CN103930806B - Wavelength cut-off light filter - Google Patents
Wavelength cut-off light filter Download PDFInfo
- Publication number
- CN103930806B CN103930806B CN201380003842.6A CN201380003842A CN103930806B CN 103930806 B CN103930806 B CN 103930806B CN 201380003842 A CN201380003842 A CN 201380003842A CN 103930806 B CN103930806 B CN 103930806B
- Authority
- CN
- China
- Prior art keywords
- light filter
- wavelength
- wavelength cut
- dyestuff
- cut
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
Abstract
The present invention provides that incident angle dependency is low, thermostability is high and is capable of the wavelength cut-off light filter of slimming.Specifically, a kind of wavelength cut-off light filter is provided, it is characterized in that, its be have on a face of glass substrate (A) coating layer (B) containing dyestuff and on another face of glass substrate (A) stacking infrared reflection film (C) form.Preferably providing a kind of wavelength cut-off light filter, wherein, the above-mentioned coating layer (B) containing dyestuff contains cyanine compound 0.01～10.0 mass parts as dyestuff, particularly acid stain relative to resin solid content 100 mass parts.
Description
Technical field
The present invention relates to the wavelength by the coating layer containing dyestuff, glass substrate and infrared reflection film are laminated cut
Only light filter (alternatively referred to as wavelength cut-off wave filter).
Background technology
Solid-state imager (CCD and C-MOS etc.) used in digital camera, video camera, mobile phone photographing unit etc.
Sensitivity from the ultraviolet region of optical wavelength until region of ultra-red.On the other hand, the visibility of people is only the visibility region of optical wavelength.
Therefore, by arranging infrared cut off filter between pick-up lens and solid-state imager, with the visibility close to people
Mode corrects the sensitivity (such as, referenced patent document 1～3) of solid-state imager.
In the past, infrared cut off filter was: is combined by the layer containing the material without absorption characteristic and is laminated into many
Layer also make use of their Reflection Filter of specific refractivity；On transparent substrate containing or combine light absorber
Absorption-type light filter.
Reflection Filter causes characteristic to change according to the difference of the angle of incidence of light, therefore has in picture
The disadvantages such as the heart and periphery color matching change.It addition, also have following disadvantage: reflected light becomes veiling glare in the optical path,
The reason become and cause the reduction of resolution and the stain/speckle of image, being referred to as the multiple imaging etc. of ghost image.
On the other hand, although absorption-type light filter does not has to produce the characteristic variations caused by the angle of incidence of light, but it is terrible
To target property, need suitable thickness.
In recent years, various units are required, and significantly miniaturization, conventional absorption-type light filter can not tackle it
The requirement of miniaturization.It addition, Reflection Filter especially because incident angle dependency and be difficult to reach required characteristic.
Prior art literature
Patent documentation
Patent documentation 1: No. 2005/253048 publication description of U.S. Patent Application Publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-118255 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-008532 publication
Summary of the invention
Invent problem to be solved
Therefore, it is an object of the invention to provide that incident angle dependency is low, thermostability is high and is capable of slimming
Wavelength cut-off light filter.
Means for solving the above
The present inventor has been repeated in-depth study, it was found that the angle of incidence of following wavelength cut-off light filter relies on
Property is low, and this wavelength cut-off light filter is characterised by, it is to have the coating containing dyestuff on a face of glass substrate (A)
Layer (B) and on another face of glass substrate (A) stacking infrared reflection film (C) form, thus complete the present invention.
The present invention provides a kind of wavelength cut-off light filter, it is characterised in that it is to have on a face of glass substrate (A)
Have the coating layer containing dyestuff (B) and on another face of glass substrate (A) stacking infrared reflection film (C) form.
It addition, the present invention provides a kind of solid camera head, it possesses above-mentioned wavelength cut-off light filter.
It addition, the present invention provides a kind of camera module, it possesses above-mentioned wavelength cut-off light filter.
Invention effect
The wavelength cut-off light filter of the present invention is excellent at the aspect that incident angle dependency is low.It addition, the wavelength of the present invention cuts
Only light filter is suitable for solid camera head and camera module.
Accompanying drawing explanation
Fig. 1 is the sectional view of the outline of the Rotating fields of the wavelength cut-off light filter representing the present invention.
Fig. 2 is the sectional view of a scheme of the composition of the camera module representing the present invention.
Fig. 3 is the sectional view of another scheme of the composition of the camera module representing the present invention.
Detailed description of the invention
Hereinafter, about the wavelength cut-off light filter of the present invention, based on preferred embodiment illustrating.
The wavelength cut-off light filter of the present invention is as it is shown in figure 1, use and have on a face of glass substrate (A) containing having illicit sexual relations
Material coating layer (B) and on another face of glass substrate (A) the Rotating fields of stacking infrared reflection film (C), will
There is the side light incident side as light of coating layer (B).Hereinafter, each layer is illustrated successively.
<glass substrate (A)>
Glass substrate (A) used in wavelength cut-off light filter as the present invention, can be from saturating in visibility region
Bright glass material suitably selects use, it is possible to use soda-lime glass, blank glass, pyrex, safety glass, stone
English glass, phosphate-based glass etc., wherein, soda-lime glass is cheap and is readily available, and is therefore preferred；Blank glass, borosilicate
Acid glass and safety glass is readily available, hardness is high, excellent processability, is therefore preferred.
It addition, after glass substrate (A) is implemented the pre-treatment such as silane coupler, applied coating solution form described later containing
When having coating layer (B) of dyestuff, the adhesiveness of glass substrate is increased by the dried coating layer (B) containing dyestuff of coating fluid.
As above-mentioned silane coupler, can list: γ-glycidoxypropyltrimethoxy silane, γ-epoxy the third oxygen
The epoxy functional alkoxyl silicones such as hydroxypropyl methyl diethoxy silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane
Alkane, N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N-phenyl-γ-ammonia
The Mercaptofunctionals such as amino functional alkoxy silane, γ mercaptopropyitrimethoxy silane such as base propyl trimethoxy silicane
Alkoxy silane etc..
The thickness of glass substrate (A) is not particularly limited, but preferably 0.05～8mm, from lightweight and the sight of intensity
Point sets out, and more preferably 0.05～1mm.
In the present invention, owing to substrate is glass plate, therefore, it is possible to directly coating on substrate, carry out cutting after drying and add
Work, structure and technique become simple.Further, since substrate is glass plate, therefore with thermostability (260 compared with the situation of plastics
DEG C backflow toleration) high.
<coating layer (B)>
The coating layer (B) containing dyestuff used in the wavelength cut-off light filter of the present invention can be come by following method
Formed: dyestuff, resin and other composition of coordinating as required are dissolved in suitable solvent or disperse to prepare coating
Liquid, by obtained coating solution on glass substrate (A).
As coating process, can list: spin-coating method, dip coating, spraying process, pearl are coated with (bead coating) method, gas
Cutter rubbing method, curtain coating processes, rolling method, wire rod rubbing method, gravure coating process, die coating method, the extrusion coated of use funnel
Method etc..
As above-mentioned dyestuff, be not particularly limited, it is possible to use known dyestuff, for example, it is possible to list azoles and
Diazole compounds, coumarin compound, hydroxyquinoline compounds, phthalocyanine compound, naphthalene lactam compound, fluorenes and derivative
Thing, anthracene and derivant thereof, ton compound (Pai Luoning system, rhodamine system, fluorescence prime system), stilbene (1,2-stilbene) chemical combination
Thing, cyanine compound, azo-compound, azomethine compounds, indigo compound, thioindigo compounds, oxonol compound,
Side acid compound, benzazolyl compounds, compound of styryl, porphin compound, compound, crocic acid methylene ester
(croconic methine) compound, pyrylium compound, thio-pyrylium compound, triaryl methane compounds, hexichol
Methylmethane compound, tetrahydrochysene compound choline, indophenols compound, anthraquinone compounds, naphthoquinone compound, thiazine compounds, spiral shell pyrrole
Mutter compound, benzylidene compound, indane compound, compound, compound, phthaloperine (phthaloperine) change
Compound, azines, acridine compounds, thiazine compounds, piperazine compound, polyacetylene compound, phenylacetylene compound, benzene
Sub-acetylide, five-membered ring and the heterocyclic compound etc. of hexatomic ring, these can be used in mixed way multiple.
In above-mentioned dyestuff, from the viewpoint of dissolubility, preferably ton compound, phthalocyanine compound, cyanine compound, idol
The acid staiies such as nitrogen compound, oxonol compound, anthraquinone compounds.
In above-mentioned acid stain, from the viewpoint of the easy degree and MOLECULE DESIGN of synthesis, more preferably spend
Blue or green compound.
As above-mentioned cyanine compound, for example, it is possible to list the compound represented by following formula (1).
A-Q-A (1)
pAn-q
(in formula, A represents the group in (a)～(m) of following group of I, A ' represent selected from following group of II (a ')～
Group in (m '),
Q represents and constitutes methine chain that carbon number is 1～9, can contain the link group of circular structure in chain, this time
Hydrogen atom in methyl chain can use hydroxyl, halogen atom, cyano group ,-NRR ', aryl, aralkyl or alkyl to replace, should-NRR ', virtue
Base, aralkyl and alkyl can use hydroxyl, halogen atom, cyano group or-NRR ' to replace further, it is also possible to-O-,-S-,-
CO-、-COO-、-OCO-、-SO2-,-NH-,-CONH-,-NHCO-,-N=CH-or-CH=CH-interrupt,
R and R ' represents aryl, aralkyl or alkyl,
Anq-Representing the anion of q valency, q represents 1 or 2, p to represent electric charge to remain the coefficient of neutrality).
Group I
Group II
(in formula, ring C and ring C ' represents phenyl ring, naphthalene nucleus, phenanthrene ring or pyridine ring,
R1And R1’Represent hydroxyl, halogen atom, nitro, cyano group ,-SO3H, carboxyl, amino, amide groups, ferrocenyl, carbon are former
Subnumber be 6～30 aryl, carbon number be the aralkyl of 7～30 or alkyl that carbon number is 1～8,
Above-mentioned R1And R1’In the aryl that carbon number is 6～30, carbon number be 7～30 aralkyl and carbon atom
Number be 1～8 alkyl can use hydroxyl, halogen atom, nitro, cyano group ,-SO3H, carboxyl, amino, amide groups or ferrocenyl take
Generation, it is also possible to-O-,-S-,-CO-,-COO-,-OCO-,-SO2-,-NH-,-CONH-,-NHCO-,-N=CH-or-CH=
CH-interrupts,
R2～R9And R2’～R9’Represent and R1And R1’Same group or hydrogen atom,
X and X ' represents oxygen atom, sulphur atom, selenium atom ,-CR51R52-, carbon number be 3～6 cycloalkane-1,1-two
Base ,-NH-or-NY2-,
R51And R52Represent and R1And R1’Same group or hydrogen atom,
Y, Y ' and Y2Represent hydrogen atom or hydroxyl, halogen atom, cyano group, carboxyl, amino, amide groups, ferrocene can be used
Base ,-SO3H or alkyl that the substituted carbon number of nitro is 1～20, carbon number be 6～30 aryl or carbon number be 7
～the aralkyl of 30,
Above-mentioned Y, Y ' and Y2In the alkyl that carbon number is 1～8, carbon number be 6～30 aryl and carbon atom
Number is that the methylene in the aralkyl of 7～30 can also use-O-,-S-,-CO-,-COO-,-OCO-,-SO2-、-NH-、-
CONH-,-NHCO-,-N=CH-or-CH=CH-interrupt,
R and r ' represent 0 or (a)～(e), (g)～(j), (l), (m), (a ')～(e '), (g ')～(j '), (l ') and
Can substituted number in (m ')).
As the R in above-mentioned formula (1)1～R9And R1’～R9’And in X and X ' by R51And R52The halogen atom represented,
Can list: fluorine, chlorine, bromine, iodine,
As the aryl that carbon number is 6～30, can list: phenyl, naphthyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl,
4-aminomethyl phenyl, 4-ethenylphenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 4-butyl phenyl, 4-isobutyl phenenyl, 4-
Tert-butyl-phenyl, 4-hexyl phenyl, 4-cyclohexyl phenyl, 4-octyl phenyl, 4-(2-ethylhexyl) phenyl, 4-stearyl benzene
Base, 2,3-3,5-dimethylphenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, 3,4-dimethyl benzene
Base, 3,5-3,5-dimethylphenyl, 2,4-di-t-butyl phenyl, 2,5-di-t-butyl phenyl, 2,6-di-t-butyl phenyl, 2,4-
Two-tertiary pentyl phenyl, 2,5-bis--tertiary pentyl phenyl, 2,5-bis--t-octyl phenyl, 2,4-dicumylphenyl, 4-cyclohexyl benzene
Base, (1,1 '-biphenyl)-4-base, 2，4，5-trimethylphenyl, ferrocenyl etc.,
As the aralkyl that carbon number is 7～30, can list: benzyl, phenethyl, 2-phenyl-propane-2-base, two
Phenyl methyl, trityl group, styryl, cinnamyl, ferrocenyl methyl, ferrocenyl propyl group etc.,
As the alkyl that carbon number is 1～8, can list: methyl, ethyl, propyl group, isopropyl, butyl, Zhong Ding
Base, the tert-butyl group, isobutyl group, amyl group, isopentyl, tertiary pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptan
Base, 2-heptyl, 3-heptyl, different heptyl, tertiary heptyl, 1-octyl group, iso-octyl, t-octyl etc..
Above-mentioned carbon number be 6～30 aryl, carbon number be 7～30 aralkyl and carbon number be 1～8
Alkyl can use hydroxyl, halogen atom, nitro, cyano group ,-SO3H, carboxyl, amino, amide groups or ferrocenyl replace, it is also possible to
With-O-,-S-,-CO-,-COO-,-OCO-,-SO2-,-NH-,-CONH-,-NHCO-,-N=CH-or-CH=CH-interrupt, this
A little numbers replaced and interrupt and position are arbitrary.
Such as, replace the group obtained as the alkyl halogen atom that above-mentioned carbon number is 1～8, for example, it is possible to row
Enumerate: chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, nine fluorine butyl etc.,
Interrupt the group obtained as the alkyl that above-mentioned carbon number is 1～8 with-O-, can list: methoxyl group,
Ethyoxyl, isopropoxy, propoxyl group, butoxy, amoxy, isoamoxy, hexyloxy, epoxide in heptan, octyloxy, 2-ethyl hexyl oxygen
The alkoxyls such as base, 2-methoxy ethyl, 2-(2-methoxyl group) ethoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 4-first
The alkoxyalkyls etc. such as epoxide butyl, 3-methoxybutyl,
Replace as the alkyl halogen atom that above-mentioned carbon number is 1～8 and interrupt the group obtained, example with-O-
As, can list: chloromethane epoxide, dichloromethane epoxide, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy,
Nine fluorine butoxy etc..
In above-mentioned formula (1), as cycloalkane-1 that the carbon number represented by X and X ' is 3～6,1-diyl, Ke Yilie
Enumerate: cyclopropane-1,1-diyl, Tetramethylene .-1,1-diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-diformazan basic ring fourth
Alkane-1,1-diyl, Pentamethylene .-1,1-diyl, hexamethylene-1,1-diyl etc..
In above-mentioned formula (1), as by Y, Y ' and Y2The halogen atom of expression, carbon number are alkyl, the carbon atom of 1～20
Number is the aryl of 6～30 and aralkyl that carbon number is 7～30, can list above-mentioned R1Deng explanation in illustrated in go out
Group, the hydrogen atom in these substituent groups can use hydroxyl, halogen atom, cyano group, carboxyl, amino, amide groups, ferrocenyl ,-
SO3H or nitro replace with arbitrary number.
It addition, these Y, Y ', Y2In alkyl, aryl and aralkyl in methylene can also use-O-,-S-,-
CO-、-COO-、-OCO-、-SO2-,-NH-,-CONH-,-NHCO-,-N=CH-or-CH=CH-interrupt.For example, it is possible to enumerate
Go out: methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, isobutyl group, amyl group, isopentyl, tertiary pentyl, hexyl, 2-
Hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, different heptyl, tertiary heptyl, 1-octyl group, different pungent
Base, t-octyl, 2-ethylhexyl, nonyl, different nonyl, decyl, dodecyl, tridecyl, myristyl, pentadecyl, ten
The alkyl such as six alkyl, heptadecyl, octadecyl；Phenyl, naphthyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 4-
Ethenylphenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 4-butyl phenyl, 4-isobutyl phenenyl, 4-tert-butyl-phenyl, 4-
Hexyl phenyl, 4-cyclohexyl phenyl, 4-octyl phenyl, 4-(2-ethylhexyl) phenyl, 4-stearyl phenyl, 2,3-dimethyl benzene
Base, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, 3,4-3,5-dimethylphenyl, 3,5-dimethyl benzene
The aryl such as base, 2,4-di-t-butyl phenyl, cyclohexyl phenyl；Benzyl, phenethyl, 2-phenyl-propane-2-base, diphenyl methyl,
The group that the aralkyl such as trityl group, styryl, cinnamyl etc. interrupt with ehter bond, thioether bond etc. and obtain, such as 2-first
Epoxide ethyl, 3-methoxy-propyl, 4-methoxybutyl, 2-butoxyethyl group, methoxyethoxyethyl, methoxy ethoxy
Ethoxyethyl group, 3-methoxybutyl, 2-Phenoxyethyl, 3-phenoxy propyl, 2-methylmercaptoethyl, 2-phenylthio ethyl
Deng.
Constituting methine chain that carbon number is 1～9, can contain in chain as being represented by Q in above-mentioned formula (1)
The link group of circular structure, any one in following (Q-1)～(Q-11) group represented is owing to easily manufacturing, therefore
It is preferred.Carbon number is that the carbon number in the methine chain of 1～9 does not includes to comprise in methine chain or methine chain
The carbon atom of the group that is further substituted with of ring structure (carbon such as, linking two ends in group (Q-1)～(Q-11) is former
Son, Z ' or R14～R19This carbon atom containing during carbon atom).
(in formula, R14、R15、R16、R17、R18、R19And Z ' separately represents hydrogen atom, hydroxyl, halogen atom, cyanogen
Base ,-NRR ', aryl, aralkyl or alkyl ,-NRR ', aryl, aralkyl and alkyl should can use hydroxyl, halogen atom, cyano group
Or-NRR ' replaces, it is also possible to-O-,-S-,-CO-,-COO-,-OCO-,-SO2-,-NH-,-CONH-,-NHCO-,-N=CH-
Or-CH=CH-interrupts, R and R ' represents aryl, aralkyl or alkyl).
As above-mentioned by R14、R15、R16、R17、R18、R19And halogen atom, aryl, aralkyl or the alkyl that Z ' represents, can
To list R1Deng explanation in illustrated in go out those；As the aryl represented by R and R ', aralkyl or alkyl, Ke Yilie
Enumerate R1Deng explanation in illustrated in go out those.
As in above-mentioned formula (1) by pAnq-The anion of q valency represented, can list: Loprazolam root cloudy from
Son, dodecyl sodium sulfonate root anion, benzenesulfonate anion, toluenesulfonate anion, trifluoromethayl sulfonic acid root anion,
Naphthalenesulfonate anion, diphenylamine-4-azochlorosulfonate acid anion, 2-amino-4-methyl-5-chloro benzenesulfonate anion, 2-ammonia
Base-5-nitrobenzene-sulfonic acid root anion, Japanese Unexamined Patent Publication 10-235999, Japanese Unexamined Patent Publication 10-337959, Japanese Unexamined Patent Publication 11-
102088, Japanese Unexamined Patent Publication 2000-108510, Japanese Unexamined Patent Publication 2000-168223, Japanese Unexamined Patent Publication 2001-209969, Japanese Unexamined Patent Publication
2001-322354, Japanese Unexamined Patent Publication 2006-248180, Japanese Unexamined Patent Publication 2006-297907, Japanese Unexamined Patent Publication 8-253705 publication,
In special table 2004-503379 publication, Japanese Unexamined Patent Publication 2005-336150 publication, No. 2006/28006 publication of International Publication etc.
The organic sulfonic acid root aniones such as the azochlorosulfonate acid anion recorded, and chloride ion, bromide ion, iodide ion, fluorine
Compound ion, chloranion, thiocyanate ion, perchlorate, hexafluorophosphoricacid acid ions, hexafluoro-antimonic acid radical ion,
Tetrafluoroborate ion, octylphosphonic acid radical ion, dodecylphosphoric acid radical ion, octadecyl phosphate anion, phosphenylic acid
Radical ion, nonyl phenyl phosphate anion, 2,2 '-di-2-ethylhexylphosphine oxide (4,6-di-t-butyl phenyl) phosphonium acid ion, four (five fluorine
Phenyl) borate ion, there is the quencher anion of the function of the bioactive molecule deexcitation (quencher) making to be in excited state
With there is on cyclopentadiene ring the metallocenes such as the ferrocene of anionic property group, ruthenocene such as carboxyl, phosphonate group, sulfonic group
Compound anion etc..
O.1～102 as the object lesson of cyanine compound used in the present invention, following compound N can be listed.
It should be noted that in following illustration, illustrate eliminating the cyanine cation of anion.
The manufacture method of above-mentioned cyanine compound is not particularly limited, can be by utilizing well-known General reactions
Method obtains, for example, it is possible to list shown in the approach as described in Japanese Unexamined Patent Publication 2010-209191, by having this structure
The reaction of compound and the imine derivative method that carries out synthesizing.
The maximum absorption wavelength (λ max) of the preferred film of dyestuff used in the present invention is 650～1200nm, more preferably
650～900nm.During more than the 1200nm that maximum absorption wavelength (λ max) is the present invention of film, it is impossible to play the effect of the present invention
Really, when the maximum absorption wavelength of film (λ max) is less than 650nm, luminous ray can be absorbed, be therefore undesirable.
In the coating fluid forming the above-mentioned coating layer (B) containing dyestuff, the content of dyestuff with individually one or more
Preferably 0.01～50 mass %, more preferably 0.1～30 mass % from the point of view of He Jiing.The content of dyestuff is less than 0.01 mass %
Time, sometimes can not obtain sufficient characteristic, and when the content of dyestuff is more than 50 mass %, in coating layer, sometimes cause dyestuff
Separate out.
It addition, in the above-mentioned coating layer (B) containing dyestuff, the content of dyestuff is with relative from the point of view of individually one or more add up to
It is preferably 0.01～10.0 mass parts, more preferably 0.25～5.0 mass parts in resin solid content 100 mass parts.
As above-mentioned resin, use the natural polymers such as such as gelatin, casein, starch, cellulose derivative, alginic acid
Material or poly-methylpropanoic acid methyl ester, polyvinyl butyral resin, polyvinyl pyrrolidone, polyvinyl alcohol, polrvinyl chloride, benzene second
The synthesis macromolecular material such as alkene-butadiene copolymer, polystyrene, Merlon, polyamide.
As above-mentioned other composition coordinated as required, can list: benzotriazole system, triazine system, benzoate
It it is UV absorbent；Phenol system, phosphorus system, sulfur system antioxidant；By cation system surfactant, anion system surface activity
The antistatic additive that agent, nonionic system surfactant, amphoteric surfactant etc. are constituted；Halogen based compound, phosphate ester system
Compound, phosphoamide based compound, tripolycyanamide based compound, fluorine resin or metal-oxide, (gathering) melamine phosphate,
The fire retardants such as (gathering) piperazine phosphate；Hydrocarbon system, fatty acid series, aliphatic alcohol system, aliphatic ester system, aliphatic amide system or metallic soap
Base lubricant；Fumed silica, silica particle, Silicon stone, diatom great soil group, clay, Kaolin, kieselguhr, silicon dioxide are solidifying
Glue, calcium silicates, sericite, kaolinite, firestone, feldspar powder, Vermiculitum, attapulgite, Talcum, Muscovitum, minnesotaite
(minesotite), the silicic acid such as pyrophyllite, silicon dioxide system inorganic additive；The filler such as glass fibre, calcium carbonate；Nucleation
The caoutchouc elasticity imparting agents etc. such as crystallization agent, silane coupler, the flexible polymer such as agent, crystallization promoter.About these its
The usage amount of its composition, is adding up to below 50 mass % in being formed containing the coating fluid of the coating layer (B) of dyestuff.
As above-mentioned solvent, it is not particularly limited, can suitably use known various solvents, for example, it is possible to list:
The alcohols such as isopropanol；The ether alcohol classes such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, butanediol；Acetone, methyl ethyl ketone,
The ketones such as methyl iso-butyl ketone (MIBK), Ketohexamethylene, DAA；The esters such as ethyl acetate, butyl acetate, methoxy ethyl acetate；Third
The fluorination alcohols such as the esters of acrylic acids such as olefin(e) acid ethyl ester, butyl acrylate, 2,2,3,3-C3-Fluoroalcohol.；Hexane, benzene, toluene, diformazan
The hydro carbons such as benzene；The chlorinated hydrocarbons etc. such as dichloromethane, dichloroethanes, chloroform.These organic solvents can be used alone or mix
Use.
The thickness of the coating layer (B) containing dyestuff is 1～can obtain uniform film during 200 μm, favourable to filming, because of
This is preferred.When the thickness of the coating layer (B) containing dyestuff is less than 1 μm, it is impossible to demonstrate function fully, and containing dyestuff
The thickness of coating layer (B) more than 200 μm time, the likely residual solvent when coating.
<infrared reflection film (C)>
Infrared reflection film (C) used in the cut-off filter of the present invention has the wavelength stopping 700～1200nm
The function of the light in region, is formed by the multilayer dielectric film of alternately laminated low-index layer and high refractive index layer.
As the material constituting above-mentioned low-index layer, it is possible to use refractive index is the material of 1.2～1.6, for example, it is possible to
List: silicon dioxide, aluminium oxide, lanthanum fluoride, Afluon (Asta), lithium aluminum sodium etc..
As the material constituting above-mentioned high refractive index layer, it is possible to use refractive index is the material of 1.7～2.5, for example, it is possible to
List titanium dioxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthana, yittrium oxide, zinc oxide, zinc sulfide, Indium sesquioxide. etc.,
Further, it is also possible to list using these materials above-mentioned as main constituent and containing a small amount of titanium dioxide, stannum oxide, cerium oxide etc.
Material etc..
About the above-mentioned low-index layer of stacking and the method for high refractive index layer, as long as being formed the electricity of these layer stackup
Dielectric multilayer-film just, is not particularly limited, for example, it is possible to list: by CVD, sputtering method, vacuum vapour deposition etc. at glass
The method forming the multilayer dielectric film of alternately laminated low-index layer and high refractive index layer on glass substrate.Additionally, it is possible to
To be pre-formed multilayer dielectric film, it is fitted on the glass substrate with binding agent.
Stacking number is 10～80 layers, from the viewpoint of technique and intensity, and preferably 25～50 layers.
The thickness of above-mentioned low-index layer and high refractive index layer typically respectively wants the wavelength X (nm) of the light of obstruction
The thickness of 1/10～1/2.When thickness is less than 0.1 λ or more than 0.5 λ, refractive index (n) and physical film thickness (d) long-pending (nd) with by λ/
The blooming that the multiple of 4 represents differs considerably, it is possible to can not stop/through specific wavelength.
As above-mentioned infrared reflection film (C), in addition to above-mentioned multilayer dielectric film, it is also possible to use containing greatly inhaling
Receive wavelength be 700～1100nm the film of dyestuff, the film of stacking macromolecule, have employed coating cholesteric crystal formed
The film of the organic material such as film.
The preferred transmitance of wavelength cut-off light filter of the present invention meets following (i)～(iii).It addition, above-mentioned transmitance
Mensuration is to be measured by Japan Spectroscopy Corporation UV, visible light near infrared spectrometer V-570.
(i) transmitance when wavelength is to measure from the vertical direction of wavelength cut-off light filter in the range of 430～580nm
Meansigma methods be more than 75%.
(ii) transmitance when wavelength is to measure from the vertical direction of wavelength cut-off light filter at 800～1000nm is flat
Average is less than 5%.
(iii) passing through when wavelength is to measure from the vertical direction of wavelength cut-off light filter in the range of 560～800nm
Rate reach the value (Ya) of the wavelength of 80% with from relative to during the goniometry that vertical direction is 35 ° of wavelength cut-off light filter
The absolute value of the difference that transmitance reaches the value (Yb) of the wavelength of 80% is below 30nm.
In wavelength cut-off light filter, the wavelength of above-mentioned (i) is the meansigma methods of the transmitance in the range of 430～580nm
During less than 75%, hardly through the light in visible region；The wavelength of above-mentioned (ii) is the transmitance at 800～1000nm
Meansigma methods more than 5% time, hardly cut-off infrared spectral range in light, it is therefore possible to be difficult to correcting sensitivity with close to people
Visibility.
During it addition, the absolute value of the difference of Ya Yu Yb of above-mentioned (iii) is more than 30nm, the dependency that the angle of incidence of light is caused
Increase, make the characteristic of cut-off filter change according to the difference of the angle of incidence wavelength of light, drawing it is therefore possible to produce
The disadvantages such as the center in face and periphery color matching change.
As the particular use of the wavelength cut-off light filter of the present invention, can list: at the window glass of automobile and building
The upper heat ray cut-off filter installed such as glass；Digital camera, DV, monitoring photographing unit, vehicle-mounted photographing unit, net
The visibility correction of the solid-state imagers such as CCD and CMOS in the solid camera heads such as network photographic head, mobile phone photographing unit is used；
Automatic exposure meter；The display devices etc. such as plasma scope.
Then, solid camera head and camera module to the present invention illustrate.
The solid camera head of the present invention except possessing the wavelength cut-off light filter of the present invention at the front surface of imaging apparatus
In addition, constitute in the same manner as known solid camera head.The wavelength cut-off light filter 1 of the present invention can be as shown in Figure 2
In the part that the light incident side of solid-state imager 2 is fixed on beyond solid-state imager, it is also possible to the most solid
It is scheduled on the front surface of solid-state imager 2.
In the solid camera head of the present invention, as required, can configure optical low-pass filter, antireflection filters
Device, color filter etc., be not particularly limited the order that these devices carry out stacking.
Hereinafter, about the camera module of one of the solid camera head as the present invention, the wavelength cut-off to the present invention
The light filter 1 situation in the part that the light incident side of solid-state imager 2 is fixed on beyond solid-state imager is specifically carried out
Explanation.
Fig. 2 is cutting of a scheme of the composition of the camera module of one of the solid camera head being denoted as the present invention
Face figure.Camera module includes: be formed on a semiconductor substrate to overlook the solid-state imager 2 for rectangular-shaped；With solid
The opposition side of the light accepting part 3 of body imaging apparatus 2 stacks gradually coating layer (the B)/glass substrate containing dyestuff from light inlet side
(A) the wavelength cut-off light filter 1 of/infrared reflection film (C), except being subject on a surface of solid-state imager 2
Region beyond light portion 3 is formed, and solid-state imager 2 and wavelength cut-off light filter 1 binding agent 4 is engaged.Take the photograph as solid
As the camera module of device absorbs from outside light by wavelength cut-off light filter 1, by being subject at solid-state imager 2
In light portion 3, the photo detector of configuration receives light.
As binding agent 4, it is possible to use the UV curing adhesive such as acrylic resin, epoxy system resin or Thermocurable
Resin, after being coated with this binding agent 4 equably, uses known photoetching technique by binding agent 4 Butut as required, passes through heat cure
Engage.During joint, vacuum pressed can be carried out after fitting in vacuum environment.
Installation base plate 8 is the rigid substrates using glass epoxy substrate and ceramic substrate etc., is provided with controlling solid and takes the photograph
The substrate of the control circuit of element 2.
Installation base plate 8 configures solid-state imager 2, then, on the position of the fixed mirror headstock 7 of installation base plate 8
It is pre-coated with binding agent 4.
Lens cap 6 protects camera lens 5.It addition, lens bracket 7 keeps camera lens 5, it possesses: is installed on installation base plate 8 and covers
The basilar part 7a of the box like of lid solid-state imager 2；Lens barrel portion 7b with the drum keeping camera lens 5.
Then, in the way of the lower surface of lens bracket 7 contacts, on installation base plate 8, camera lens is configured with the binding agent 4 of coating
Frame 7, it addition, with the focus of the distance between the camera lens 5 in the light accepting part 3 of solid-state imager 2 and lens bracket 7 and camera lens 5 away from
The regulation of the position of lens bracket 7 is carried out from consistent mode.
After the position adjustments carrying out lens bracket 7, to binding agent 4 irradiation ultraviolet radiation, make binding agent 4 solidify, can manufacture
Camera module.
Installation base plate 8 entirety being fixed with lens bracket 7 can also be heated at about 85 DEG C, more be filled by heat cure
Ground is divided to carry out the solidification of binding agent 4.
It addition, because contain installation base plate in the manufacture method of camera module after the operation of irradiation ultraviolet radiation
The operation of 8 overall heating, therefore lens bracket 7, camera lens 5 and wavelength cut-off light filter 1 are required to the material using thermostability high.
Specifically, in addition to being previously discussed for the heating of the heat cure of binding agent 4, will join on the lower surface of installation base plate 8
The multiple solder put carries out heating melt process at about 260 DEG C, thus welds with other substrate, the most preferably by having backflow
The material of toleration is formed.
Embodiment
Hereinafter, enumerate embodiment etc. and the present invention is given the account in greater detail, but the present invention is not by these embodiments etc.
Restriction.
Manufacture example 1～11 show for be formed at used in the wavelength cut-off light filter of the present invention containing dyestuff
The preparation example of the coating fluid of coating layer (B), compares manufacture example 2～4 and shows and use wavelength cut-off light filter for being formed to compare
Used in the preparation example of comparison coating fluid of the coating layer (B) containing dyestuff, embodiment 1～11 shows the present invention's
The manufacture example of wavelength cut-off light filter, comparative example 1～4 shows and compares by the manufacture example of wavelength cut-off light filter, in evaluation Example 1
～in 11, have rated the wavelength cut-off light filter of the present invention manufactured by embodiment 1～11, in comparative evaluation example 1～4, comment
The comparison wavelength cut-off light filter that valency is manufactured by comparative example 1～4.
[manufacture example 1～11 and compare manufacture example 2～4] coating fluid No.1～No.11 and compare and use coating fluid No.2
～the preparation of No.4
Mix each composition with the proportioning shown in table 1 and table 2, obtain coating fluid No.1～No.11 and compare with coating
Liquid No.2～No.4.
Table 1
Table 2
[embodiment 1～11 and comparative example 1～4] wavelength cut-off light filter No.1～No.11 and comparing cuts with wavelength
The only manufacture of light filter No.1～No.4
By the alternately laminated silicon dioxide of vacuum vapour deposition on a face of the glass substrate (B) that thickness is 100 μm
(SiO2) layer and titanium dioxide (TiO2) layer, formed total number of plies be 30 layers, thickness be about the infrared reflection film (C) of 3 μm.
The face different from this infrared reflection film (C) at the obtained glass substrate (B) being formed with infrared reflection film (C)
On, after coating fluid No.1～No.11 obtained by being manufactured in example 1～11 by metering bar coater #30 coating (thickness is 10 μm),
It is dried 10 minutes at 100 DEG C and forms coating layer, make wavelength cut-off light filter No.1～No.11 of the present invention.
The glass substrate defining infrared reflection film (C) obtained above is used wavelength cut-off light filter as comparing
No.1。
It addition, on a face of the glass substrate (B) that thickness is 100 μm, be coated with (thickness by metering bar coater #30
It is 10 μm) compare with after coating fluid No.2～No.4, it is dried 10 minutes at 100 DEG C and forms coating layer (A), comparison is used
Wavelength cut-off light filter No.2～No.4.
[evaluation Example 1～11 and comparative evaluation example 1～4]
About wavelength cut-off light filter No.1～No.11 of the present invention obtained in embodiment 1～11 and comparative example 1～
Comparison wavelength cut-off light filter No.1～No.4 obtained in 4, obtains and i) cuts from wavelength in the range of wavelength 430～580nm
The meansigma methods of transmitance when only the vertical direction of light filter measures, ii) filter from wavelength cut-off in wavelength is 800～1000nm
The meansigma methods of the transmitance when vertical direction of light device measures and iii) it is from wavelength in the range of 560～800nm at wavelength
The transmitance when vertical direction of cut-off filter measures reaches the value (Ya) of the wavelength of 80% and filters with from relative to wavelength cut-off
The vertical direction of light device is the absolute value that the transmitance during goniometry of 35 ° reaches the difference of the value (Yb) of the wavelength of 80%.Will
Result is shown in table 1 and table 2.It addition, the mensuration of above-mentioned transmitance is the reddest by Japan Spectroscopy Corporation's UV, visible light
Outer spectrophotometer V-570 is measured.
From above-mentioned table 1 and the result of table 2, the wavelength of the comparative example 1 without the coating layer containing dyestuff (B) cuts
Only the incident angle dependency of light filter is high, not there is infrared reflection film (C) though the wavelength cut-off light filter of comparative example 2～4
So incident angle dependency is low, but is that in the range of 430～580nm, transmitance is low at wavelength or is at 800～1000nm at wavelength
Transmitance is high, be i.e. not transmitted through light in visible region, and not cut-off light in infrared spectral range therefore cannot correcting sensitivity
With the visibility close to people.
On the other hand, the wavelength cut-off light filter of the present invention is that in the range of 430～580nm, transmitance is high at wavelength,
Wavelength is that at 800～1000nm, transmitance is low, and incident angle dependency is low.
As can be known from the above results, the incident angle dependency of the wavelength cut-off light filter of the present invention is low, it is characterised in that its
It is by there is on a face of glass substrate (A) coating layer (B) containing dyestuff and at another of glass substrate (A)
On face, stacking infrared reflection film (C) forms.Thus, the wavelength cut-off light filter of the present invention is to solid camera head and photograph
Machine module is useful.
Symbol description
(A). glass substrate
(B). coating layer
(C). infrared reflection film (evaporation film)
1. wavelength cut-off light filter 2. solid-state imager 3. light accepting part
4. binding agent 5. camera lens 6. lens cap
7. lens bracket 7a. basilar part 7b. lens barrel portion
8. installation base plate
Claims (7)
1. a wavelength cut-off light filter, it is characterised in that it is to have containing dyestuff on a face of glass substrate (A)
Coating layer (B) and on another face of glass substrate (A) stacking infrared reflection film (C) form,
The transmitance of described wavelength cut-off light filter meets following (i)～(iii):
Putting down of (i) transmitance when wavelength is to measure from the vertical direction of wavelength cut-off light filter in the range of 430～580nm
Average is more than 75%；
(ii) meansigma methods of the transmitance when wavelength is to measure from the vertical direction of wavelength cut-off light filter at 800～1000nm
It is less than 5%；
(iii) transmitance when wavelength is to measure from the vertical direction of wavelength cut-off light filter in the range of 560～800nm reaches
To the wavelength of 80% value (Ya) with from relative to the passing through during goniometry that vertical direction is 35 ° of wavelength cut-off light filter
The absolute value of the difference that rate reaches the value (Yb) of the wavelength of 80% is below 30nm.
Wavelength cut-off light filter the most according to claim 1, it is characterised in that described dyestuff is acid stain.
Wavelength cut-off light filter the most according to claim 1 and 2, it is characterised in that the described coating layer (B) containing dyestuff
Dyestuff 0.01～10.0 mass parts is contained relative to resin solid content 100 mass parts.
Wavelength cut-off light filter the most according to claim 1 and 2, it is characterised in that described dyestuff is cyanine compound.
Wavelength cut-off light filter the most according to claim 3, it is characterised in that described dyestuff is cyanine compound.
6. a solid camera head, it is characterised in that possess the wavelength cut-off according to any one of Claims 1 to 5 and filter
Device.
7. a camera module, it is characterised in that possess the wavelength cut-off light filter according to any one of Claims 1 to 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012100275 | 2012-04-25 | ||
| JP2012-100275 | 2012-04-25 | ||
| PCT/JP2013/058986 WO2013161492A1 (en) | 2012-04-25 | 2013-03-27 | Wavelength cut filter |
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| Publication Number | Publication Date |
|---|---|
| CN103930806A CN103930806A (en) | 2014-07-16 |
| CN103930806B true CN103930806B (en) | 2016-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380003842.6A Active CN103930806B (en) | 2012-04-25 | 2013-03-27 | Wavelength cut-off light filter |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6305331B2 (en) |
| KR (1) | KR101987926B1 (en) |
| CN (1) | CN103930806B (en) |
| TW (1) | TWI634352B (en) |
| WO (1) | WO2013161492A1 (en) |
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| JP6020746B2 (en) * | 2013-12-26 | 2016-11-02 | 旭硝子株式会社 | Optical filter |
| JP6312241B2 (en) * | 2014-03-19 | 2018-04-18 | Ｈｏｙａ Ｃａｎｄｅｏ Ｏｐｔｒｏｎｉｃｓ株式会社 | Transparent substrate |
| JP6535979B2 (en) | 2014-04-16 | 2019-07-03 | ソニー株式会社 | Imaging device and imaging device |
| JP2016162946A (en) * | 2015-03-04 | 2016-09-05 | Jsr株式会社 | Solid state image sensor |
| JP6720969B2 (en) * | 2015-05-12 | 2020-07-08 | Ａｇｃ株式会社 | Optical filter and imaging device |
| JP6642313B2 (en) * | 2015-07-28 | 2020-02-05 | Jsr株式会社 | New cyanine compound, optical filter and device using optical filter |
| WO2017022708A1 (en) * | 2015-08-06 | 2017-02-09 | 株式会社Adeka | Thermally reactive composition |
| JP6619627B2 (en) * | 2015-11-20 | 2019-12-11 | 株式会社Adeka | Coloring composition |
| JPWO2017094672A1 (en) | 2015-11-30 | 2018-09-13 | Jsr株式会社 | Optical filters, ambient light sensors and sensor modules |
| KR101832114B1 (en) | 2015-12-01 | 2018-02-23 | 아사히 가라스 가부시키가이샤 | Optical Filters and Imaging Devices |
| KR20180097178A (en) * | 2016-01-21 | 2018-08-30 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Optical Camouflage Filters |
| WO2017124664A1 (en) | 2016-01-21 | 2017-07-27 | 3M Innovative Properties Company | Optical camouflage filters |
| CN108603038A (en) | 2016-02-02 | 2018-09-28 | Ａｇｃ株式会社 | Near infrared absorbing coloring matter, optical filter and photographic device |
| US11163098B2 (en) * | 2016-06-08 | 2021-11-02 | Jsr Corporation | Optical filter and optical sensor device |
| JP6339755B1 (en) * | 2016-11-14 | 2018-06-06 | 日本板硝子株式会社 | Light absorbing composition and optical filter |
| KR102476708B1 (en) * | 2017-11-01 | 2022-12-09 | 삼성전자주식회사 | Optical filter, and camera module and ectronic device comprising thereof |
| WO2022181422A1 (en) * | 2021-02-26 | 2022-09-01 | Ａｇｃ株式会社 | Optical filter |
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| US6049419A (en) * | 1998-01-13 | 2000-04-11 | 3M Innovative Properties Co | Multilayer infrared reflecting optical body |
| JP4412867B2 (en) * | 2000-07-06 | 2010-02-10 | 富士フイルム株式会社 | Optical filter |
| US6929864B2 (en) * | 2002-08-17 | 2005-08-16 | 3M Innovative Properties Company | Extensible, visible light-transmissive and infrared-reflective film and methods of making and using the film |
| JP2004133174A (en) * | 2002-10-10 | 2004-04-30 | Mitsubishi Chemicals Corp | Optical filter |
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| JP2006106570A (en) * | 2004-10-08 | 2006-04-20 | Adl:Kk | Light absorbing filter |
| JP2008009142A (en) * | 2006-06-29 | 2008-01-17 | Dainippon Printing Co Ltd | Composite filter |
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2013
- 2013-03-27 JP JP2014512430A patent/JP6305331B2/en active Active
- 2013-03-27 CN CN201380003842.6A patent/CN103930806B/en active Active
- 2013-03-27 KR KR1020147012499A patent/KR101987926B1/en active IP Right Grant
- 2013-03-27 WO PCT/JP2013/058986 patent/WO2013161492A1/en active Application Filing
- 2013-04-11 TW TW102112912A patent/TWI634352B/en active
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| JP6305331B2 (en) | 2018-04-04 |
| KR101987926B1 (en) | 2019-06-11 |
| KR20150003712A (en) | 2015-01-09 |
| TW201346350A (en) | 2013-11-16 |
| WO2013161492A1 (en) | 2013-10-31 |
| CN103930806A (en) | 2014-07-16 |
| JPWO2013161492A1 (en) | 2015-12-24 |
| TWI634352B (en) | 2018-09-01 |
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