably following resin.

R¹The aralkyl that the alkyl and carbon number that preferably carbon number is 1~8 are 7~30, more preferably carbon atom Number is 1~4 alkyl.

Y¹It is the combination base of divalence, in the case of the structure that above-mentioned formula (1) represents, X²Preferably carbon number be 1~ 15 alkylidene, the more preferably carbon number with cycloalkylidene are 7~15 alkylidene.Hydrogen atom in above-mentioned alkylidene It can also be substituted by halogen atom, hydroxyl or nitro atom, in addition, the methylene in the chain alkylene moiety in alkylidene is sometimes Also replaced by-O- ,-S- ,-CO- ,-COO- ,-OCO- or-NH- bases.

Z¹And Z²Preferably Direct Bonding.

The acid number of above-mentioned resin (β) is preferably 10~200mg/KOH, more preferably 30~150mg/KOH.If acid number is low In 10mg/KOH, then alkali-developable can not be fully obtained sometimes, if greater than 200mg/KOH, it is likely that the manufacture of resin (β) It is difficult.

Here, acid number refers to the value obtained according to JIS K0050 and JISK 0211.

In the heat reactivity composition of the present invention, the content of above-mentioned resin (β) is in heat reactivity composition of the invention It is preferably 30~99 mass %, particularly preferably 60~95 mass % in solid constituent.The content of above-mentioned resin (β) if less than 30 mass %, then solidfied material mechanical strength deficiency, are cracked sometimes, if greater than 99 mass %, then rely on consolidating for exposure Change becomes insufficient, sometimes tacky.

<Thermal polymerization (γ)>

As above-mentioned thermal polymerization (γ), previously known compound can be used, such as can include 2,2 '- Azodiisobutyronitrile, 2,2 '-azo two (methyl isobutyrate), 2,2 '-azo two -2,4- methyl pentane nitriles, 1,1 '-azo two Azo system polymerization initiators such as (1- acetoxyl group -1- diphenylphosphino ethanes)；Benzoyl peroxide, di-t-butyl benzoyl mistake The peroxide systems such as oxide, t-butylperoxy pivarate, two (4- tert-butylcyclohexyls) peroxy dicarbonates polymerize Persulfates such as initiator, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate etc..They can make one or two or more kinds mixing With.

In above-mentioned thermal polymerization (γ), from the viewpoint of heat resistance, preferred azo system polymerization initiator, more preferably The based compound of azo two.As the based compound of azo two, from the viewpoint of industrial be readily available, can preferably include down State the compound of formula (A) expression.

[changing 18A]

(in formula, R₁₀₁The alkyl for being 1~10 for the carbon number of the branch with substituent or straight chain sometimes, R₁₀₂To have When have substituent branch or straight chain carbon number be 1~10 alkyl or following formulas (B) represent group, foregoing alkane Methylene in base can also be replaced by-O- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- or carbon-to-carbon double bond, with identical The R that carbon atom combines₁₀₁And R₁₀₂Ring can also be interconnected to form.X₁₀₁For cyano group ,-CONR₁₀₃R₁₀₄、-COOR₁₀₅,-C= N-R₁₀₆Or there is the branch of substituent or the carbon number of straight chain sometimes for 1~10 alkyl, R₁₀₃、R₁₀₄、R₁₀₅And R₁₀₆Respectively Hydrogen atom or carbon number independently are as 1~4 alkyl.)

[changing 18B]

(in formula, R₁₁₁、R₁₁₂And R₁₁₃It is separately hydrogen atom or with the carbon number of substituent is sometimes 1~4 Alkyl, R₁₁₁、R₁₁₂Ring can also be interconnected to form, * represents bonded portion.)

As R₁₀₁、R₁₀₂、X₁₀₁、R₁₀₃、R₁₀₄、R₁₀₅、R₁₀₆、R₁₁₁、R₁₁₂And R₁₁₃The alkyl of expression, conduct can be included Above-mentioned R¹¹Deng meet in the group cited by the alkyl of expression it is above-mentioned as defined in carbon number group.

As R₁₀₁And R₁₀₂The ring being interconnected to form, can include cycloalkyl ring, preferably carbon number be 3~ 8 cycloalkyl ring.

As R₁₁₁、R₁₁₂The ring being interconnected to form, imidazole ring can be included.

As R₁₀₁、R₁₀₂、X₁₀₁、R₁₁₁、R₁₁₂And R₁₁₃The alkyl of expression has substituent during substituent, can include Carbon number is 1~4 alkoxy, carboxyl or hydroxyl.

In the heat reactivity composition of the present invention, the content of above-mentioned thermal polymerization (γ) is in heat reactivity of the invention It is preferably 0.1~30 mass %, particularly preferably 0.5~10 mass % in the solid constituent of composition.Above-mentioned thermal polymerization triggers The content of agent (γ) is if less than 0.1 mass %, it is likely that sufficient heat resistance can not be obtained, if greater than 30 mass %, Thermal polymerization (γ) is then separated out in heat reactivity composition sometimes.

<Monomer (ω) with unsaturated bond>

In the heat reactivity composition of the present invention, the monomer (ω) with unsaturated bond can also be further added.As The above-mentioned monomer with unsaturated bond, it is different can to include 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, acrylic acid The different nonyl ester of butyl ester, n-octyl, Isooctyl acrylate monomer, acrylic acid, stearyl acrylate ester, methoxyethyl acrylate, third Olefin(e) acid dimethylamino ethyl ester, zinc acrylate resin, 1,6- hexanediyl esters, trimethylolpropane trimethacrylate, methyl 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy propyl esters, butyl methacrylate, Tert-butyl Methacrylate, methyl Cyclohexyl acrylate, trimethylol-propane trimethacrylate, Dipentaerythritol Pentaacrylate, the propylene of dipentaerythritol six It is acid esters, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (methyl) acrylate, double Phenol F diglycidyl ethers (methyl) acrylate, bisphenol Z diglycidyl ether (methyl) acrylate, (first of tripropylene glycol two Base) acrylate etc..In above-mentioned compound, have multiple unsaturated bonds monomer can improve infrared ray shielding can and it is resistance to It is hot, thus be preferable.

<Solvent (σ)>

In the heat reactivity composition of the present invention, solvent (σ) can also be further added.As the solvent, it is typically Can dissolve or disperse the solvent of above-mentioned each composition (cyanine compound (α) etc.) as needed, can include such as MEK, The ketones such as methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, 2-HEPTANONE；Ether, two The ether series solvents such as oxane, tetrahydrofuran, 1,2- dimethoxy-ethanes, 1,2- diethoxyethane, dimethyl ether；Second Sour methyl esters, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, butanedioic acid two The ester series solvents such as methyl esters, 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates (texanol)；Glycol monoethyl ether, ethylene glycol The cellosolve series solvent such as single ether；Methanol, ethanol, isopropanol or normal propyl alcohol, isobutanol or n-butanol, amylalcohol, DAA etc. Alcohol series solvent；Ethylene glycol monomethyl acetic acid esters, ethylene glycol list ethylhexoate, propane diols -1- monomethyl ether -2- acetic acid esters (PGMEA), DPGME acetic acid esters, 3- methoxybutyls acetic acid esters, ethoxy ethyl propionate, the 1- tert-butyl groups- The ether-ether series solvents such as 2- propyl alcohol, 3- methoxybutyls acetic acid esters, adnoral acetate；The BTX series solvents such as benzene,toluene,xylene； The aliphatic hydrocarbon series solvent such as hexane, heptane, octane, hexamethylene；The terpenic series hydrocarbon ils such as turpentine oil, D- limonenes, firpene；Dormant oils The alkane such as essence, SWAZOL#310 (Cosmo Guia Hills oil Co., Ltd.), SOLVESSO#100 (Exxon KCCs) Series solvent；The halogenated aliphatic hydrocarbon system solvents such as carbon tetrachloride, chloroform, trichloro ethylene, dichloromethane, 1,2- dichloroethanes；Chlorobenzene Deng halogenated aromatic hydrocarbon system solvent；Carbitol series solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- bis- NMF, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide, water etc., these solvents can use a kind, Mixed solvent of more than two kinds can also be made and use.Wherein, ketone, ether-ether series solvent etc., particularly propane diols -1- list first Ether -2- acetic acid esters, cyclohexanone etc. make it that the compatibility of resin (β) and thermal polymerization (γ) in heat reactivity composition is good It is good, thus preferably.

In the heat reactivity composition of the present invention, the usage amount of above-mentioned solvent (σ) is preferably such that beyond solvent (σ) The concentration of composition is 5~30 mass %.When the concentration of composition beyond solvent (σ) is less than 5 mass %, it is difficult to increase film Thickness, or desired wavelength light can not be fully absorbed sometimes, and during more than 30 mass %, cause sometimes because of the precipitation of composition The keeping quality of composition declines, or viscosity increases and declines treatability.

In the heat reactivity composition of the present invention, it can also further contain inorganic compound.As the inorganic chemical Thing, such as nickel oxide, iron oxide, yttrium oxide, titanium oxide, zinc oxide, magnesia, calcium oxide, potassium oxide, oxidation can be included The metal oxides such as silicon, aluminum oxide；Layered clay mineral, milori blue, calcium carbonate, magnesium carbonate, cobalt system, manganese systems, glass powder, Mica, talcum, kaolin, ferrocyanide, various metal sulfates, sulfide, selenides, alumina silicate, calcium silicates, hydroxide Aluminium, platinum, gold, silver, copper etc., wherein, preferably titanium oxide, silica, layered clay mineral, silver etc..The heat reactivity of the present invention In composition, the content of above-mentioned inorganic compound is preferably 0.1~50 mass parts relative to the mass parts of above-mentioned resin (β) 100, more Preferably 0.5~20 mass parts, these inorganic compounds can use one kind or two or more.

It is strong that above-mentioned inorganic compound may be used as such as filler, antireflection agent, conductive agent, stabilizer, fire retardant, machinery Spend enhancer, special wavelength absorbent, oil resistant ink agent etc..

In the heat reactivity composition of the present invention, when using pigment and/or inorganic compound, it can add scattered Agent.As the dispersant, as long as pigment and/or inorganic compound can be made scattered or stabilized dispersant, then without spy Do not limit, commercially available dispersant can be used, such as the BYK series of BYK-Chemie company systems, wherein, by with alkaline official Can group polyester, polyethers, polyurethane form macromolecule dispersing agent, with nitrogen-atoms as basic functionality and with nitrogen-atoms The dispersant that functional group is amine and/or its quaternary ammonium salt and amine value is 1~100mgKOH/g can preferably use.

In addition, in the heat reactivity composition of the present invention, can add as needed to methyl phenyl ethers anisole, quinhydrones, burnt catechu The thermal polymerization inhibitors such as phenol, tert-butyl catechol, phenthazine；Plasticizer；Adhesion promoters；Filler；Defoamer；Levelling agent； Surface conditioner；Antioxidant；Ultra-violet absorber；Dispersing aid；Anticoalescent；Catalyst；Curing accelerator；Crosslinking agent； The conventional additive such as thickener.

In the heat reactivity composition of the present invention, above-mentioned cyanine compound (α), resin (β) and thermal polymerization The content of any condition (wherein, except monomer (ω) and solvent (σ) with unsaturated bond) beyond (γ) can be according to it Application target suitably selects, and is not particularly limited, but it is preferred that relative to the mass parts of above-mentioned resin (β) 100, by total amount It is set as below 50 mass parts.

In the heat reactivity composition of the present invention, by being used together other organic polymers with above-mentioned resin (β), The characteristic of the solidfied material formed by the heat reactivity composition of the present invention can be improved.As above-mentioned organic polymer, can enumerate Go out such as polystyrene, polymethyl methacrylate, Eudragit NE30D, poly- (methyl) propylene Acid, styrene-(methyl) acrylic copolymer, (methyl) acryl acid-methyl methacrylate copolymer, ethylene-vinyl chloride Copolymer, ethylene-vinyl base co-polymer, Corvic, ABS resin, nylon 6, nylon66 fiber, nylon 12, polyurethane tree It is fat, makrolon polyvinyl butyral resin, cellulose esters, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, poly- Amide imide resin, polyamic acid resin, epoxy resin etc., wherein it is preferred that polystyrene, (methyl) acrylic acid-methyl-prop E pioic acid methyl ester copolymer, epoxy resin.

When using other organic polymers, its usage amount relative to the mass parts of above-mentioned resin (β) 100, preferably 10~ 500 mass parts.

Can be further and with chain-transferring agent, sensitizer, surfactant, silane in the heat reactivity composition of the present invention Coupling agent, melamine compound etc..

As above-mentioned chain-transferring agent or sensitizer, the general compound for using sulfur atom-containing.Such as sulfydryl can be included Acetic acid, thiomalic acid, thiosalicylic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids, 3- mercaptobutyric acids, N- (2- mercapto radical propionyl groups) Glycine, 2- mercaptonicotinic acids, 3- [N- (2- mercaptoethyls) carbamoyl] propionic acid, 3- [N- (2- mercaptoethyls) amino] third Acid, N- (3- mercapto radical propionyl groups) alanine, mistabrom, 3- thiohydracrylic acids, 4- sulfydryl fourths sulfonic acid, dodecyl (4- Methyl mercapto) phenyl ether, 2 mercapto ethanol, 3- sulfydryls -1,2-PD, 1- sulfydryl -2- propyl alcohol, 3- sulfydryl -2- butanol, sulfydryl benzene Phenol, 2-MEA, 2- mercaptoimidazoles, 2-mercaptobenzimidazole, 2- sulfydryl -3- pyridones, 2-mercaptobenzothiazole, sulfydryl The sulfhydryl compounds such as acetic acid, trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3-thiopropionate), by the mercapto The iodine such as disulphide, iodoacetic acid, iodopropionic acid, ethylene iodohydrin, 2- iodine ethyl sulfonic acid, 3- iodine propane sulfonic acid obtained from based compound oxidation Substituted alkyl compound, trimethylolpropane tris (3- mercaptoisobutanoics acid esters), butanediol double (3- mercaptoisobutanoics acid esters), oneself two sulphur Alcohol, the mercaptan of the last of the ten Heavenly stems two, Isosorbide-5-Nitrae-dimethyl sulfydryl benzene, butanediol dithiopropionic acid ester, butanediol dimercapto acetic acid esters, ethylene glycol two Mercaptoacetate, trimethylolpropane tris mercaptoacetate, butanediol dithiopropionic acid ester, trimethylolpropane tris propane thioic acid Ester, trimethylolpropane tris mercaptoacetate, pentaerythrite tetrathio propionic ester, the mercaptoacetate of pentaerythrite four, trihydroxy The aliphatic such as the thiopropionate of ethyl three, following compound C1, tri-thiol propionic acid three (2- ethoxys) isocyanuric acid ester are multifunctional Mercaptan compound, KARENZ MT BD1 of Showa electrician's company system, PE1, NR1 etc..

[changing 19]

Compound N o.C1

As above-mentioned surfactant, the fluorochemical surfaces such as perfluoralkyl phosphate, perfluoroalkyl carboxylate can be used to live The anion system surfactants such as property agent, higher aliphatic acid alkali metal salt, alkylsulfonate, alkyl sulfate；Higher amines hydracid The cation such as salt, quaternary ammonium salt system surfactant；Polyethylene glycol alkyl ether, cithrol, sorbitan esters of fatty The nonionic surfactants such as acid esters, glycerine monofatty ester；Amphoteric surfactant；Live on the surfaces such as silicone-based surfactant Property agent, they can also combine use.

As above-mentioned silane coupler, the silane coupler of such as chemical company of SHIN-ETSU HANTOTAI can be used, wherein, KBE- 9007th, KBM-502, KBE-403 etc. have NCO, methylacryloyl, epoxy radicals silane coupler can be with excellent Choosing uses.

As above-mentioned melamine compound, can include (poly-) melamine methylol, (poly-) methylol glycoluril, Active methylol (CH in the nitrogen compounds such as (poly-) methylolbenzoguanamine, (poly-) methylolurea₂OH yls) whole or one Point (at least two) is by the compound after alkyl etherified.Wherein, as the alkyl for forming alkyl ether, methyl, ethyl can be included Or butyl, mutually can be with identical, can also be different.In addition, not alkyl etherified methylol can be carried out certainly in an intramolecular Condensation, can also two it is intermolecular be condensed, as a result formed oligomer composition.Specifically, hexamethoxy methyl can be used Melamine, six butoxymethyl melamines, tetramethoxymethylglycoluril, four butoxymethyl glycolurils etc..Wherein, preferably six Melamine after methoxy melamine, six butoxymethyl melamines etc. are alkyl etherified.

The heat reactivity composition of the present invention can in a solvent dissolve or divide in the case of solvent-free solid state Dissipate after, with spinner, sized roller applicator, rod coaters, die coating device, curtain coaters, slot coated device, dip coated device, it is various printing, Means known to impregnating are applied in the support substrates such as soda-lime glass, quartz glass, semiconductor substrate, metal, paper, plastics.This Outside, it is transferred to again in other support substrates after can also being briefly applied in the support substrates such as film, its application process does not limit System.

Heating condition when making the heat reactivity composition solidification of the present invention is 1~100 minute at 70~250 DEG C.Can be with After prebake conditions, pressurizeed, then toasted after carrying out, can also be toasted at a temperature of different several stages.

Heating condition is different and different according to the species of each composition and mixing ratio, such as, at 70~180 DEG C, dry Heat 5~15 minutes if case, heated 1~5 minute if hot plate.Then, in order that curing of coating, 100~250 DEG C, it is excellent 180~250 DEG C are selected in, more preferably heats 30~90 minutes at 200~250 DEG C, if baking oven, if hot plate at heating Reason 5~30 minutes, it becomes possible to obtain cured film.

The heat reactivity composition (or its solidfied material) of the present invention can be used for heat reactivity coating or varnish, heat reactivity The liquid crystal of the colored display such as bonding agent, printed circuit board or colour television set, PC monitors, portable information terminal, digital camera The colour filter of colour filter, ccd image sensor, the electrode material of plasma display, powder in display panel apply Layer, printing-ink, galley, bonding agent, gear division are with composition, three-dimensional contouring with resin, gel coat, electronic engineering Photoresist, platedresist, etch both resist, liquid and desciccator diaphragm, solder resist, used for manufacturing various displays The colour filter on way is used to be formed in plasma display, el display device and LCD manufacturing process The resist of structure, for sealing the electrically or electronically composition of part, solder resist, magnetic recording material, milli machine part, ripple Lead, optical switch, plating mask, etching mask, color test system, glass fiber cable coatings, silk-screen printing masterplate, For manufacturing material, holographic recording material, image recording material, the fine electricity of three-dimensional body by stereolithography Road, decoloring material, the decoloring material for image recording material, the decoloring material of the image recording material using micro-capsule, print Circuit board processed prints with photo anti-corrosion agent material, UV and visible laser through image system photo anti-corrosion agent material, for being formed In the various uses such as the photo anti-corrosion agent material or diaphragm of the dielectric layer in the gradually lamination of circuit substrate processed, its purposes is simultaneously It is not particularly limited.

The heat reactivity composition of the present invention is used to interdict the purpose of specific infrared ray, especially as It is useful for forming the heat reactivity composition of wavelength cut-off filter.

Below, the wavelength cut-off filter of the present invention is illustrated.

In the wavelength cut-off filter of the present invention, have on a face of glass substrate (A) by the thermal response of the present invention The coating layer (B) that property composition obtains, and there is infrared reflection film (C) on another face of glass substrate (A).Coating Layer (B) and infrared reflection film (C) are laminated on each face of glass substrate (A) respectively.As shown in figure 1, will can have by this Light incident side of the side for the coating layer (B) that the heat reactivity composition of invention obtains as light, as shown in Fig. 2 will can also have There is light incident side of the side of infrared reflection film (C) as light.Hereinafter, each layer is illustrated successively.

<Glass substrate (A)>

, can be from transparent in visibility region as the glass substrate (A) that uses in the wavelength cut-off filter of the present invention It is appropriate in glass material to select to use, soda-lime glass, blank glass, pyrex, strengthened glass, quartzy glass can be used Glass, phosphate-based glass etc., wherein, soda-lime glass is cheap and is readily available, thus preferably, blank glass, pyrex With strengthened glass due to being readily available, and hardness is high, excellent processability, thus preferably.

And then if coating is anti-by the heat of the present invention after the pre-treatment of silane coupler etc. is implemented to glass substrate (A) Answering property composition form coating fluid and form coating layer (B), then the dried coating layer (B) containing dyestuff of coating fluid is to glass The adherence of glass substrate improves.

As above-mentioned silane coupler, γ-glycidoxypropyltrimethoxy silane, the third oxygen of γ-epoxy third can be included The epoxy functional alkoxy silanes such as ylmethyl diethoxy silane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, N- β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N- phenyl-gamma-amino The Mercaptofunctional alkane such as the amino functional such as propyl trimethoxy silicane alkoxy silane, γ mercaptopropyitrimethoxy silane TMOS etc..

In addition, there can also be bottom between glass substrate (A) and coating layer (B).Bottom is obtained as below：Will be flat The metal oxide that the average aggregate particle size that the primary particle cohesion that equal primary particle size is 5~100nm forms is 20~250nm is micro- The agglomerate of grain is scattered in following shown solvents, obtains coating fluid, the coating fluid is entered with following shown coating methods Row is coated with and obtains bottom, and thickness is 30~1000nm.The agglomerate of above-mentioned metal oxide microparticle is relative to coating fluid total amount Preferably 0.1~50 mass %.

The thickness of glass substrate (A) is not particularly limited, but preferably 0.05~8mm, from lightweight and the viewpoint of intensity Set out, more preferably 0.05~1mm.

In the present invention, because base material is glass plate, so can be directly coated with base material, cut-out is carried out after drying and is added Work, construction and technique become simple.Further, since substrate is glass plate, so compared with the situation of plastics, (260 DEG C of heat resistance Resistance to soft heat) it is higher.

<Coating layer (B)>

Coating layer being used in the wavelength cut-off filter of the present invention, being obtained by the heat reactivity composition of the present invention (B) as set forth above, it is possible to by the way that the heat reactivity composition of the present invention is coated on glass substrate (A) to be formed.Obtain Film heats and makes its solidification as needed.

When the thickness of coating layer (B) containing dyestuff is 1~200 μm, uniform film can be obtained, is advantageous to filming, because It is but preferable.It if less than 1 μm, can not fully show function, if it exceeds 200 μm, then be possible to remain when being coated with molten Agent.

<Infrared reflection film (C)>

The infrared reflection film (C) used in the wavelength cut-off filter of the present invention has 700~1200nm of blocking ripple The function of the light in long region, formed by the alternately laminated dielectric multilayer film formed of low-index layer and high refractive index layer.

As the material for forming above-mentioned low-index layer, the material that refractive index is 1.2~1.6 can be used, such as can be with Include silica, aluminum oxide, lanthanum fluoride, magnesium fluoride, lithium aluminium sodium etc..

As the material for forming above-mentioned high refractive index layer, the material that refractive index is 1.7~2.5 can be used, can be enumerated Go out such as titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthana, yittrium oxide, zinc oxide, zinc sulphide, indium oxide, this Outside, can also include using their materials as principal component and containing a small amount of titanium oxide, tin oxide, cerium oxide etc. etc..

About being laminated the method for above-mentioned low-index layer and high refractive index layer, as long as can be formed above-mentioned layer stackup and Into dielectric multilayer film, be just not particularly limited, for example, can include on the glass substrate, using CVD, sputtering method, The method that low-index layer and high refractive index layer are alternately stacked to form dielectric multilayer film by vacuum vapour deposition etc..In addition, also Dielectric multilayer film can be pre-formed, and is fitted in bonding agent on glass substrate.

Stacking number is 10~80 layers, is preferable from the viewpoint of technique and intensity when being 25~50 layers.

The thickness of above-mentioned low-index layer and high refractive index layer is usually the 1/ of the wavelength X (nm) for the light to be interdicted respectively 10~1/2 thickness.If thickness is less than 0.1 λ or more than 0.5 λ, refractive index (n) and the product (nd) and use of physical film thickness (d) The blooming that the multiple of λ/4 represents is different greatly, thus is possible to carry out the Zhe Duan transmissions of specific wavelength.

As above-mentioned infrared reflection film (C), in addition to foregoing dielectric multilayer film, can also use containing maximum Absorbing wavelength for 700~1100nm dyestuff film, be laminated high molecular film, film for being formed of coating cholesteric crystal etc. The film of organic material is used.

The wavelength cut-off filter preferred transmission rate of the present invention meets following (i)~(iii).In addition, the measure of transmissivity It is to be determined using the UV, visible light near infrared spectrometer V-570 of Japan Spectroscopy Corporation.

(i) from the vertical direction (plate with glass substrate of wavelength cut-off filter in the range of 430~580nm of wavelength It is the vertical direction in face, following same) measure when the average value of transmissivity be more than 75%.

(ii) in 800~1000nm of wavelength from the vertical direction of wavelength cut-off filter measure when transmissivity be averaged It is worth for less than 5%.

(iii) transmissivity when in the range of 560~800nm of wavelength from the vertical direction measure of wavelength cut-off filter Reach the value (Ya) of 80% wavelength with from be 35 ° of goniometry relative to the vertical direction of wavelength cut-off filter when it is saturating The poor absolute value that the rate of penetrating reaches the value (Yb) of 80% wavelength is below 30nm.

For wavelength cut-off filter, transmissivity in the range of the 430~580nm of wavelength of above-mentioned (i) it is flat If average is less than 75%, the light of visible region can hardly be transmitted.In the range of the 430~580nm of wavelength of (i) The average value of transmissivity is more preferably more than 80%.The average value of transmissivity in the 800~1000nm of wavelength of above-mentioned (ii) If it exceeds 5%, then it can hardly end the light of infrared spectral range, it is possible to be difficult in a manner of the visibility close to people Correcting sensitivity.(ii) average value of the transmissivity in 800~1000nm of wavelength is more preferably less than 1%.

In addition, the Ya and Yb of above-mentioned (iii) poor absolute value is if it exceeds 30nm, then to the dependence of the incidence angle of light Uprise, the characteristic of wavelength cut-off filter can change with the change of the incidence angle of light, and it is possible to color occurs to draw The center and periphery in face such as change at the drawback.(iii) Ya and Yb poor absolute value is more preferably below 5nm, further Preferably below 3nm.

As the specific purposes of the wavelength cut-off filter of the present invention, it can include and be installed on automobile and building Heat ray cut-off filter on glass pane etc.；Digital camera, digital camera, supervision camera, vehicle-mounted camera, network The solid-state imagers such as CCD and CMOS in the solid camera heads such as camera, mobile phone camera are corrected with visibility and used；From Dynamic exposure meter；Display devices such as plasma scope etc..

Below, the solid camera head and camera module of the present invention are illustrated.

The solid camera head of the present invention is except possessing the wavelength cut-off filter of the present invention on the preceding surface of photographing element In addition, formed in the same manner as conventional solid camera head.The wavelength cut-off filter 1 of the present invention can be as shown in Figure 5 and Figure 6 Like that, it is fixed in the light incident side of solid-state imager 2 on the part beyond solid-state imager, can also be such as Fig. 3 and Fig. 4 It is shown such, it is directly fixed on the preceding surface of solid-state imager 2.

The present invention solid camera head on, can also configure as needed optical low-pass filter, anti-reflection filter, Colour filter etc., the order that they are laminated are not particularly limited.

As shown in Figure 3 and Figure 4, the camera module about one of the solid camera head as the present invention, below to this The wavelength cut-off filter 1 of invention is carried out in the situation that the light incident side of solid-state imager 2 is laminated on solid-state imager Illustrate.

Fig. 3 and Fig. 4 is a shape of the composition of the camera module of one of the solid camera head for being denoted as the present invention The sectional view of state.Camera module has：Be formed as overlooking rectangular-shaped solid-state imager 2 on a semiconductor substrate；With The opposite side of the light accepting part 3 of solid-state imager 2, coating layer (B), glass containing dyestuff are stacked gradually since light incident side The wavelength cut-off filter 1 (Fig. 3)/or stacked gradually infrared reflection film that glass substrate (A), infrared reflection film (C) form (C), the wavelength cut-off filter 1 (Fig. 4) that glass substrate (A), the coating layer (B) containing dyestuff form, by solid-state image pickup The bonding agent 4 formed on region beyond the removing light accepting part 3 of the one side of element 2 filters solid-state image pickup sub-prime 2 and wavelength cut-off Light device 1 engages.Camera module as solid camera head is taken into the light from outside by wavelength cut-off filter 1, and By being configured at the photo detector in the light accepting part 3 of solid-state imager 2 come light.

As shown in Figure 5 and Figure 6, the camera module about one of the solid camera head as the present invention, below to this The wavelength cut-off filter 1 of invention is fixed on the part beyond solid-state imager in the light incident side of solid-state imager 2 Situation be specifically described.

Fig. 5 and Fig. 6 is a shape of the composition of the camera module of one of the solid camera head for being denoted as the present invention The sectional view of state.Camera module has：Be formed as overlooking rectangular-shaped solid-state imager 2 on a semiconductor substrate；With The opposite side of the light accepting part 3 of solid-state imager 2, coating layer (B), glass containing dyestuff are stacked gradually since light incident side The wavelength cut-off filter 1 (Fig. 5)/or stacked gradually infrared reflection film that glass substrate (A), infrared reflection film (C) form (C), the wavelength cut-off filter 1 (Fig. 6) that glass substrate (A), the coating layer (B) containing dyestuff form, in solid-state imager 2 One side removing light accepting part 3 beyond region on formed.Camera module as solid camera head passes through wavelength cut-off Filter 1 is taken into the light from outside, and by being configured at the photo detector in the light accepting part 3 of solid-state imager 2 come light.

As bonding agent 4, UV curability bonding agent or the Thermocurables such as acrylic resin, epoxy system resin can be used Resin, equably it is coated with after the bonding agent 4, is as needed patterned bonding agent using well-known photoetching technique, And engaged by heat cure.During engagement, vacuum pressed is carried out after can also being bonded in vacuum environment.

Installation base plate 8 is to have used the hard substrates such as glass epoxy substrate or ceramic substrate, and is provided with control solid and takes the photograph The control circuit of element 2.

Solid-state imager 2 is configured on installation base plate 8, then on the position of the set lens bracket 7 of installation base plate 8 It is pre-coated with bonding agent 4.

Lens cap 6 is for protecting camera lens 5.In addition, lens bracket 7 is used to keep camera lens 5, has and be installed on installation base On plate 8 and cover the basal disc portion 7a of the box-like of solid-state imager 2 and keep the lens barrel portion 7b of the drum of camera lens 5.

Then, lens bracket 7 is configured in the way of the lower surface of lens bracket 7 contacts with the bonding agent 4 being coated with On installation base plate 8, then with the distance of the camera lens 5 in the light accepting part 3 of solid-state imager 2 and lens bracket 7 and the focus of camera lens 5 The regulation of the position of lens bracket 7 is carried out apart from consistent mode.

After the position adjustments for having carried out lens bracket 7, ultraviolet is irradiated to bonding agent 4, solidifies bonding agent 4, thus may be used To manufacture camera module.

The entirety of installation base plate 8 for securing lens bracket 7 can also be heated at about 85 DEG C, make to glue by heat cure The solidification for connecing agent 4 is fully carried out.

In addition, in the manufacture method of camera module, due to after the process of irradiation ultraviolet, being installed comprising heating The overall process of substrate 8, so lens bracket 7, camera lens 5 and wavelength cut-off filter 1 must use the high material of heat resistance. Specifically, in addition to the heating carried out for the heat cure of bonding agent 4 as described above, due to installation will be configured at The many places soft solder of the lower surface of substrate 8 carries out carrying out solder with other substrates after heating melt process at about 260 DEG C, because This is preferably formed by the material with resistance to soft heat.

Embodiment

Hereinafter, embodiment etc. is enumerated the present invention is described in more detail, but the present invention is not limited by these embodiments etc..

[Production Example 1] resin (β) No.1 modulation

The mass parts of acrylic acid 40 and the mass parts of butyl methacrylate 50 are dissolved in propane diols -1- monomethyl ether -2- second In the mass parts of acid esters (PGMEA) 200, the mass parts of azodiisobutyronitrile 4 are added into the solution as radical polymerization initiator, Stirred 3 hours at 80 DEG C.Then, add with the CELLOXIDE 2021P of acrylic acid modified mistake (Daicel chemical companies Alicyclic epoxy resin) 10 mass parts, stir 3 hours at 120 DEG C, obtain resin (β) No.1.

Resin (β) No.1 is following resins (β)：In above-mentioned logical formula (I), X¹For hydrogen atom or methyl, Y¹To be above-mentioned Combination base (the X for the divalence that formula (1) represents²The group represented for following formula (n), Z¹And Z²For Direct Bonding), R¹For carbon atom Count the alkyl for 1~8, R²~R³For hydrogen atom, R⁴For methyl.

[changing 20]

[Production Example 2] resin (β) No.2 modulation

By the mass parts of methacrylic acid 20, the mass parts of GMA 20 and the matter of benzyl methacrylate 50 Amount part is dissolved in the mass parts of cyclohexanone 500, the mass parts of azodiisobutyronitrile 4 is added as radical polymerization initiator, 80 Stirred 3 hours at DEG C.Then, the mass parts of acrylic acid 20 are added, is stirred 3 hours at 120 DEG C, obtains resin (β) No.2.

[Production Example 3] resin (β) No.3 modulation

The mass parts of GMA 50,5 parts of benzyl methacrylate and the mass parts of styrene 40 are dissolved In propane diols -1- monomethyl ether -2- acetic acid esters (PGMEA) 500 mass parts, 1- bis- (tert-butyl hydroperoxide) -3,3,5- is added The mass parts of trimethyl-cyclohexane 1 stir 2 hours as radical polymerization initiator at 140 DEG C.Then, acrylic acid 20 is added Mass parts, stirred 3 hours at 120 DEG C, obtain resin (β) No.3.

[Production Example 4] resin (β) No.4 modulation

The mass parts of GMA 40,5 parts of benzyl methacrylate, the mass parts of styrene 40 are dissolved in In propane diols -1- monomethyl ether -2- acetic acid esters (PGMEA) 500 mass parts, using the mass parts of azodiisobutyronitrile 10 as freely Base polymerization initiator, stirred 3 hours at 80 DEG C.Then, the mass parts of acrylic acid 20 are added, stirs 3 hours, obtains at 120 DEG C To resin (β) No.4.

[Production Example 5] resin (β) No.5 modulation

The mass parts of GMA 40,5 parts of metering system benzyl ester, the mass parts of styrene 40 are dissolved in third In glycol -1- monomethyl ether -2- acetic acid esters (PGMEA) 500 mass parts, the mass parts of azodiisobutyronitrile 5 are added as free radical Polymerization initiator, stirred 3 hours at 80 DEG C.Then, the mass parts of acrylic acid 20 are added, are stirred 3 hours at 120 DEG C.Then, The mass parts of tetrabydrophthalic anhydride 5 are added, after being stirred 3 hours at 120 DEG C, obtain resin (β) No.5.

[embodiment 1-1~1-10 and comparative example 1-1~1-5] heat reactivity composition No.1~No.11 and comparison combination Thing No.1~No.5 modulation

<Step 1>Dye solution No.1~No.10 and the modulation for comparing dye solution No.1~No.5

Solvent (σ), stirring and dissolving are added in the cyanine compound (α) shown in [table 1] as (A) composition~[table 3] After obtain dye solution No.1~No.10 and comparing dye solution No.1~No.5.

<Step 2>Heat reactivity composition No.1~No.10 and comparative composition No.1~No.5 modulation

According to the proportioning of [table 1]~[table 3], in above-mentioned dye solution No.1~No.10 and compare dye solution No.1~No.5 It is middle to add resin (β), polymerization initiator (γ) (or (γ ')) and monomer (ω) with unsaturated bond and solvent (σ) and stir Mix, modulate heat reactivity composition No.1~No.10 and comparative composition No.1~No.5.

Table 1

A-1：The hexafluorophosphate of compound N o.76

A-2：The hexafluorophosphate of compound N o.100

A-3：Double (trifluoro methylsulfonyl) the imines hydrochlorates of compound N o.100

A-4：Double (trifluoro methylsulfonyl) the imines hydrochlorates of compound N o.102

A-5：Double (trifluoro methylsulfonyl) the imines hydrochlorates of compound N o.103

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

B-2：ACA Z251 (the propylene acidifying acrylate of Daicel-Allnex company systems)

B-3：ACA Z250 (the propylene acidifying acrylate of Daicel-Allnex company systems)

B-4：ACA 200M (the propylene acidifying acrylate of Daicel-Allnex company systems)

B-5：SPC-1000 (acrylic resin of Showa electrician's company system)

B-6：SPC-3000 (acrylic resin of Showa electrician's company system)

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 (and oil-soluble azo polymerization initiator of the pure medicine company system of light)

C-2：V-70 (and oil-soluble azo polymerization initiator of the pure medicine company system of light)

C-3：V-65 (and oil-soluble azo polymerization initiator of the pure medicine company system of light)

C-4：V-59 (and oil-soluble azo polymerization initiator of the pure medicine company system of light)

C-5：V-40 (and oil-soluble azo polymerization initiator of the pure medicine company system of light)

C-6：VAm-110 (and oil-soluble azo polymerization initiator of the pure medicine company system of light)

C’-1：Irg-907 (Photoepolymerizationinitiater initiater of BASF AG)

C’-2：SP-246 (Photoepolymerizationinitiater initiater of ADEKA company systems)

C’-3：OXE-01 (Photoepolymerizationinitiater initiater of BASF AG)

C’-4：OXE-02 (Photoepolymerizationinitiater initiater of BASF AG)

D-1：Aronix M450 (acrylic monomer of East Asia Synesis Company)

D-2：Aronix M315 (acrylic monomer of East Asia Synesis Company)

E-1：Cyclohexanone

E-2：Diacetone alcohol

E-3：MEK

Table 2

Table 3

[evaluation example 1-1~1-10 and comparative evaluation example 1-1~1-5]

By in the heat reactivity composition No.1~No.10 and comparative example 1-1~1-5 that are obtained in embodiment 1-1~1-10 Obtained comparative composition No.1~No.5 is coated on glass substrate under conditions of 410rpm × 7 second respectively, is made with hot plate It dries (90 DEG C, 10 minutes).After drying, being heated 10 minutes at 150 DEG C with hot plate makes curing of coating.By the film after solidification Heated under conditions of 150 DEG C × 1 hour to evaluate heat resistance.Evaluation is the maximum absorption wavelength front and rear by calculating heating Transmissivity changes to carry out.Transmissivity variable quantity is obtained with following formula.

(X is the transmissivity of the maximum absorption wavelength before heating to transmissivity variable quantity (%)=(X-Y)/X × 100, and Y is to add The transmissivity at the wavelength determined after heat)

Above-mentioned result is shown in Table 4.

Table 4

	Composition	Transmissivity variable quantity (%)
			Evaluate example 1-1	No.1	1.2
Evaluate example 1-2	No.2	1.3
			Evaluate example 1-3	No.3	0.9
Evaluate example 1-4	No.4	1.2
			Evaluate example 1-5	No.5	1.3
Evaluate example 1-6	No.6	1.2
			Evaluate example 1-7	No.7	1.2
Evaluate example 1-8	No.8	1.0
			Evaluate example 1-9	No.9	0.8
Evaluate example 1-10	No.10	1.4
			Comparative evaluation example 1-1	Compare No.1	6.8
Comparative evaluation example 1-2	Compare No.2	7.7
			Comparative evaluation example 1-3	Compare No.3	9.6
Comparative evaluation example 1-4	Compare No.4	10.4
			Comparative evaluation example 1-5	Compare No.5	-

(in table 4, "-" represent can not equably film forming, so can not be evaluated.)

From the result of above-mentioned table 4, the change of the aberration of heat reactivity composition of the invention is less, heat resistance compared with It is high.

[embodiment 2-1~2-10] wavelength cut-off filter No.1~No.10 manufacture

On a face of the glass substrate (A) that thickness is 100 μm, pass through the alternately laminated silica of vacuum vapour deposition (SiO₂) layer and titanium oxide (TiO₂) layer, form the infrared reflection film (C) that total number of plies is 30 layers, thickness is about 3 μm.

On the faces different from infrared reflection film of the obtained glass substrate (A) for being applied with infrared reflection film (C), With rod coaters #30 be coated with (10 μm of thickness) embodiment 1-1~1-10 in obtain heat reactivity composition (coating fluid) No.1~ After No.10, dried 10 minutes at 100 DEG C, make wavelength cut-off filter No.1~No.10.

[evaluation example 2-1~2-10]

For the wavelength cut-off filter No.1~No.10 of the invention obtained in embodiment 2-1~2-10, obtain and i) exist Average value, the ii of transmissivity when being determined in the range of 430~580nm of wavelength from the vertical direction of wavelength cut-off filter) The average value and iii of transmissivity when being determined in 800~1000nm of wavelength from the vertical direction of wavelength cut-off filter) in ripple Transmissivity when being determined in the range of long 560~800nm from the vertical direction of wavelength cut-off filter reaches 80% wavelength Value (Ya) with from be 35 ° of goniometry relative to the vertical direction of wavelength cut-off filter when transmissivity reach 80% ripple The poor absolute value of long value (Yb).As a result it is shown in Table 5.In addition, the measure of above-mentioned transmissivity is with Japan's light splitting strain formula meeting The UV, visible light near infrared spectrometer V-570 of society is determined.

Table 5

From the result of above-mentioned table 5, wavelength cut-off filter of the invention is saturating in the range of 430~580nm of wavelength It is higher to penetrate rate, it is relatively low in wavelength 800~1000nm internal transmission factors, and incident angle dependency is relatively low.

As can be known from the above results, to form the coating layer (B) containing dyestuff, simultaneously on a face of glass substrate (A) And the wavelength cut-off filter of the invention that there is infrared reflection film (C) to be characterized on another face of glass substrate (A) Incident angle dependency it is relatively low.Therefore, wavelength cut-off filter of the invention is for solid camera head and camera module Useful.

Claims (8)

1. a kind of heat reactivity composition, it contains：At least one of cyanine compound (α), at least there is ethylenic insatiable hunger With the resin of key and hydrophilic radical (β) and thermal polymerization (γ).

2. heat reactivity composition according to claim 1, it is characterised in that at least with ethylenic unsaturated bond and parent Unit that unit that the resin (β) of water-based group represents containing following formulas (I-1), following formulas (I-2) represent and following logical The unit that formula (I-3) represents,

In formula, X¹Represent hydrogen atom or methyl, Y¹It is the combination base of divalence, R¹Represent that alkyl, carbon that carbon number is 1~20 are former The aralkyl that the aryl or carbon number that subnumber is 6~30 are 7~30, the alkyl, aryl and aralkyl also can be by halogen atom, hydroxyls Base or nitro substitution, methylene in the alkyl and aralkyl also can by-O- ,-S- ,-CO- ,-COO- ,-OCO- or-NH- or The combination base displacement of combinations thereof, R²、R³And R⁴It is separately hydrogen atom or methyl.

3. heat reactivity composition according to claim 1 or 2, it is characterised in that thermal polymerization (γ) is azo Thermal polymerization.

4. according to heat reactivity composition according to any one of claims 1 to 3, it is characterised in that relative at least having The mass parts of solid constituent 100 of the resin of ethylenic unsaturated bond and hydrophilic radical (β), containing adding up to 0.01~10.0 matter Measure at least one of the cyanine compound of part (α).

5. a kind of wavelength cut-off filter, it is characterised in that have on a face of glass substrate (A) by Claims 1 to 4 Any one of the obtained coating layer (B) of heat reactivity composition, and have on another face of glass substrate (A) Infrared reflection film (C).

6. wavelength cut-off filter according to claim 5, it is characterised in that the transmissivity of the wavelength cut-off filter Meet following (i)~(iii)：

(i) in the range of 430~580nm of wavelength, from the vertical direction of wavelength cut-off filter measure when transmissivity it is flat Average is more than 75%,

(ii) in 800~1000nm of wavelength, the average value of transmissivity when being determined from the vertical direction of wavelength cut-off filter For less than 5%,

(iii) in the range of 560~800nm of wavelength, transmissivity when being determined from the vertical direction of wavelength cut-off filter reaches To 80% wavelength value (Ya) with from be 35 ° of goniometry relative to the vertical direction of wavelength cut-off filter when transmission The poor absolute value that rate reaches the value (Yb) of 80% wavelength is below 30nm.

7. a kind of solid camera head, it is characterised in that it possesses the wavelength cut-off filter described in claim 5 or 6.

8. a kind of camera module, it is characterised in that it possesses the wavelength cut-off filter described in claim 5 or 6.