KR101474351B1 - Near infra red cut filter, and solid state imaging device and camera module comprising the same - Google Patents

Abstract

An object of the present invention is to obtain a near-infrared cut filter having a wide viewing angle, excellent near-infrared cut function, low hygroscopicity, and free from foreign matter or warping.

(Solution) A near infrared ray cut filter characterized in that the transmittance satisfies the following (A) to (D):

(A) The average value of the transmittance in the wavelength range of 430 to 580 nm is 75% or more.

(B) The average value of the transmittance is 20% or less at a wavelength of 800 to 1000 nm.

(C) Absolute value of the longest wavelength at which the transmittance is 70% in the wavelength region of 800 nm or shorter and the shortest wavelength difference at which the transmittance becomes 30% in the wavelength region of 580 nm or longer wavelength is less than 75 nm.

(D) a wavelength value in which the transmittance when measured in the vertical direction is 50% and the transmittance when measured at an angle of 30 ° with respect to the vertical direction is 50% in a wavelength range of 560 to 800 nm The absolute value of the car is less than 15 nm.

    Near-infrared cut filter, viewing angle, transmittance, visibility correction filter

Description

TECHNICAL FIELD [0001] The present invention relates to a near-infrared cut filter, a solid-state image pickup device and a camera module having the filter,

The present invention relates to a near-infrared cut filter. More specifically, the present invention relates to a near-infrared ray cut filter having a sufficient viewing angle, and which can be suitably used as a visual sensitivity correction filter for solid-state image pickup devices such as CCD and CMOS, and a solid-state image pickup device and a camera module .

2. Description of the Related Art In recent years, a television equipped with a plasma display panel (PDP) has become commercially available and widely used in general households. This PDP is a display that operates using plasma discharge, but it is known that near infrared rays (wavelength: 800 to 1000 nm) are generated at the time of plasma discharge.

On the other hand, in the home, near infrared rays are often used for remote control of home appliances such as televisions, stereos or air conditioners, and furthermore, information exchange of personal computers, and near infrared rays generated in the PDP cause malfunction of these devices It is always pointed out that there is a high possibility.

Therefore, a majority of commercially available PDPs are provided with a filter function for cutting off near-infrared rays generated by themselves on the front plate thereof.

CCD or CMOS image sensors, which are solid-state image pickup devices for color images, are used for video cameras, digital still cameras, cellular phones with camera functions, and the like. However, these solid-state image pickup devices have a silicon photodiode It is necessary to perform visibility correction, and a near-infrared ray cut filter is often used.

As such a near-infrared ray cut filter, those produced by various methods have been used conventionally. For example, a near-infrared ray is reflected by depositing a metal such as silver on the surface of a transparent substrate such as glass, and a near infrared ray-absorbing dye is added to a transparent resin such as acrylic resin or polycarbonate resin.

However, a near-infrared cut filter obtained by depositing a metal on a glass substrate has a problem in that it is costly to manufacture, and a glass piece of the substrate is mixed as a foreign matter at the time of cutting. Further, when an inorganic material is used as the base material, there is a limit in coping with the recent trend toward thinning and miniaturization of the solid-state imaging device.

Japanese Patent Application Laid-Open No. 6-200113 (Patent Document 1) discloses a near infrared ray cut filter in which a transparent resin is used as a base material and a near infrared absorbing dye is contained in the transparent resin.

However, the near-infrared cut filter described in Patent Document 1 has a case where the near infrared ray absorbing ability is not necessarily sufficient.

The applicant of the present invention has proposed a near infrared ray cut filter having a norbornene resin substrate and a near infrared ray reflective film in Japanese Patent Application Laid-Open No. 2005-338395 (Patent Document 2).

The near-infrared cut filter described in Patent Document 2 has a near-infrared cut function, moisture absorption resistance, and impact resistance, but a sufficient viewing angle value can not be obtained.

[Patent Document 1] JP-A-6-200113

[Patent Document 2] JP-A-2005-338395

It is an object of the present invention to obtain a near-infrared ray cut filter which can be suitably used for a solid-state image pickup device having a wide viewing angle, excellent near infrared ray cutting function, low hygroscopicity, . It is another object of the present invention to provide a solid-state imaging device and a camera module which are thin and excellent in impact resistance by having the near-infrared ray cut filter.

The near-infrared cut filter according to the present invention is characterized in that the transmittance satisfies the following (A) to (D).

(A) the average value of the transmittance in the wavelength range of 430 to 580 nm when measured in the vertical direction of the near-infrared cut filter is 75% or more,

(B) an average value of the transmittance measured in the vertical direction of the near-infrared cut filter is 20% or less at a wavelength of 800 to 1000 nm,

(C) In a wavelength region of 800 nm or shorter, the longest wavelength Xa where the transmittance measured in the vertical direction of the near-infrared cut filter is 70% and the longest wavelength Xa in the vertical direction of the near- And the shortest wavelength Xb at which the transmittance of 30% is measured, is less than 75 nm,

(D) a wavelength value (Ya) at which the transmittance is 50% when measured in the vertical direction of the near-infrared cut filter in a wavelength range of 560 to 800 nm and at a 30 ° angle with respect to the vertical direction of the near- And the absolute value of the difference in the wavelength value (Yb) at which the transmittance becomes 50% in one case is less than 15 nm.

The near-infrared cut filter of the present invention has an absorption maximum at a wavelength of 600 to 800 nm and a wavelength (Aa) at which the transmittance is 70% or less at the absorption maximum or lower in the wavelength range of 430 to 800 nm, It is preferable to have a transparent resin substrate and a near infrared ray reflective film containing an absorbent having an absolute value of a difference between the wavelength of 580 nm or longer and the shortest wavelength (Ab) having a transmittance of 30% of less than 75 nm.

In the near infrared ray cut filter of the present invention, it is preferable that the transparent resin substrate satisfies the following (E) and (F).

(E) has an absorption maximum at a wavelength of 600 to 800 nm,

(F) In the wavelength range of 430 to 800 nm, in the wavelength range of 580 nm or more and the longest wavelength (Za) at which the transmittance measured in the vertical direction of the substrate is 70% And the shortest wavelength Zb at which the transmittance of 30% is measured in the vertical direction is less than 75 nm.

In the near infrared ray cut filter of the present invention, it is preferable that the transparent resin substrate is a substrate made of norbornene resin, and the absorbent is 0.01 to 10.0 parts by weight relative to 100 parts by weight of the transparent resin contained in the transparent resin substrate It is preferable that the near-infrared reflecting film is a dielectric multilayer film.

The near-infrared cut filter according to the present invention can be suitably used for a solid-state imaging device.

The solid-state imaging device and the camera module according to the present invention are characterized by including the near-infrared cut filter.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to manufacture a near infrared ray cut filter having a small viewing angle dependence of absorption (transmission) wavelength and a small viewing angle by using a transparent resin substrate containing an absorbent having an absorption maximum at a specific wavelength and a near- have.

According to the present invention, the solid-state image pickup device and the camera module can be made thinner and smaller by providing the near-infrared cut filter.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

[Near infrared ray cut filter]

The near-infrared cut filter of the present invention is characterized in that its transmittance satisfies the following (A) to (D).

(A) It is preferable that the average value of the transmittance measured in the vertical direction of the near-infrared cut filter is in the range of 430 to 580 nm, preferably 75% or more, preferably 78% or more, more preferably 80% or more Do. In the present invention, by using a transparent resin having a high total light transmittance at a thickness of 0.1 mm and an absorbent having no absorption in the wavelength range, a near infrared ray cut filter having a high transmittance at such a wavelength of 430 to 580 nm is obtained .

When the near-infrared cut filter is used as a filter for visual sensitivity correction in a lens unit such as a solid-state image pickup device or a camera module, an average value of the transmittance at a wavelength of 430 to 580 nm is preferably in the above range and is preferably constant.

The average value of the transmittance is preferably high. When the average value of the transmittance is high, the intensity of the light passing through the filter is sufficiently secured, and the filter can be suitably used for the above purposes.

On the other hand, if the average value of the transmittance is low, the intensity of light passing through the filter can not be sufficiently secured, and there is a possibility that it can not be suitably used for the above purposes.

(B) The average value of the transmittance measured in the vertical direction of the near-infrared cut filter is 20% or less, preferably 15% or less, more preferably 10% or less, in the wavelength range of 800 to 1000 nm desirable. In the present invention, a near infrared ray cut filter having a sufficiently low transmittance at such a wavelength of 800 to 1000 nm can be obtained by having a predetermined near infrared ray reflective film having a high near infrared ray reflectivity on a transparent resin substrate.

Since the near-infrared cut filter of the present invention selectively reduces the wavelength of near infrared rays (800 nm or more), it is preferable that the average value of the transmittance is low. When the average value of the transmittance is low, the near-infrared cut filter can sufficiently cut near infrared rays.

On the other hand, if the average value of the transmittance in the wavelength range of 800 to 1000 nm is high, the filter can not sufficiently cut the near infrared rays, and if the filter is used for the PDP, malfunction of the electronic devices in the vicinity of the PDP can not be prevented in the home There is a concern.

(C) In a wavelength region of 800 nm or shorter, the longest wavelength Xa where the transmittance measured in the vertical direction of the near-infrared cut filter is 70% and the longest wavelength Xa in the vertical direction of the near- (Xa-Xb |) of the difference from the shortest wavelength (Xb) at which the transmittance is 30% when measured at a wavelength of 550 nm is less than 75 nm, preferably less than 72 nm, more preferably less than 70 nm desirable. In the present invention, by using the following specific absorbent for transparent resin, it is possible to obtain a near infrared ray cut filter in which the absolute value of the wavelength difference having a predetermined transmittance falls within the above-mentioned predetermined range.

When the absolute value of the difference between (Xa) and (Xb) of the near-infrared cut filter is within the above range, the transmittance rapidly changes between the wavelengths Xa and Xb near the wavelength range of near infrared rays. Furthermore, the absolute value of the difference between (Ya) and (Yb) below becomes small, and the near-infrared ray cut filter having a small angle of incidence dependence of the absorption wavelength and a wide viewing angle can be obtained.

(D) A wavelength value (Ya) in which the transmittance of the near-infrared cut filter measured in the vertical direction is 50% in a wavelength range of 560 to 800 nm, preferably 580 to 800 nm, (Ya-Yb |) of the difference in the wavelength value (Yb) at which the transmittance becomes 50% when measured at an angle of 30 ° with respect to the wavelength of the laser beam is less than 15 nm, preferably less than 13 nm, more preferably less than 10 nm . In the present invention, by using the following specific absorbent for transparent resin, it is possible to obtain a near infrared ray cut filter in which the absolute value of the wavelength difference having a predetermined transmittance falls within the above-mentioned predetermined range.

Thus, when the absolute value of the difference between (Ya) and (Yb) in the wavelength range of 560 to 800 nm is within the above range, when the filter is used for a PDP or the like, even if viewed from the oblique direction, It is possible to obtain a near-infrared ray cut filter having a brightness and a hue equivalent to those of the case where the incident angle dependency of the absorption wavelength is small and the viewing angle is large.

On the other hand, if a near-infrared cut filter having an absolute value of the difference between (Ya) and (Yb) of 15 nm or more is used for a PDP or the like, there is a fear that the brightness may remarkably decrease or hue may be reversed, Which may not suitably be used for the above purposes.

Here, the " viewing angle " refers to an index indicating to what degree an image can be normally viewed when a display or the like is viewed from up and down and right and left.

In the present invention, it refers to an index indicating to what degree an image can be normally viewed when the near-infrared ray cut filter is viewed from up and down and right and left.

As a judgment as to whether or not it can be normally viewed, in the present invention, the wavelength value Ya in which the transmittance measured in the vertical direction of the filter is 50% in the wavelength range of 560 to 800 nm, And the absolute value of the difference in the wavelength value Yb at which the transmittance is 50% when measured at an angle of 30 DEG is less than 15 nm.

The thickness of the near-infrared cut filter is not particularly limited as long as the transmittance of the filter satisfies the above requirements (A) to (D), but is 50 to 250 탆, preferably 50 to 200 탆, more preferably 80 to 150 탆 .

When the thickness of the near-infrared cut filter is within the above range, the filter can be made smaller and lighter, and can be suitably used for various applications such as solid-state imaging devices. Particularly, when the lens unit is used in a lens unit such as a camera module, it is preferable because the lens unit can be lowered in height.

The near-infrared cut filter of the present invention has an absorption maximum at a wavelength of 600 to 800 nm and a wavelength (Aa) at which the transmittance is 70% or less at the absorption maximum or lower in the wavelength range of 430 to 800 nm, It is preferable to have a transparent resin substrate containing an absorbent having an absolute value of a difference between the wavelength of 580 nm or longer and the shortest wavelength (Ab) having a transmittance of 30% of less than 75 nm and a near infrared ray reflective film.

&Quot; Transparent resin substrate &

The transparent resin substrate used in the present invention is a transparent resin substrate having a transmittance of 70% at a wavelength range of 600 to 800 nm and at a wavelength of 430 to 800 nm, , And the absorber having an absolute value of the difference between the longest wavelength (Aa) in the wavelength range of 580 nm or more and the shortest wavelength (Ab) having a transmittance of 30% is less than 75 nm.

It is preferable that the transmittance of the transparent resin substrate satisfies the following (E) and (F).

(E) the absorption maximum has a wavelength of 600 to 800 nm.

When the absorption maximum wavelength of the substrate is in this range, the substrate can selectively and efficiently cut the near infrared rays.

(F) In the wavelength range of 430 to 800 nm, in the wavelength range of 580 nm or more and the longest wavelength (Za) at which the transmittance measured in the vertical direction of the substrate is 70% (| Za-Zb |) of the difference from the shortest wavelength Zb at which the transmittance measured in the vertical direction of 30% is less than 75 nm, preferably less than 50 nm, more preferably less than 30 nm .

When the absolute value of the difference between the absorption maximum wavelength of the transparent resin substrate and (Za) and (Zb) is within the above range, when light is incident on the substrate, the wavelength between the wavelengths Za and Zb in the near- The transmittance is rapidly changed.

When such a substrate is used in a near-infrared cut filter, the absolute value of the difference between (Ya) and (Yb) of the filter becomes small, and the dependence of the incident wavelength on the incident angle is small , A near-infrared cut filter having a wide viewing angle can be obtained.

In addition, when the near-infrared cut filter using such a substrate is used for a lens unit such as a camera module, it is preferable because the lens unit can be reduced in thickness.

The thickness of the transparent resin substrate is not limited as long as the substrate satisfies the above conditions (E) and (F), but is preferably 250 to 50 占 퐉, preferably 200 to 50 占 퐉, more preferably 150 to 80 占 퐉 desirable.

When the thickness of the transparent resin substrate is within the above range, the near-infrared cut filter using the substrate can be downsized and lightweight, and can be suitably used for various applications such as solid-state imaging devices. Particularly, when the lens unit is used in a lens unit such as a camera module, it is preferable because the lens unit can be downsized.

<Transparent resin>

The transparent resin used in the present invention is not particularly limited as long as it does not impair the effect of the present invention. For example, it is preferable that the transparent resin has thermal stability and moldability to a film, A resin having a glass transition temperature (Tg) of 110 to 380 deg. C, preferably 110 to 370 deg. C, and more preferably 120 to 360 deg. C can be used in order to obtain a film capable of forming a dielectric multilayer film by vapor deposition. Also, when the glass transition temperature of the transparent resin is 120 deg. C or higher, preferably 130 deg. C or higher, more preferably 140 deg. C or higher, a film capable of vapor-depositing the dielectric multilayer film at a higher temperature can be obtained.

It is also possible to use a resin having a total light transmittance of 75 to 94%, preferably 78 to 93%, more preferably 80 to 92% at a thickness of 0.1 mm. If the total light transmittance is in this range, the base film obtained from the transparent resin exhibits good transparency as an optical film.

Examples of such transparent resins include cyclic olefin resins such as norbornene resins, polyarylate resins (PAR), polysulfone resins (PSF), polyether sulfone resins (PES), polyparaphenylene resins (PPP) , Polyarylene ether phosphine oxide resin (PEPO), polyimide resin (PPI), polyetherimide resin (PEI), polyamideimide resin (PAI), (modified) acrylic resin, polycarbonate (PC) Naphthalate (PEN), and organic-inorganic nanohybrid materials. Of the transparent resins, norbornene resins having high transparency are preferable.

&Lt; Norbornene resin &gt;

As the transparent resin to be used in the present invention, a resin obtained by polymerizing a monomer composition containing at least one norbornene-based compound and, if necessary, further hydrogenating it is preferable.

&Quot; Monomer composition &quot;

Examples of the norbornene-based compound used as the monomer composition include a norbornene-based compound represented by the following formula (1).

Wherein x represents 0 or an integer of 1 to 3, y represents 0 or 1,

R ¹ to R ⁴ each independently represent a group selected from the following (i) to (v), or (vi) or (vii).

(I) a hydrogen atom,

(Ii) a halogen atom,

(Iii) a polar group,

(Iv) a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms having a connecting group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom,

(V) a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms,

(Ⅵ) R ¹ and R ² and or R ³ and R ⁴ are each represents an alkylidene group formed by combining each other, R ¹ ~R ⁴ does not participate in the art bond, independently of one another, the (ⅰ) ~ ( v), &lt; / RTI &gt;

(Iii) R ¹ and R ² , and R ³ and R ⁴ represent a monocyclic or polycyclic fused or heterocyclic ring formed by bonding to each other, and R ¹ to R ⁴ not involved in the bond are, independently of each other, (I) to (v).

Examples of the halogen atom (ii) include a fluorine atom, a chlorine atom and a bromine atom.

The (iii) polar group includes, for example, a hydroxyl group; An alkoxy group having 1 to 10 carbon atoms such as methoxy group and ethoxy group; A carbonyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; An amino group; Acyl; Sulfo group; A carboxyl group and the like.

Examples of the linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom include a carbonyl group (-CO-), an oxycarbonyl group (-O (CO) -), a carbonyloxy group (-COO-) -SO ₂ -), ether bond (-O-), thioether bond (-S-), an imino group (-NH-), amide bond (-NHCO -, - CONH-), and siloxane bond (-OSi ( R) -) (wherein R is an alkyl group such as methyl or ethyl), or a linking group containing a plurality of these groups. Among them, a carbonyloxy group (* -COO-) and a siloxane bond (-OSi (R) -) are preferable from the viewpoints of excellent adhesiveness and adhesiveness to the near-infrared reflection film layer and from the viewpoint of dispersibility or solubility of the absorbent desirable. And * is bonded to the ring of formula (1).

The hydrocarbon group is preferably a hydrocarbon group of 1 to 15 carbon atoms, and examples thereof include alkyl groups such as methyl group, ethyl group and propyl group; A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; An alkenyl group such as a vinyl group, an allyl group and a propenyl group, and the like. Among these groups, a methyl group and an ethyl group are preferable from the viewpoint of heat stability.

R ¹ and R ² or R ³ and R ⁴ may be united to form a divalent organic group or R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a monocyclic structure or A polycyclic structure may be formed.

x represents 0 or an integer of 1 to 3, and y represents 0 or 1. Most preferably, x = 0 and y = 1. Use of a cyclic olefin compound having x = 0 and y = 1 is preferable because a polymer having a high glass transition temperature and excellent mechanical strength can be obtained.

 Specific examples of the norbornene monomer represented by the formula (1) include, for example, the following compounds, but are not limited to these examples.

· Bicyclo [2.2.1] hept-2-ene (norbornene)

· 5-Methyl-bicyclo [2.2.1] hept-2-ene

· 5-Ethyl-bicyclo [2.2.1] hept-2-ene

· 5-Propylbicyclo [2.2.1] hept-2-ene

· 5-Butylbicyclo [2.2.1] hept-2-ene

· 5-t-Butylbicyclo [2.2.1] hept-2-ene

· 5-Isobutylbicyclo [2.2.1] hept-2-ene

· 5-Pentylbicyclo [2.2.1] hept-2-ene

· 5-hexylbicyclo [2.2.1] hept-2-ene

· 5-heptylbicyclo [2.2.1] hept-2-ene

· 5-Octylbicyclo [2.2.1] hept-2-ene

· 5-Decylbicyclo [2.2.1] hept-2-ene

· 5-Dodecylbicyclo [2.2.1] hept-2-ene

· 5-Cyclohexyl-bicyclo [2.2.1] hept-2-ene

· 5-Phenyl-bicyclo [2.2.1] hept-2-ene

· 5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene

· 5-Methoxycarbonyl-bicyclo [2.2.1] hept-2-ene

· 5-Phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene

· 5-Phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene

· 5-Phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene

· 5-vinyl-bicyclo [2.2.1] hept-2-ene

· 5-Ethylidene-bicyclo [2.2.1] hept-2-ene

· 5-Trimethoxysilyl-bicyclo [2.2.1] hept-2-ene

· 5-Triethoxysilyl-bicyclo [2.2.1] hept-2-ene

· 5,5-Dimethyl-bicyclo [2.2.1] hept-2-ene

· 5,6-Dimethyl-bicyclo [2.2.1] hept-2-ene

· 5-Fluoro-bicyclo [2.2.1] hept-2-ene

· 5-Chloro-bicyclo [2.2.1] hept-2-ene

Bromo-bicyclo [2.2.1] hept-2-ene

· 5,6-Difluoro-bicyclo [2.2.1] hept-2-ene

· 5,6-Dichloro-bicyclo [2.2.1] hept-2-ene

· 5,6-dibromo-bicyclo [2.2.1] hept-2-ene

· 5-Hydroxy-bicyclo [2.2.1] hept-2-ene

· 5-Hydroxyethyl-bicyclo [2.2.1] hept-2-ene

· 5-Cyano-bicyclo [2.2.1] hept-2-ene

· 5-Amino-bicyclo [2.2.1] hept-2-ene

· Tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· Tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene

Methyl 7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Ethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

Cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

Phenyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7- (4-biphenyl) -tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8-Dimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8,9-Trimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

Methyl-tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene

- 8-Phenyl-tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene

· 7-Fluoro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-Bromo-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7,8-Dichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7,8,9-Trichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Dichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-Hydroxy-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-Amino-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene

· Pentacyclo [7.4.0.1 ^2,5 .1 ^8,11 .0 ^7,12 ] pentadec-3-ene

· 8-Methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Ethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Cyclohexyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene

· 8-Methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

- 8-Phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene

· 8-Phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene

8-Methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene

8-Methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-Methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene

· 8-vinyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Ethylidene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

- 8,8-Dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

- 8,9-Dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Chloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Bromo-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8,8-Dichloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

- 8,9-Dichloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8,8,9,9-tetrachloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-Methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene

· 8-Cyano-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Amino-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

These norbornene-based compounds may be used singly or in combination of two or more.

The kind and amount of the norbornene-based compound used in the present invention are appropriately selected according to the properties required for the obtained resin.

Among them, when a compound having a structure containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom in the molecule (hereinafter referred to as a "polar structure") is used, And has an advantage of being excellent in adhesiveness and adhesion to other materials. Particularly, in Formula 1, R ¹ and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and any one of R ² and R ⁴ is a group having a polar structure And the other is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable since the absorption (wettability) of the resin is low. Further, the norbornene-based compound in which the group having a polar structure is a group represented by the following general formula (2) can be preferably used since it is easy to balance the heat resistance and the absorption (wet) performance of the resulting resin.

- (CH ₂ ) _z COOR ... (2)

(In the formula (2), R represents a substituted or unsubstituted hydrocarbon group of 1 to 15 carbon atoms, and z represents 0 or an integer of 1 to 10.)

In the above general formula (2), the lower the value of z, the higher the glass transition temperature of the obtained hydrogenated product is, and the better the heat resistance, so z is preferably 0 or an integer of 1 to 3, Monomers are preferred because they are easy to synthesize. In addition, the R in the general formula (2) tends to decrease in the absorption (wettability) of the hydrogenated product of the obtained polymer as the number of carbon atoms increases. However, since the glass transition temperature tends to decrease, , A hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.

In the above formula (1), an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is preferably bonded to the carbon atom bonded with the group represented by the general formula (2) from the viewpoint of balance between heat resistance and absorption (wettability). In the above formula (1), a compound wherein x is 0 and y is 0 or 1 has high reactivity and can obtain a polymer at a high yield, and also can obtain a polymer hydrogenation product with high heat resistance, It is suitably used in terms of easy accessibility.

In order to obtain the norbornene resin to be used in the present invention, the monomers copolymerizable with the norbornene-based compound may be added to the monomer composition and polymerized within the range not impairing the effect of the present invention.

As these copolymerizable monomers, for example, cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and cyclododecene, and cyclic olefins such as 1,4-cyclooctadiene, dicyclopentadiene and cyclododecatriene Non-conjugated cyclic polyenes.

These copolymerizable monomers may be used singly or in combination of two or more kinds.

&Quot; Polymerization process &

The polymerization method of the monomer composition containing the norbornene-based compound is not particularly limited as long as the polymerization of the monomer composition is possible, but the polymerization can be carried out by, for example, ring-opening polymerization or addition polymerization.

&Quot; Hydrogenation reaction &quot;

The polymer obtained by the ring-opening polymerization reaction has an olefinic unsaturated bond in its molecule. Also in the addition polymerization reaction, the polymer sometimes has an olefinic unsaturated bond in its molecule. As such, when olefinic unsaturated bonds are present in the polymer molecules, such olefinic unsaturated bonds sometimes cause deterioration such as coloration or gelation with the lapse of time, and therefore, hydrogen which converts the olefinic unsaturated bonds into saturated bonds It is preferable to carry out an addition reaction.

The hydrogenation reaction can be carried out in a conventional manner, that is, a known hydrogenation catalyst is added to a solution of a polymer having olefinic unsaturated bonds, hydrogen gas of atmospheric pressure to 300 atm, preferably 3 to 200 atm, Deg.] C, preferably 20 to 180 [deg.] C.

The hydrogenation rate of the hydrogenated polymer, 500MHz, ¹ is a value measured by H-NMR usually not less than 50%, preferably at least 70%, more preferably at least 90%, particularly preferably at least 98%, and most preferably Is more than 99%. The higher the hydrogenation rate, the better the stability against heat and light, and it is preferable to use it as a molded article because stable characteristics over a long period of time can be obtained.

&Lt; Polyimide resin &

As the transparent resin usable in the present invention, a polyimide resin can be mentioned. The polyimide resin that can be used in the present invention is not particularly limited and may be any polymer having an imide bond in the repeating unit. The polyimide resin can be synthesized by a generally known method. For example, Can be synthesized by the method illustrated in Japanese Patent Application Laid-Open No. 2008-163107.

Commercially available products of the transparent resin usable in the present invention include the following commercially available products. Examples of commercially available products of cyclic olefin resins such as norbornene resins include ARTON manufactured by JSR Corporation, ZEONOR manufactured by Nippon Zeon Co., Ltd., Mitsui Kagaku Kogyo K.K., , TOPAS manufactured by Polyplastics Co., Ltd., and the like. Commercially available products of the polyethersulfone resin include SUMIKAEXCEL PES manufactured by Sumitomo Chemical Co., Ltd., Sumilite manufactured by Sumitomo Bakelite Co., Ltd., and the like. And Neoprim L manufactured by Mitsubishi Chemical Corporation as a commercially available polyimide resin. As a commercially available product of polycarbonate resin, PURE ACE manufactured by Teijin Co., Ltd. and the like can be given. As a commercially available product of the organic-inorganic nanohybrid material, SILPLUS manufactured by Shinnitetsu Kagaku Kogyo Co., Ltd. and the like can be mentioned.

<Absorbent>

The transparent resin used in the present invention has an absorption maximum at a wavelength of 600 to 800 nm and a wavelength Aa at which the transmittance is 70% at a wavelength of 430 to 800 nm, At least one absorbent having an absolute value of the difference (| Aa-Ab |) with respect to the shortest wavelength (Ab) having a transmittance of 30% is less than 75 nm, preferably less than 65 nm, in a wavelength region of a wavelength of 580 nm or more . As the absorbent, for example, a dye or a pigment or a metal complex system compound which absorbs near-infrared rays can be used.

It is preferable to use a transparent resin, particularly a norbornene resin, as the substrate when preparing a substrate containing an absorbent. This is for the reason that the dispersibility of the absorbent into the norbornene resin is excellent and the molding processability of the substrate containing the absorbent is excellent.

In addition, in the conventional near-infrared cut filter, since the absorbent has a steep slope of the transmittance curve, when the near-infrared cut filter is manufactured by mixing the absorbent in the near infrared ray region with a substrate such as glass or the like, Is not used in the near-infrared cut filter because it can not withstand the molding temperature of glass. As a result, a near-infrared ray cut filter capable of achieving both a high transmittance of visible light and a small incident angle dependency can not be obtained as in the present invention.

The absorbent used in the present invention is a solution in which when the absorbent having an absorption maximum at 600 to 800 nm is dissolved in a good solvent and the spectral transmittance of the absorption maximum measured at an optical path length of 1 cm is 30% Are preferred.

Depending on the application such as the front plate for a PDP, it may be required that the total light transmittance measured under the above conditions is 50% or more, preferably 65% or more, in a so-called visible light range of 400 to 700 nm .

Since the transparent resin substrate containing such an absorbent has the feature (F), the near infrared ray cut filter of the present invention has the characteristics of (A), (C) and (D) in particular. Therefore, it is possible to obtain a near infrared ray cut filter having a small incident angle dependency and a wide viewing angle.

In addition, when a near-infrared reflective film described later is formed on a transparent resin substrate by vapor deposition or the like, the performance such as narrowing the viewing angle of the near-infrared cut filter may deteriorate. In the present invention, The deterioration of the performance of the near-infrared cut filter caused by forming the reflective film can be prevented. By using such an absorbent, it is possible to obtain a near-infrared ray cut filter having a stable absorption wavelength region without depending on the incident angle of the incident light irrespective of the near-infrared ray reflection film.

As such an absorbent, metal complex system compounds, dyes and pigments which act as a dye absorbing near-infrared rays can be used, and phthalocyanine compounds, naphthalocyanine compounds, dithiol metal complex compounds and the like can be mentioned. Specifically, for example, Lumogen IR765, Lumogen IR788 (manufactured by BASF), ABS643, ABS654, ABS667, ABS670T, IRA693N, IRA735 (manufactured by Exciton), SDA3598, SDA6075, SDA8030, SDA8303, SDA8470, SDA3039, SDA3040, SDA3922 , SDA7257 (manufactured by HWSANDS), TAP-15 and IR-706 (manufactured by YAMADA Kakuko Co., Ltd.).

As the absorbent of the present application, it is preferable to use a cyanine dye containing only C, H, O and N without containing a metal because Aa-Ab is particularly small. Examples of such an absorbent include ABS643, ABS654, ABS667, ABS670T and the like.

These absorbents may be used alone, or two or more of them may be used in combination.

In the present invention, the above-mentioned absorbent is appropriately selected according to desired properties, but it is usually 0.01 to 10.0 parts by weight, preferably 0.01 to 8.0 parts by weight, more preferably 0.01 To 5.0 parts by weight.

When the amount of the absorbent to be used is within the above range, the near-infrared cut filter having a small incident angle dependence of the absorption wavelength, a wide viewing angle, a near-infrared cut function, and excellent transmittance and intensity in the range of 430 to 580 nm can be obtained.

If the amount of the absorbent used is larger than the above range, the near-infrared cut filter in which the characteristics of the absorbent are more strongly exhibited may be obtained. However, the transmittance in the range of 430 to 580 nm may be lower than a desired value. The near-infrared cut filter having a high transmittance in the range of 430 to 580 nm may be obtained if the amount of the absorbent used is less than the above range. However, And it is difficult to obtain a transparent resin substrate or a near-infrared ray cut filter having a small angle of incidence of absorption wavelength and a wide viewing angle.

<Other components>

In the present invention, in addition to the transparent resin, an additive such as an antioxidant or an ultraviolet absorber may be added to the extent that the effect of the present invention is not impaired.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t- butyl-5,5'-dimethyldiphenylmethane , And tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like. When a transparent resin substrate is produced by the solution casting method described later, the leveling agent and the defoaming agent can be added to facilitate the production of the resin substrate.

These additives may be mixed together with a transparent resin or the like when the transparent resin substrate used in the present invention is produced, or may be added when the transparent resin is produced. The addition amount is appropriately selected according to the desired characteristics, but it is preferably 0.01 to 5.0 parts by weight, and preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the transparent resin.

&Lt; Method of producing transparent resin substrate containing absorbent &gt;

The transparent resin substrate containing the absorbent used in the present invention can be obtained by, for example, a method of melt-molding a pellet obtained by melt-kneading a transparent resin and an absorbent, a method of dissolving a liquid resin composition containing a transparent resin, , Or a method of casting (casting) the liquid resin composition described above.

(A) melt molding

The transparent resin substrate used in the present invention can be produced by melt-molding a resin composition containing a transparent resin and an absorbent. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding, and the like.

 (B) Casting

The transparent resin substrate used in the present invention may be produced by casting a liquid resin composition containing a transparent resin, an absorbent, and a solvent on a suitable substrate to remove the solvent. For example, a transparent resin substrate can be obtained by applying the aforementioned liquid resin composition onto a substrate such as a steel belt, a steel drum, or a polyester film, drying the solvent, and then peeling the coating film from the substrate. Further, by coating the above liquid composition on an optical component made of glass, quartz or transparent plastic and drying the solvent, a transparent resin substrate can be formed on the original optical component.

The amount of the residual solvent in the transparent resin substrate obtained by the above method is preferably as small as possible and is usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. When the amount of the residual solvent exceeds 3% by weight, the resin substrate may be deformed or its characteristics may change with time, and the desired function may not be exhibited.

«Near infrared ray reflective film»

The near-infrared reflecting film used in the present invention is a film having an ability to reflect near infrared rays.

Examples of the near-infrared reflective film include an aluminum vapor deposition film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and containing a small amount of tin oxide are dispersed, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated Can be used.

Since the near-infrared cut filter of the present invention has such a near-infrared reflecting film, it has the characteristic of (B) in particular. Therefore, it is possible to obtain a filter capable of sufficiently cutting near infrared rays.

In the present invention, the near-infrared reflection film may be formed on one surface of a transparent resin substrate or on both surfaces thereof. It is possible to obtain a near infrared ray cut filter which is excellent in manufacturing cost and manufacturability when formed on one side and has high strength when it is formed on both sides and which is less prone to warping.

Among these near-infrared reflective films, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated can be suitably used.

As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of usually 1.7 to 2.5 is selected.

Examples of these materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide and indium oxide as main components and a small amount of titanium oxide, tin oxide, And the like.

As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of usually 1.2 to 1.6 is selected.

These materials include, for example, silica, alumina, lanthanum fluoride, magnesium fluoride, aluminum sodium hexafluoride, and the like.

The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, by a CVD method, a sputtering method, A dielectric multilayer film in which a material layer and a low refractive index material layer are alternately laminated is formed and adhered to each other with an adhesive on a transparent resin substrate or directly formed on the transparent resin substrate by a CVD method, a sputtering method, Refractive-index material layer and a low-refractive-index material layer are alternately laminated on the dielectric multilayer film.

The thickness of each layer of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ, where λ (nm) is an infrared wavelength to be blocked. When the thickness is out of the above range, the product (nxd) of the refractive index (n) and the film thickness (d) largely differs from the optical film thickness calculated by? / 4, It tends to become impossible to control the blocking and transmission of the wavelength.

It is also preferable that the number of layers in the dielectric multilayer film is 5 to 50, preferably 10 to 40.

In the case where the substrate is warped when the dielectric multilayer film is deposited, a dielectric multi-layer film is deposited on both surfaces of the substrate and the surface of the substrate on which the dielectric multilayer film is deposited is irradiated with radiation such as ultraviolet rays . Further, in the case of irradiating the radiation, the irradiation may be performed while the dielectric multilayer film is being deposited, or may be separately irradiated after the deposition.

<Use of near-infrared cut filter>

The near-infrared cut filter obtained in the present invention has a wide viewing angle and excellent near-infrared cut function. Accordingly, the present invention is useful for correction of visual sensitivity for a solid-state image pickup device such as CCD or CMOS of a camera module. In particular, the present invention relates to a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, a car camera, a portable information terminal, a personal computer, a video game, It is useful for players, toy robots, toys and the like. It is also useful as a hot-wire cut filter or the like mounted on a glass such as an automobile or a building.

Here, the case where the near-infrared cut filter obtained in the present invention is used in a camera module will be described in detail.

1 shows a schematic view of a camera module.

Fig. 1 (a) is a schematic view of a conventional camera module structure, and Fig. 1 (b) is a view showing one structure of a camera module that can be taken when the near-infrared cut filter 6 'obtained in the present invention is used .

1 (b), the near-infrared cut filter 6 'obtained in the present invention is used in the upper portion of the lens 5. However, the near-infrared cut filter 6' It may be used between the lens 5 and the sensor 7 as well.

In the conventional camera module, light has to be incident almost perpendicularly to the near-infrared cut filter 6. Therefore, the filter 6 needs to be disposed between the lens 5 and the sensor 7.

Here, the sensor 7 is highly sensitive, and there is a fear that it will not operate correctly just by touching about 5 mu of dust or dust. Therefore, the filter 6 used in the upper portion of the sensor 7 is not dust or dust And it was necessary to not include the foreign object. In addition, in the characteristic of the sensor 7, it is necessary to form a predetermined gap between the filter 6 and the sensor 7, which is a factor that hinders the lowering of the camera module.

In contrast, in the near-infrared cut filter 6 'obtained by the present invention, the absolute value of the difference between (Ya) and (Yb) is less than 15 nm. That is, since there is no large difference in the transmission wavelength of the light incident from the vertical direction of the filter 6 'and the light incident at the angle of 30 from the vertical direction of the filter 6' (the incident angle dependency of the absorption , The filter 6 'does not need to be disposed between the lens 5 and the sensor 7, and may be disposed at the top of the lens.

For this reason, when the near-infrared cut filter 6 'obtained in the present invention is used in a camera module, handling of the camera module is facilitated, and the filter 6' It is possible to reduce the camera module in size.

(Example)

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples at all. "Parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

First, the method of measuring each property value and the method of evaluating properties will be described.

(1) Molecular weight:

Using a gel permeation chromatography (GPC) apparatus (150C type) manufactured by WATERS equipped with an H type column manufactured by Toyo Seisakusho Co., Ltd., o-dichlorobenzene solvent was used as a standard polystyrene- Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured.

(2) Glass transition temperature (Tg):

(DSC6200) manufactured by Seiko Instruments Inc., and the temperature was measured at a rate of temperature rise of 20 占 폚 and a nitrogen flow rate.

(3) Saturated absorption rate:

According to ASTM D570, the test piece was immersed in water at 23 DEG C for one week, and the absorptivity was measured from the weight change of the test piece.

(4) Spectral transmittance:

Was measured using a spectrophotometer (U-4100) manufactured by Hitachi Seisakusho Co., Ltd.

Here, the transmittance measured in the vertical direction of the near-infrared cut filter measured light transmitted perpendicularly to the filter as shown in Fig.

The transmittance of the near infrared ray cut filter measured at an angle of 30 degrees with respect to the vertical direction was measured as the light transmitted through the filter at an angle of 30 degrees with respect to the vertical direction of the filter as shown in Fig.

The transmittance is measured using the spectrophotometer under the condition that light is incident perpendicularly to the substrate and the filter, except when measuring (Yb). (Yb) is measured using the spectrophotometer under the condition that light is incident at an angle of 30 degrees with respect to the vertical direction of the filter.

[Synthesis Example 1]

(100 parts) of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene (hereinafter also referred to as "DNM" 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring opening polymerization reaction) were placed in a nitrogen-purged reaction vessel, and the solution was heated to 80 占 폚. Subsequently, 0.2 part of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and 0.9 part of methanol-modified toluene solution of tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel, Was heated and stirred at 80 占 폚 for 3 hours to carry out a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was placed in an autoclave and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to this ring-opening polymer solution to obtain a hydrogen gas pressure of 100 kg / Deg.] C for 3 hours to conduct a hydrogenation reaction.

After the obtained reaction solution (hydrogenation polymer solution) was cooled, hydrogen gas was purged. The reaction solution was poured into a large amount of methanol to separate and recover a solid product, which was then dried to obtain a hydrogenated polymer (hereinafter also referred to as &quot; resin A &quot;). The resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 占 폚.

[Synthesis Example 2]

Cyclohexane dehydrated with 6 ppm of water in a 1 liter stainless steel autoclave thoroughly dried and replaced with nitrogen; 420.4 g, p-xylene; 180.2 g, 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene; 48.75 mmol (10.43 g), bicyclo [2.2.1] hept-2-ene; 1,425 mmol (134.1 g) were charged, and gaseous ethylene was introduced so that the autoclave internal pressure became 0.1 MPa.

The autoclave was heated to 75 占 폚 to obtain palladium 2-ethylhexanoate (as Pd atom) as a catalyst component; 0.003 milligram atoms and tricyclohexylphosphine; 0.0015 millimoles of toluene; The total amount of the solution in 10 ml of the reaction solution at 25 캜 for 1 hour, triphenylcarbenium pentafluorophenylborate; And 0.00315 mmol were added in this order to initiate polymerization.

5-trimethoxytoxysilyl-bicyclo [2.2.1] hept-2-ene after 90 minutes of polymerization initiation; (2.41 g), then 7.5 millimoles (1.61 g), 3.75 millimoles (0.80 g), and 3.75 millimoles per 30 minutes.

After the polymerization reaction was carried out at 75 캜 for 4 hours, tributylamine; Was added to terminate the polymerization to obtain a solution of the addition polymer B having a solid content of 19.9% by weight. A part of the solution of the addition polymer B was put into isopropanol, solidified and further dried to obtain an addition polymer B (hereinafter also referred to as &quot; resin B &quot;).

As a result of 270 MHz-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) of this polymer B, the proportion of the structural units derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept- (Mw) of 185,000, a glass transition temperature (Tg) of 360 占 폚, and a saturation absorption rate of 0.35%. The weight average molecular weight

[Synthesis Example 3]

In a 500-mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with a side tube, a Dean-Stark and a cooling tube, 10.0 parts by weight of 4,4'-diaminodiphenyl ether (0.05 mole) and 85 parts by weight of N-methyl-2-pyrrolidone as a solvent were dissolved and then 11.2 parts by weight (0.05 mole) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was dissolved at room temperature The mixture was added in portions in a solid state over 1 hour, and the mixture was stirred at room temperature for 2 hours.

Then, 30.0 parts by weight of xylene was added as an azeotropic dehydrating solvent, and the mixture was heated to 180 DEG C and reacted for 3 hours. Then, dianthracene was refluxed to separate water from the azeotropic mixture. After 3 hours, it was confirmed that the water had been removed by distillation. After the temperature was raised to 190 DEG C over 1 hour, xylene was removed by distillation to recover 29.0 parts by weight, followed by cooling in air until the internal temperature reached 60 DEG C To obtain 105.4 parts by weight of a polyimide N-methyl-2-pyrrolidone solution (hereinafter referred to as polyimide solution C).

[Example 1]

To 100 parts by weight of the resin A obtained in Synthesis Example 1, 0.12 parts by weight of an absorbent "Lumogen IR765 (absorption maximum; 765 nm, | Aa-Ab | = 62 nm)" manufactured by BASF Co., Ltd. was added, dissolved in toluene, To obtain a solution having a solid content of 30%. Subsequently, this solution was cast on a smooth glass plate, dried at 60 DEG C for 8 hours, at 100 DEG C for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 100 DEG C for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side length of 60 mm.

The spectral transmittance curve of this substrate was measured to determine the absorption maximum wavelength and (Za) and (Zb).

The results are shown in Table 1.

The maximum absorption wavelength of this substrate was 759 nm. In addition, in the wavelength range of 430 to 800 nm, the longest wavelength (Za) at which the transmittance is 70% or less at the absorption maximum or less and the shortest wavelength (Zb) at which the transmittance becomes 30% (| Za-Zb |) was 65 nm.

Subsequently, a multilayer evaporated film (silica (SiO _2: film thickness 120 to 190 nm) layer and titania (TiO _2: film thickness 70 to 120 nm) layer) alternately laminated on one surface of this substrate for reflecting near infrared rays at a deposition temperature of 150 ° C. , A lamination number of 40) was formed to obtain a near infrared ray cut filter having a thickness of 0.105 mm. The spectral transmittance curves of the near-infrared cut filter were measured to obtain (Xa), (Xb), (Ya) and (Yb). The results are shown in Table 1.

The average transmittance at a wavelength of 430 to 580 nm was 86%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

The absolute value of the difference between the longest wavelength Xa having a transmittance of 70% and the shortest wavelength Xb having a transmittance of 30% in a wavelength region of 580 nm or more in a wavelength region of 800 nm or less in wavelength | Xa-Xb |) was 60 nm.

Further, it is preferable that a wavelength value (Ya) in which the transmittance measured in the vertical direction of the filter is 50% and a transmittance in the case where the transmittance measured at an angle of 30 ° with respect to the vertical direction of the filter is 50 The absolute value (| Ya-Yb |) of the difference in the wavelength value (Yb) as% is 5 nm.

[Example 2]

A substrate having a thickness of 0.1 mm and a side length of 60 mm was obtained in the same manner as in Example 1 except that the absorbent was changed to 0.04 parts by weight of ABS 670T (manufactured by Exciton, absorption maximum: 670 nm, | Aa-Ab | = 34 nm).

The spectral transmittance curve of this substrate was measured.

The absorption maximum wavelength of this substrate was 668 nm. The absolute value of the difference between (Za) and (Zb) was 38 nm. The results are shown in Table 1.

Further, a near infrared ray cut filter having a thickness of 0.105 mm was produced in the same manner as in Example 1. The spectral transmittance of this near-infrared cut filter was measured in the same manner as in Example 1. [

The average transmittance at a wavelength of 430 to 580 nm was 90%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 31 nm.

The absolute value of the difference between (Ya) and (Yb) was 3 nm. The results are shown in Table 1.

[Example 3]

A substrate having a thickness of 0.1 mm and a side length of 60 mm was obtained in the same manner as in Example 1 except that Resin B obtained in Synthesis Example 2 was used instead of Resin A and cyclohexane was used instead of toluene.

The spectral transmittance curve of this substrate was measured.

The maximum absorption wavelength of this substrate was 759 nm. The absolute value of the difference between (Za) and (Zb) was 65 nm. The results are shown in Table 1.

Further, a near infrared ray cut filter having a thickness of 0.105 mm was produced in the same manner as in Example 1. The spectral transmittance of the near-infrared cut filter was measured in the same manner as in Example 1 to obtain (Xa), (Xb), (Ya) and (Yb).

The average transmittance at a wavelength of 430 to 580 nm was 86%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 60 nm.

The absolute value of the difference between (Ya) and (Yb) was 5 nm. The results are shown in Table 1.

[Example 4]

0.04 parts by weight of ABS 670T (manufactured by Exciton Corporation; absorption maximum: 670 nm, | Aa-Ab | = 34 nm) was added to 100 parts by weight of a norbornene resin "ATON G" manufactured by JSR Corporation, To obtain a solution having a solid content of 20%. Subsequently, this solution was cast on a smooth glass plate, dried at 20 ° C for 8 hours, and then peeled off from the oil pan. The peeled resin was further dried under reduced pressure at 100 DEG C for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side length of 60 mm.

The spectral transmittance curve of this substrate was measured.

The absorption maximum wavelength of this substrate was 668 nm. The absolute value of the difference between (Za) and (Zb) was 38 nm. The results are shown in Table 1.

Further, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced. The spectral transmittance of the near-infrared cut filter was measured in the same manner as in Example 1 to obtain (Xa), (Xb), (Ya) and (Yb).

The average transmittance at a wavelength of 430 to 580 nm was 90%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 31 nm.

The absolute value of the difference between (Ya) and (Yb) was 4 nm. The results are shown in Table 1.

[Example 5]

0.20 parts by weight of ABS 670T (manufactured by Exciton, absorption maximum: 670 nm, | Aa-Ab | = 34 nm) was added to 100 parts by weight of a norbornene resin "Zeonor 1400R" manufactured by Nippon Zeon Co., And a 7: 3 mixed solution of xylene were added and dissolved to obtain a solution having a solid content of 20%. Subsequently, this solution was cast on a smooth glass plate and dried at 60 ° C for 8 hours and at 80 ° C for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 100 DEG C for 24 hours to obtain a substrate having a thickness of 0.1 mm and a side length of 60 mm.

The spectral transmittance curve of this substrate was measured.

The absorption maximum wavelength of this substrate was 664 nm. The absolute value of the difference between (Za) and (Zb) was 31 nm. The results are shown in Table 1.

Further, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced. The spectral transmittance of the near-infrared cut filter was measured in the same manner as in Example 1 to obtain (Xa), (Xb), (Ya) and (Yb).

The average transmittance at a wavelength of 430 to 580 nm was 90%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 25 nm.

The absolute value of the difference between (Ya) and (Yb) was 4 nm. The results are shown in Table 1.

[Example 6]

0.12 parts by weight of ABS 670T (manufactured by Exciton, absorption maximum: 670 nm, | Aa-Ab | = 34 nm) was added to 100 parts by weight of a norbornene resin "APEL # 6015" manufactured by Mitsui Chemicals, A 99: 1 mixed solution of hexane and methylene chloride was added and dissolved to obtain a solution having a solid content of 20%. Subsequently, this solution was cast on a smooth glass plate, dried at 40 ° C for 4 hours and then at 60 ° C for 4 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 100 DEG C for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side length of 60 mm.

The spectral transmittance curve of this substrate was measured.

The absorption maximum wavelength of this substrate was 666 nm. The absolute value of the difference between (Za) and (Zb) was 32 nm. The results are shown in Table 1.

Further, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced. The spectral transmittance of the near-infrared cut filter was measured in the same manner as in Example 1 to obtain (Xa), (Xb), (Ya) and (Yb).

The average transmittance at a wavelength of 430 to 580 nm was 89%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 24 nm.

The absolute value of the difference between (Ya) and (Yb) was 4 nm. The results are shown in Table 1.

[Example 7]

0.04 parts by weight of ABS 670T (manufactured by Exciton, absorption maximum: 670 nm, | Aa-Ab | = 34 nm) was added to 100 parts by weight of a polycarbonate resin "PUREACE" manufactured by Teijin K.K., To obtain a solution having a solid content of 20%. Next, this solution was cast on a smooth glass plate, dried at 20 ° C for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 100 DEG C for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side length of 60 mm.

The spectral transmittance curve of this substrate was measured.

The maximum absorption wavelength of this substrate was 680 nm. The absolute value of the difference between (Za) and (Zb) was 46 nm. The results are shown in Table 1.

Further, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced. The spectral transmittance of the near-infrared cut filter was measured in the same manner as in Example 1 to obtain (Xa), (Xb), (Ya) and (Yb).

The average transmittance at a wavelength of 430 to 580 nm was 85%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 42 nm.

The absolute value of the difference between (Ya) and (Yb) was 4 nm. The results are shown in Table 1.

[Example 8]

0.02 parts by weight of ABS 670T (manufactured by Exciton, absorption maximum: 670 nm, | Aa-Ab | = 34 nm) was added to 100 parts by weight of polyether sulfone "FS-1300" manufactured by Sumitomo Bakelite Co., Methyl-2-pyrrolidone was added and dissolved to obtain a solution having a solid content of 20%. Subsequently, this solution was cast on a smooth glass plate, dried at 60 DEG C for 4 hours and then at 80 DEG C for 4 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 120 DEG C for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side length of 60 mm.

The spectral transmittance curve of this substrate was measured.

The maximum absorption wavelength of this substrate was 684 nm. The absolute value of the difference between (Za) and (Zb) was 47 nm. The results are shown in Table 1.

Further, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced. The spectral transmittance of the near-infrared cut filter was measured in the same manner as in Example 1 to obtain (Xa), (Xb), (Ya) and (Yb).

The average transmittance at a wavelength of 430 to 580 nm was 85%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 41 nm.

The absolute value of the difference between (Ya) and (Yb) was 5 nm. The results are shown in Table 1.

[Example 9]

0.2 parts by weight of ABS 670T (manufactured by Exciton, absorption maximum: 670 nm, | Aa-Ab | = 34 nm) was added to the polyimide solution C obtained in Synthesis Example 3 to obtain a solution having a solid content of 20%. Subsequently, this solution was cast on a smooth glass plate, dried at 60 DEG C for 4 hours and then at 80 DEG C for 4 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 120 DEG C for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side length of 60 mm.

The spectral transmittance curve of this substrate was measured.

The absorption maximum wavelength of this substrate was 683 nm. The absolute value of the difference between (Za) and (Zb) was 48 nm. The results are shown in Table 1.

Further, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced. The spectral transmittance of the near-infrared cut filter was measured in the same manner as in Example 1 to obtain (Xa), (Xb), (Ya) and (Yb).

The average transmittance at a wavelength of 430 to 580 nm was 85%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 42 nm.

The absolute value of the difference between (Ya) and (Yb) was 5 nm. The results are shown in Table 1.

[Example 10]

0.02 parts by weight of ABS 670T (manufactured by Exciton, absorption maximum: 670 nm, | Aa-Ab | = 34 nm) was added to 100 parts by weight of a norbornene resin "ATON G" manufactured by JSR Corporation, To obtain a solution having a solid content of 20%. Next, this solution was cast on a smooth glass plate, dried at 20 ° C for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 100 DEG C for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side length of 60 mm.

The spectral transmittance curve of this substrate was measured.

The absorption maximum wavelength of this substrate was 668 nm. The absolute value of the difference between (Za) and (Zb) was 31 nm. The results are shown in Table 1.

Further, in the same manner as in Example 1, a near-infrared cut filter having a thickness of 0.105 mm was produced. The spectral transmittance of the near-infrared cut filter was measured in the same manner as in Example 1 to obtain (Xa), (Xb), (Ya) and (Yb).

The average transmittance at a wavelength of 430 to 580 nm was 90%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 23 nm.

The absolute value of the difference between (Ya) and (Yb) was 4 nm. The results are shown in Table 1.

[Comparative Example 1]

A substrate having a thickness of 0.1 mm and a side length of 60 mm was obtained in the same manner as in Example 1 except that a resin solution having a solid content of 30% obtained by dissolving the resin A in toluene was used.

The spectral transmittance curve of this substrate was measured.

Since this substrate contains no absorbent, the absorption maximum wavelength was not observed. The results are shown in Table 1.

Further, a near infrared ray cut filter having a thickness of 0.105 mm was produced in the same manner as in Example 1. The spectral transmittance of this near-infrared cut filter was measured in the same manner as in Example 1. [ The results are shown in Table 1.

The average transmittance at a wavelength of 430 to 580 nm was 91%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 10 nm.

The absolute value of the difference between (Ya) and (Yb) was 25 nm. The results are shown in Table 1.

[Comparative Example 2]

A substrate having a thickness of 0.1 mm and a side length of 60 mm was obtained in the same manner as in Example 1 except that the absorbent was changed to SIR159 (manufactured by Mitsui Chemicals, Inc., absorption maximum 828 nm, | Aa-Ab | = 60 nm).

The spectral transmittance curve of this substrate was measured.

The absorption maximum wavelength of this substrate was 828 nm. The absolute value of the difference between (Za) and (Zb) was 60 nm. The results are shown in Table 1.

Further, a near infrared ray cut filter having a thickness of 0.105 mm was produced in the same manner as in Example 1. The spectral transmittance of this near-infrared cut filter was measured in the same manner as in Example 1. [ The results are shown in Table 1.

The average transmittance at a wavelength of 430 to 580 nm was 85%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 10 nm.

The absolute value of the difference between (Ya) and (Yb) was 25 nm. The results are shown in Table 1.

[Comparative Example 3]

A substrate having a thickness of 0.1 mm and a side length of 60 mm was obtained in the same manner as in Example 1, except that the absorbent was changed to SDB3535 (manufactured by H.W.SANDS, absorption maximum 1048 nm, | Aa-Ab | = 80 nm).

The maximum absorption wavelength of this substrate was 1030 nm. The absolute value of the difference between (Za) and (Zb) was 86 nm. The results are shown in Table 1.

Further, a near infrared ray cut filter having a thickness of 0.105 mm was produced in the same manner as in Example 1. The spectral transmittance of this near-infrared cut filter was measured in the same manner as in Example 1. [

The average transmittance at a wavelength of 430 to 580 nm was 85%, and the average transmittance at a wavelength of 800 to 1000 nm was 1% or less.

And the absolute value of the difference between (Xa) and (Xb) was 10 nm.

The absolute value of the difference between (Ya) and (Yb) was 25 nm. The results are shown in Table 1.

The near-infrared ray cut filter of the present invention is applicable to a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, a car camera, a portable information terminal, a personal computer, a video game, Authentication systems, digital music players, toy robots, toys, and the like.

In addition, it can be suitably used as a heat-ray cut filter to be mounted on a glass such as an automobile or a building.

1 (a) shows a conventional camera module.

Fig. 1 (b) shows an example of a camera module when the near-infrared cut filter 6 'obtained in the present invention is used.

Fig. 2 shows a method of measuring the transmittance in the case of measuring in the vertical direction of the near-infrared cut filter.

3 shows a method of measuring the transmittance when measured at an angle of 30 DEG with respect to the vertical direction of the near-infrared cut filter.

DESCRIPTION OF THE REFERENCE NUMERALS (S)

1: Camera module

2: lens barrel

3: Flexible substrate

4: Hollow package

5: Lens

6: near-infrared cut filter

6 ': The near infrared ray cut filter obtained in the present invention

7: CCD or CMOS image sensor

8: Near infrared ray cut filter

9: Spectrophotometer

Claims (9)

A transparent resin substrate containing an absorbent having an absorption maximum at a wavelength of 600 to 800 nm and a near infrared ray reflective film, Wherein the transmittance satisfies the following (A) to (D): (A) the average value of the transmittance in the case of measurement in the vertical direction of the near-infrared cut filter in the range of 430 to 580 nm is 75% or more, (B) an average value of the transmittance measured in the vertical direction of the near-infrared cut filter is 1% or less at a wavelength of 800 to 1000 nm, (C) In a wavelength region of 800 nm or shorter, the longest wavelength Xa where the transmittance measured in the vertical direction of the near-infrared cut filter is 70% and the longest wavelength Xa in the vertical direction of the near- And the shortest wavelength Xb at which the transmittance of 30% is measured, is less than 75 nm, (D) a wavelength value (Ya) in which the transmittance of the near-infrared cut filter measured in the vertical direction is 50% and a wavelength at a 30 ° angle with respect to the vertical direction of the near-infrared cut filter in a wavelength range of 560 to 800 nm The absolute value of the difference in the wavelength value Yb where the transmittance of 50% is less than 15 nm. The method according to claim 1, Wherein the transparent resin substrate satisfies the following (E) and (F): (E) has an absorption maximum at a wavelength of 600 to 800 nm, (F) In the wavelength range of 430 to 800 nm, in the wavelength range of 580 nm or more and the longest wavelength (Za) at which the transmittance measured in the vertical direction of the substrate is 70% And the shortest wavelength (Zb) at which the transmittance of 30% is measured in the vertical direction is less than 75 nm. 3. The method according to claim 1 or 2, Wherein the transparent resin substrate is a norbornene resin substrate. 3. The method according to claim 1 or 2, Wherein the absorbent is contained in an amount of 0.01 to 10.0 parts by weight based on 100 parts by weight of the transparent resin contained in the transparent resin substrate. 3. The method according to claim 1 or 2, Wherein the near-infrared ray reflection film is a dielectric multilayer film. 3. The method according to claim 1 or 2, Wherein the thickness of the near infrared ray cut filter is 50 to 250 占 퐉. 3. The method according to claim 1 or 2, Wherein the near-infrared cut filter is a solid-state image pickup device. A solid-state imaging device comprising the near-infrared cut filter according to claim 1 or 2. A camera module comprising the near-infrared cut filter according to claim 1 or 2.

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