KR20150003712A

KR20150003712A - Wavelength cut filter

Info

Publication number: KR20150003712A
Application number: KR20147012499A
Authority: KR
Inventors: 요스케 마에다; 마사아키 시미즈
Original assignee: 가부시키가이샤 아데카
Priority date: 2012-04-25
Filing date: 2013-03-27
Publication date: 2015-01-09
Also published as: JP6305331B2; KR101987926B1; TW201346350A; WO2013161492A1; CN103930806A; JPWO2013161492A1; CN103930806B; TWI634352B

Abstract

The present invention provides a wavelength cut filter that has a low incident angle dependency and a high heat resistance and is capable of being thinned. More specifically, the present invention provides a wavelength cut filter having a coating layer (B) containing a dye on one surface of a glass substrate And an infrared reflecting film (C) laminated on the other surface of the transparent substrate (A). Preferably, the coating layer (B) containing the dye contains 0.01 to 10.0 parts by mass of a cyanine compound as a dye, particularly an acidic dye, per 100 parts by mass of the resin solid content.

Description

WAVELENGTH CUT FILTER [0002]

The present invention relates to a wavelength cut filter formed by laminating a coating layer containing a dye, a glass substrate and an infrared reflective film.

The sensitivity of solid-state image pickup devices (CCD, C-MOS, etc.) used in digital still cameras, video cameras, cameras for mobile phones and the like extends from the ultraviolet region to the infrared region of the wavelength of light. On the other hand, human visibility is only the visible region of the wavelength of light. For this reason, the sensitivity of the solid-state image pickup device is corrected so as to approach the human visibility by providing an infrared cut filter between the image pickup lens and the solid-state image pickup device (for example, see Patent Documents 1 to 3).

BACKGROUND ART Conventionally, an infrared cut filter is a reflection type filter in which layers containing a substance having no absorption characteristic are combined and laminated in a multilayer structure, or a reflection type filter in which a light absorbent is contained in or bonded to a transparent substrate, Respectively.

Since the characteristics of the reflection type filter change depending on the incident angle of light, there is a problem that the color tone changes in the center and the periphery of the screen. In addition, there is a problem that the reflected light becomes stray light in the optical path, causing low resolution, unevenness of image, unevenness of image, multiphase called ghost, and the like.

On the other hand, the absorptive filter has no characteristic change due to the incident angle of light, but a considerable thickness is required in order to obtain desired properties.

2. Description of the Related Art In recent years, there has been a demand for miniaturization of various devices and devices, and the conventional absorption filter can not meet the demand for miniaturization thereof. Further, in the reflection type filter, it is difficult to attain the characteristic required by the incident angle dependency.

U.S. Patent Application Publication No. 2005/253048 Japanese Laid-Open Patent Publication No. 2011-118255 Japanese Laid-Open Patent Publication No. 2012-008532

Therefore, an object of the present invention is to provide a wavelength cut filter which is low in dependence on incident angle and high in heat resistance, and can be thinned.

As a result of intensive studies, the present inventors have found that an infrared reflective film (C) is formed on the other surface of a glass substrate (A) while having a coating layer (B) containing a dye on one surface of the glass substrate The wavelength cut filter characterized in that the wavelength-cut filter is characterized in that it has low dependency on the incident angle.

The present invention is characterized in that an infrared reflecting film (C) is laminated on the other surface of a glass substrate (A) with a coating layer (B) containing a dye on one surface of the glass substrate And to provide a wavelength cut filter.

The present invention also provides a solid-state imaging device including the wavelength cut filter.

The present invention also provides a camera module including the wavelength cut filter.

The wavelength cut filter of the present invention is excellent in that it has low dependency on the incident angle. Further, the wavelength cut filter of the present invention is suitable for a solid-state image pickup device and a camera module.

1 is a cross-sectional view schematically showing the layer structure of a wavelength cut filter of the present invention.
2 is a cross-sectional view showing one configuration of a camera module of the present invention.
3 is a cross-sectional view showing another embodiment of the configuration of the camera module of the present invention.

Hereinafter, the wavelength cut filter of the present invention will be described based on preferred embodiments.

1, the wavelength cut filter of the present invention has a coating layer (B) containing a dye on one surface of a glass substrate (A) and an infrared reflecting film (C), and the side having the coating layer (B) is defined as the incident side of the light. Hereinafter, each layer will be described in order.

&Lt; Glass Substrate (A) >

As the glass substrate (A) used in the wavelength cut filter of the present invention, a transparent glass material can be appropriately selected and used in the visible region, and examples thereof include soda lime glass, white plate glass, borosilicate glass, tempered glass, quartz glass, Based glass can be used. Of these, soda-lime glass is preferable because it is inexpensive and easy to obtain, and white plate glass, borosilicate glass and tempered glass are preferable since they are easy to obtain and have high hardness and excellent workability.

When the glass substrate (A) is pretreated with a silane coupling agent or the like and then a coating liquid is applied to form a coating layer (B) containing the dye described later, the coating layer (B) containing the dye after drying the coating liquid The adhesion to the glass substrate is enhanced.

Examples of the silane coupling agent include epoxy functional alkoxysilanes such as? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, , Amino functional alkoxysilanes such as N -? (Aminoethyl) -? - aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane and N-phenyl-? -Aminopropyltrimethoxysilane, Mercapto functional alkoxysilanes such as mercaptopropyltrimethoxysilane and mercaptopropyltrimethoxysilane.

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

In the present invention, since the substrate is a glass plate, it can be directly coated on the substrate, dried, and then cut, so that the structure and the process are simplified. In addition, since the substrate is a glass plate, heat resistance (260 ° C reflow resistance) is higher than in the case of plastic.

&Lt; Coating layer (B) >

The coating layer (B) containing the dye used in the wavelength cut filter of the present invention can be prepared by dissolving or dispersing the dye, resin and other components as required in a suitable solvent in an appropriate solvent to prepare a coating solution, A). &Lt; / RTI >

Examples of the application method include spin coating, dip coating, spray coating, bead coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, die coating, An extrusion coating method, and the like.

The dye is not particularly limited and a known dye can be used. Examples thereof include oxazole and oxadiazole compounds, coumarin compounds, quinolinol compounds, phthalocyanine compounds, naphtholactam compounds, fluorene and derivatives thereof, anthracene and And a derivative thereof, a xanthene compound (pyrogenic compound, rhodamine compound, fluororesin compound), stilbene compound, cyanine compound, azo compound, azomethine compound, indigo compound, thioindigo compound, oxolin compound, squarylium compound, indole compound A thiopyrylium compound, a triarylmethane compound, a diphenylmethane compound, a tetrahydrocholine compound, an indophenol compound, an anthraquinone compound, an anthraquinone compound, Naphthoquinone compounds, thiazine compounds, spiropyran compounds, benzilidene compounds, indane compounds, azulene compounds, perylene compounds, An azine compound, an acridine compound, a thiazine compound, an oxazine compound, a polyacetylene compound, a phenylenevinylene compound, a phenyleneethynylene compound, a heterocyclic compound of a 5-membered ring and a 6-membered ring, And a plurality of these may be mixed and used.

Among these dyes, acid dyes such as a xanthene compound, a phthalocyanine compound, a cyanine compound, an azo compound, an oxolone compound, and an anthraquinone compound are preferable from the viewpoint of solubility.

Among the acid dyes, cyanine compounds are more preferable in terms of ease of synthesis and molecular design.

Examples of the cyanine compound include those represented by the following general formula (1).

(Wherein A represents a group selected from (a) to (m) of the following group I, and A 'represents a group selected from (a') to (m '

Q represents a connecting group which may form a methine chain having 1 to 9 carbon atoms and may contain a ring structure in the chain, and the hydrogen atom in the methine chain may be a hydroxyl group, a halogen atom, a cyano group, -NRR ', an aryl group, An aryl group, an arylalkyl group, and an alkyl group may be substituted with a hydroxyl group, a halogen atom, a cyano group, or -NRR ', and -O-, -S-, -CO- , -COO-, -OCO-, -SO ₂ - and may be interrupted by, -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH-,

R and R 'represent an aryl group, an arylalkyl group or an alkyl group,

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

(Wherein ring C and ring C 'represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,

R ¹ and R ^{1 'each} independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, an amide group, a ferrocenyl group, an aryl group having 6 to 30 carbon atoms, An alkyl group or an alkyl group having 1 to 8 carbon atoms,

Wherein R ¹ and R ^{1 'carbon} atoms of 6 to 30 aryl group, an alkyl group of 7 to 30 carbon atoms, an arylalkyl group and a carbon atom number of 1 to 8 are a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H in, -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO -, -N = CH- or -CH = CH-,

R ² to R ⁹ and R ^{2 '} to R ^9' represent the same groups or a hydrogen atom as R ¹ and R ^{1 '}

X and X 'represent an oxygen atom, a sulfur atom, a selenium atom, -CR ⁵¹ R ⁵² -, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, -NH- or -NY ² -

R ⁵¹ and R ⁵² represent the same groups or a hydrogen atom as R ¹ and R ^{1 '}

Y, Y 'and Y ² is a hydrogen atom, or hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an alkyl group of an amino group, an amide group, a ferrocenyl group, -SO ₃ H, or from 1 to 20 carbon atoms which may be substituted with a nitro group atoms, carbon atoms An aryl group of 6 to 30 in embroidery number or an arylalkyl group of 7 to 30 in carbon number,

The methylene group in the alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 30 carbon atoms and the arylalkyl group having 7 to 30 carbon atoms in Y, Y 'and Y ² is -O-, -S-, -CO-, COO-, -OCO-, -SO ₂ -, and may be -NH-, interrupted by -CONH-, -NHCO-, -N = CH- or -CH = CH-,

and r 'and r' are 0 or one or more of (a) to (e), (g) to (j), (l), (m) , (l ') and (m').)

Examples of the halogen atom represented by R ^{51 to} R ⁵² in R ¹ to R ⁹ and R ^{1 '} to R ^9' and X and X 'in the above general formula (1) include fluorine, chlorine, bromine and iodine ,

Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, Cyclohexylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, Dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- Di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5- 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like.

Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl,

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert- Hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl and tert-octyl.

The aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms and the alkyl group having 1 to 8 carbon atoms may be substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N = CH- Or -CH = CH-, and the number and position of substitution and termination thereof are arbitrary.

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

Examples of the group in which the alkyl group having 1 to 8 carbon atoms is interrupted by -O- include methyloxy, ethyloxy, isopropyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, heptyloxy, octyl 2-ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl, 3-methoxybutyl, 3-methoxybutyl, And alkoxyalkyl groups such as methoxybutyl, etc.,

Examples of the group interrupted by -O- while the alkyl group having 1 to 8 carbon atoms is substituted by a halogen atom include chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, difluoromethyloxy, Trifluoromethyloxy, nonafluorobutyloxy, and the like.

Examples of the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X and X 'in the above general formula (1) include cyclopropane-1,1-diyl, cyclobutane- 1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl, cyclohexane-1,1-diyl, etc. .

In the general formula (1), examples of the halogen atom represented by Y, Y 'and Y ² , the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms and the arylalkyl group having 7 to 30 carbon atoms include, R ¹ and the like and the hydrogen atoms in these substituents may be optionally substituted with a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an amino group, an amide group, a ferrocenyl group, -SO ₃ H or a nitro group do.

The methylene group in these alkyl groups, aryl groups and arylalkyl groups in Y, Y 'and Y ² is preferably -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, CONH-, -NHCO-, -N = CH- or -CH = CH-. For example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert- amyl, hexyl, Heptyl, heptyl, isoheptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, iso-nonyl, decyl, dodecyl An alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; 4-isopropylphenyl, 4-isopropylphenyl, 4-iso-butylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, 4-methylphenyl, 4-methylphenyl, butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, , Aryl groups such as 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl and cyclohexylphenyl; Arylalkyl groups such as benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl and cinnamyl are interrupted by an ether bond or thioether bond, Methoxyethyl, 3-methoxybutyl, 2-phenoxyethyl, 3-methoxypropyl, 3-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, Phenoxypropyl, 2-methylthioethyl, 2-phenylthioethyl and the like.

(Q-1) to (Q-11) which constitute a methine chain having 1 to 9 carbon atoms represented by Q in the above-mentioned general formula (1) and may contain a ring structure in the chain A group to be displayed is preferable because of easy production. The number of carbon atoms in the methine chain having 1 to 9 carbon atoms is preferably a number of carbon atoms of the group substituting the ring structure contained in the methine chain or the methine chain (for example, the linking groups (Q-1) to (Q-11) And Z ' or R < ¹⁴ > to R < ¹⁹ > include a carbon atom).

(Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z 'each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, -NRR', an aryl group, , -NRR ', an aryl group, an arylalkyl group and an alkyl group may be substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR', -O-, -S-, -CO-, -COO-, -OCO -, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH-,

R and R 'represent an aryl group, an arylalkyl group or an alkyl group.

Examples of the halogen atom, aryl group, arylalkyl or alkyl group represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z 'include those exemplified as R ¹ , Examples of the aryl group, arylalkyl group or alkyl group represented by R 'include those exemplified in the description of R ¹ and the like.

Examples of the q-valent anion represented by pAn ^q ^- in the general formula (1) include methanesulfonate anion, dodecylsulfonate anion, benzenesulfonate anion, toluenesulfonate anion, trifluoromethanesulfonate anion, naphthalenesulfonate anion, Amino-4-methyl-5-chlorobenzenesulfonic acid anion, 2-amino-5-nitrobenzenesulfonic acid anion, JP-A-10-235999, JP-A-10-337959, Japanese Patent Application Laid-Open No. 11-102088, Japanese Patent Application Laid-Open No. 2000-108510, Japanese Patent Application Laid-Open No. 2000-168223, Japanese Laid-Open Patent Application No. 2001-209969, Japanese Laid-Open Patent Application No. 2001-322354, Japanese Laid-open Patent Application No. 2006-248180, Such as the sulfonic acid anion described in Japanese Patent Application Laid-Open Nos. 2006-297907, 8-253705, 2004-503379, 2005-336150, and 2006/28006, Besides the sulfonic acid anion, A fluoride ion, a bromide ion, a bromide ion, an iodide ion, a fluoride ion, a chlorate ion, a thiocyanate ion, a perchlorate ion, a hexafluorophosphate ion, a hexafluoroantimonate ion, a tetrafluoroborate ion, (4,6-di-t-butylphenyl) phosphonic acid ion, tetrakis (pentafluorophenyl) boric acid ion, A quencher anion having a function of de-exciting (quenching) an active molecule in an excited state or an anion group such as a carboxyl group, a phosphonic acid group or a sulfonic acid group in a cyclopentadienyl ring And metallocene compound anions such as ferrocene and ruthenocene.

Specific examples of the cyanine compound used in the present invention include the following compounds No. 1 to 102. In the following examples, the term " cyanine cation "

The preparation method of the cyanine compound is not particularly limited and can be obtained by a method using a well-known general reaction. For example, as in the route described in Japanese Patent Application Laid-Open No. 2010-209191, And a method of synthesizing them by the reaction of an imine derivative.

The dye used in the present invention preferably has a maximum absorption wavelength (? Max) of the coating film of 650 to 1200 nm, more preferably 650 to 900 nm. If the maximum absorption wavelength (max) of the coating film is 1200 nm or more of the present invention, the effect of the present invention is not exerted, and if it is less than 650 nm, visible light is absorbed.

In the coating solution for forming the coating layer (B) containing the dye, the content of the dye is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass in total of the single or plural kinds. When the content of the dye is less than 0.01% by mass, sufficient characteristics may not be obtained. When the content is more than 50% by mass, precipitation of the dye may occur in the coating layer.

In the coating layer (B) containing the dye, the content of the dye is preferably 0.01 to 10.0 parts by mass, more preferably 0.25 to 5.0 parts by mass, per 100 parts by mass of the resin solid content, to be.

Examples of the resin include natural polymer materials such as gelatin, casein, starch, cellulose derivatives and arginic acid, and natural polymers such as polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, Styrene-butadiene copolymer, polystyrene, polycarbonate, and polyamide.

Examples of other components to be blended as required include benzotriazole-based, triazine-based, and benzoate-based ultraviolet absorbers; Phenolic, phosphorus, and sulfur antioxidants; An antistatic agent comprising a cationic surfactant, an anionic surfactant, a nonionic surfactant, and a positive surfactant; Flame retardants such as halogenated compounds, phosphoric acid ester compounds, phosphoric acid amide compounds, melamine compounds, fluororesins or metal oxides, (poly) phosphoric acid melamine and (poly) phosphoric acid phosphate; Hydrocarbon-based, fatty-acid-based, aliphatic-alcohol-based, aliphatic ester-based, aliphatic amide-based or metal soap-based lubricants; Fumed silica, fumed silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar, vermiculite, Silicate-based inorganic additives such as attapulgite, talc, mica, minnesotite, pyrophyllite and silica; Fillers such as glass fibers and calcium carbonate; A crystallizing agent such as a nucleating agent and a crystal accelerator, a silane coupling agent, and a rubber elasticity imparting agent such as a flexible polymer. The amount of these other components to be used is 50% by mass or less in total in the coating liquid for forming the coating layer (B) containing the dye.

The solvent is not particularly limited, and various known solvents can be suitably used. Examples thereof include alcohols such as isopropanol; Ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and butyl diglycol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol, esters such as ethyl acetate, butyl acetate and methoxyethyl acetate; Acrylic acid esters such as ethyl acrylate and butyl acrylate; fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol; Hydrocarbons such as hexane, benzene, toluene and xylene; Chlorinated hydrocarbons such as methylene dichloride, dichloroethane and chloroform, and the like. These organic solvents may be used alone or in combination.

The thickness of the coating layer (B) containing the dye is preferably 1 to 200 mu m because a uniform film can be obtained and it is advantageous to form a thin film. When the thickness is less than 1 mu m, the function can not be sufficiently manifested. When the thickness exceeds 200 mu m, the solvent may remain at the time of coating.

&Lt; Infrared reflective film (C) >

The infrared reflective film (C) used in the cut filter of the present invention has a function of blocking light in a wavelength range of 700 to 1200 nm and is formed by a dielectric multilayer film in which a low refractive index layer and a high refractive index layer are alternately laminated.

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

The material constituting the high refractive index layer may be a material having a refractive index of 1.7 to 2.5. Examples of the material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, Indium oxide, and the like, and those containing a small amount of titanium oxide, tin oxide, or cerium oxide as a main component.

The method of laminating the low refractive index layer and the high refractive index layer is not particularly limited as long as a dielectric multilayer film in which these layers are laminated is formed. For example, a CVD method, a sputtering method, a vacuum deposition method, Layer and a high-refractive-index layer are alternately laminated. It is also possible to form a dielectric multilayer film in advance and bond it to the glass substrate with an adhesive.

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

The thicknesses of the low refractive index layer and the high refractive index layer are usually 1/10 to 1/2 of the wavelength? (Nm) of the light beam to be cut, respectively. The product (nd) of the refractive index (n) and the physical film thickness (d) is significantly different from the optical film thickness expressed by a multiple of? / 4 when the thickness is less than 0.1? There is a possibility that it can not be done.

As the infrared reflective film (C), in addition to the dielectric multilayer film, a film containing a dye having a maximum absorption wavelength of 700 to 1100 nm, a laminate of polymers, a film formed by coating a cholesteric liquid crystal, May be used.

The wavelength cut filter of the present invention preferably satisfies the following (i) to (iii). The upper transmittance was measured with an ultraviolet visible near infrared spectrophotometer V-570 manufactured by Nihon Bunko Co., Ltd.

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

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

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

In the wavelength cut filter, when the average value of the transmittances in the wavelength range of 430 to 580 nm of (i) is less than 75%, the light in the visible light region is hardly transmitted, If the average value of the transmittance at 1000 nm exceeds 5%, the light in the infrared region is hardly cut, and it may be difficult to correct the sensitivity so as to approach the human visibility.

If the absolute value of the difference between Ya and Yb in (iii) exceeds 30 nm, the dependence of the light on the incident angle increases, and the characteristics of the wavelength-cut filter change due to the incident angle of light. There is a possibility that harmful effects such as the above may occur.

Specific examples of the use of the wavelength cut filter of the present invention include a heat ray cut filter mounted on a glass or the like of a car or a building; For visibility correction for solid-state image pickup devices such as CCD and CMOS in solid-state image pickup apparatuses such as digital still cameras, digital video cameras, surveillance cameras, vehicle-mounted cameras, web cameras, and mobile phone cameras; Automatic exposure meter; And a display device such as a plasma display.

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

The solid-state image pickup device of the present invention is configured in the same manner as a conventionally known solid-state image pickup device except that the wavelength cut filter of the present invention is provided on the front surface of the image pickup device. As shown in Fig. 2, the wavelength-cut filter 1 of the present invention may be fixed to a portion other than the solid-state image pickup element on the light incidence side of the solid-state image pickup device 2, 2).

In the solid-state imaging device of the present invention, an optical low-pass filter, an antireflection filter, a color filter, or the like can be disposed as needed, and there is no particular limitation on the order of lamination.

A description will now be given of a camera module which is one of the solid-state image pickup devices of the present invention. When the wavelength cut filter 1 of the present invention is fixed to a portion other than the solid-state image pickup device on the light incidence side of the solid- Will be described in detail.

2 is a cross-sectional view showing a configuration of a camera module which is one of the solid-state imaging devices of the present invention. The camera module includes a solid-state imaging element 2 formed in a rectangular shape in a plan view and a light-receiving portion 3 of the solid-state imaging element 2 on the semiconductor substrate, (1) formed on an outer surface of the solid-state image sensor (2) except for the light-receiving portion (3), the solid-state image sensor (2) The imaging element 2 and the wavelength cut filter 1 are bonded together with the adhesive 4. The camera module as the solid-state imaging device receives light from the outside through the wavelength cut filter 1 and receives the light by the light-receiving element disposed in the light-receiving portion 3 of the solid-

As the adhesive 4, a UV-curable adhesive such as an acrylic resin or an epoxy resin, or a thermosetting resin can be used. After the adhesive 4 is uniformly applied, 4) are patterned and bonded by thermal curing. When bonding, vacuum pressing may be performed after bonding in a vacuum environment.

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

The solid state image pickup device 2 is disposed on the mounting substrate 8 and the adhesive 4 is applied in advance to the position where the lens holder 7 of the mounting substrate 8 is fixed.

The lens cap 6 protects the lens 5. The lens holder 7 holds the lens 5 and includes a base portion 7a on a box which is mounted on the mounting substrate 8 and covers the solid state image pickup device 2, And a barrel portion 7b of the barrel portion 7b.

Subsequently, the lens holder 7 is placed on the mounting substrate 8 so that the lower end face of the lens holder 7 is in contact with the applied adhesive 4 and the light receiving portion 3 of the solid- The position of the lens holder 7 is adjusted so that the distance of the lens 5 in the holder 7 coincides with the focal length of the lens 5. [

After the position of the lens holder 7 is adjusted, the camera module can be manufactured by irradiating the adhesive 4 with ultraviolet rays and curing the adhesive 4.

The entire mounting substrate 8 on which the lens holder 7 is fixed may be heated to about 85 캜 and the adhesive 4 may be sufficiently cured by thermal curing.

In addition, since the manufacturing method of the camera module includes the step of heating the entire mounting substrate 8 after the step of irradiating ultraviolet rays, the lens holder 7, the lens 5 and the wavelength cut filter 1 both It is necessary to use a material having high heat resistance. Specifically, in addition to the heating for thermosetting of the adhesive 4 as described above, a plurality of solders disposed on the lower surface of the mounting substrate 8 are heated and melted at about 260 캜 and soldered to another substrate, It is preferable to be formed of a material having low resistance.

Example

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

Production Examples 1 to 11 show examples of preparing a coating solution for forming a coating layer (B) containing a dye used in the wavelength cut filter of the present invention, and Comparative Production Examples 2 to 4 are used for comparative wavelength cut filters Examples 1 to 11 show production examples of the wavelength cut filter of the present invention, and Comparative Examples 1 to 4 show comparative wavelength cuts (Comparative Examples 1 to 4) In the evaluation examples 1 to 11, the wavelength cut filter of the present invention manufactured in Examples 1 to 11 was evaluated. In Comparative Evaluation Examples 1 to 4, the wavelength cut of the comparative example prepared in Comparative Examples 1 to 4 The filters were evaluated.

[Production Examples 1 to 11 and Comparative Production Examples 2 to 4] Preparation of Coating Liquid Nos. 1 to 11 and Comparative Coating Liquids No. 2 to 4

The components shown in Table 1 and Table 2 were mixed to obtain Coating Liquid Nos. 1 to 11 and Comparative Coating Liquid Nos. 2 to 4, respectively.

[Examples 1 to 11 and Comparative Examples 1 to 4] Production of wavelength cut filters No. 1 to No. 11 and comparative wavelength cut filters No. 1 to No. 4

On one surface of 100㎛ thickness of the glass substrate (B), and by a vacuum deposition method alternately laminated in a silica (SiO ₂₎ layer and a titanium oxide (TiO ₂₎ layer, before the stories layer 30 and a thickness of about 3㎛ To form an infrared reflective film (C).

The coating liquids No. 1 to No. 11 obtained in Production Examples 1 to 11 were applied on a surface different from the infrared reflective film (C) of the glass substrate (B) provided with the obtained infrared reflective film (C) (Film thickness: 10 mu m), and then dried at 100 DEG C for 10 minutes to form a coating layer to prepare wavelength cut filters No. 1 to No. 11 of the present invention.

The glass substrate on which the infrared reflection film (C) obtained above was formed was used as a comparative wavelength cut filter No. 1.

Further, Comparative Coating Liquid Nos. 2 to 4 were coated (film thickness 10 占 퐉) on one side of a glass substrate (B) having a thickness of 100 占 퐉 by a bar coater # 30 and then dried at 100 占 폚 for 10 minutes Coating layer (A) was formed to prepare comparative wavelength cut filters No. 2 to No. 4.

[Evaluation Examples 1 to 11 and Comparative Evaluation Examples 1 to 4]

The wavelength cut filters No. 1 to No. 4 of the present invention obtained in Examples 1 to 11 and Comparative wavelength cut filters No. 1 to No. 4 obtained in Comparative Examples 1 to 4 were subjected to the following processes: i) , Ii) an average value of the transmittance measured from the vertical direction of the wavelength cut filter at a wavelength of 800 to 1000 nm, and iii) an average value of transmittance measured from the vertical direction of the wavelength cut filter at a wavelength of 560 to 800 nm (Ya) of 80% when measured from the vertical direction of the wavelength cut filter and a transmittance of 80% when measured from an angle of 35 DEG with respect to the vertical direction of the wavelength cut filter, The absolute value of the difference between the value (Yb) The results are shown in [Table 1] and [Table 2]. The transmittance was measured with an ultraviolet visible infrared spectrophotometer V-570 manufactured by Nihon Bunko Co., Ltd.

From the results of the above [Table 1] and [Table 2], the wavelength cut filter of Comparative Example 1 which does not have the coating layer (B) containing a dye has a high incident angle dependency, The wavelength cut filter of ~ 4 has a low transmittance in a wavelength range of 430 to 580 nm or a high transmittance in a wavelength of 800 to 1000 nm, that is, does not transmit light in a visible light region, It is not possible to correct the sensitivity so as to approach the human visual sensitivity.

On the other hand, the wavelength cut filter of the present invention has a high transmittance in a wavelength range of 430 to 580 nm, a low transmittance at a wavelength of 800 to 1000 nm, and a low incident angle dependency.

From the above results, it was found that an infrared reflective film (C) was laminated on the other surface of the glass substrate (A) while having a coating layer (B) containing a dye on one surface of the glass substrate The wavelength cut filter of the present invention has a low incident angle dependency. Therefore, the wavelength cut filter of the present invention is useful for a solid-state imaging device and a camera module.

(A): glass substrate (B): coating layer
(C): Infrared reflective film (vapor deposition film) 1: Wavelength cut filter
2: solid state image pickup device 3:
4: Adhesive 5: Lens
6: Lens cap 7: Lens holder
7a: base portion 7b: lens barrel portion
8:

Claims

Characterized in that an infrared reflecting film (C) is laminated on the other side of the glass substrate (A) while having a coating layer (B) containing a dye on one side of the glass substrate (A).

The method according to claim 1,
Wherein the dye is an acidic dye.

3. The method according to claim 1 or 2,
And the transmittance satisfies the following (i) - (iii).
(i) the average value of the transmittance when measured from the vertical direction of the wavelength cut filter in the wavelength range of 430 to 580 nm is 75% or more.
(ii) The average value of the transmittance when measured from the vertical direction of the wavelength cut filter at a wavelength of 800 to 1000 nm is 5% or less.
(iii) a value (Ya) of the wavelength at which the transmittance is 80% as measured from the vertical direction of the wavelength cut filter in the range of 560 to 800 nm and an angle of 35 degrees with respect to the vertical direction of the wavelength cut filter The absolute value of the difference in the value Yb of the wavelength at which the transmittance becomes 80% when measured is 30 nm or less.

4. The method according to any one of claims 1 to 3,
Characterized in that the coating layer (B) containing the dye contains 0.01 to 10.0 parts by mass of dye relative to 100 parts by mass of resin solid content.

5. The method according to any one of claims 1 to 4,
Wherein the dye is a cyanine compound.

A solid-state imaging device comprising the wavelength cut filter according to any one of claims 1 to 5.

A camera module comprising the wavelength cut filter according to any one of claims 1 to 5.