JP2005338395A - Near ir ray cut-off filter and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near IR cut-off filter which is excellent in a near IR cut-off property, is excellent in hygroscopic resistance and impact resistance as well, and is appropriately usable for a solid-state imaging apparatus, particularly such as a CCD or CMOS, and a solid-state imaging apparatus which is a thin type and small size by including the near IR cut filter. <P>SOLUTION: The near IR cut-off filter having a norbornane-based resin substrate and multilayered dielectric substance films is manufactured. Also, the solid-state imaging apparatus including the near IR cut-off filter is manufactured. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a near-infrared cut filter. Specifically, the present invention relates to a near-infrared cut filter that can sharply cut near-infrared rays, and particularly suitable for use as a visibility correction filter for a solid-state imaging device such as a CCD or CMOS, and a manufacturing method thereof.

  In recent years, televisions equipped with a plasma display panel (PDP) have been commercialized and have come to be widely used in ordinary homes. 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 during plasma discharge.

  On the other hand, in homes, near-infrared rays are often used for remote control of home appliances such as TVs, stereos or air conditioners, and also for personal computer information exchange. It has always been pointed out that there is a high possibility of causing malfunctions.

Therefore, many of commercially available PDPs are provided with a filter function for cutting near infrared rays emitted by the PDP on its entire surface.
In addition, CCDs and CMOS image sensors, which are solid-state image sensors for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, etc., and these solid-state image sensors are sensitive to near-infrared light at the light receiving part. Therefore, it is necessary to perform visibility correction, and a near-infrared cut filter is often used.

  As the near-infrared cut filter, those manufactured by various methods are conventionally used. For example, a metal such as silver deposited on the surface of a transparent substrate such as glass to reflect near infrared rays, or a transparent resin such as acrylic resin or polycarbonate resin to which a near infrared absorbing dye is added is practical. It is provided.

  However, the near-infrared cut filter in which a metal is vapor-deposited on a glass base material has a problem that not only the manufacturing cost is high, but also a glass piece of the base material is mixed as a foreign substance during cutting.

  In addition, as a near-infrared cut filter in which an infrared absorber is dispersed in a transparent substrate, a filter in which a copper compound having near-infrared absorption ability is dispersed in phosphate glass is known. Therefore, there is a problem that polishing is necessary and the manufacturing cost is high. Further, when used as a near-infrared cut filter for a solid-state imaging device, phosphate glass has a relatively high hygroscopic property, and may have an adverse effect on the solid-state imaging device. Furthermore, when an inorganic material is used as a base material, there has been a limit to cope with the recent thinning and downsizing of solid-state imaging devices.

  On the other hand, a near-infrared cut filter using a transparent resin as a substrate and containing a near-infrared absorbing dye in the transparent resin is also known (see, for example, Patent Document 1). However, the near-infrared cut filter using a transparent resin as a base material may not always have sufficient near-infrared absorbing ability as compared with the near-infrared cut filter based on phosphate glass.

As a result of intensive studies in view of such circumstances, the present inventors have found that a film made of a resin obtained by polymerizing a monomer composition containing a norbornene-based compound, a near-infrared reflective film, particularly The filter having a dielectric multilayer film is excellent in moisture absorption resistance, productivity, etc., and in particular, it is found that the filter is a near infrared cut filter excellent in the protection function of a solid-state imaging device such as CCD, CMOS, etc., and the present invention is completed. It came to.
JP-A-6-200113

It is an object of the present invention to obtain a near-infrared cut filter that is excellent in near-infrared cut ability, has low hygroscopicity, is free of foreign matter and warpage, and can be suitably used for solid-state imaging devices such as CCD and CMOS. . It is another object of the present invention to provide a solid-state imaging device that is thin and excellent in impact resistance by including the near infrared cut filter.

  The near-infrared cut filter according to the present invention has a norbornene-based resin substrate and a near-infrared reflective film. The near-infrared reflective film is preferably a dielectric multilayer film. The norbornene-based resin substrate may contain a near infrared absorber. The near-infrared cut filter according to the present invention can be suitably used as a near-infrared cut filter for a solid-state imaging device.

  The solid-state imaging device according to the present invention includes the near infrared cut filter.

  According to the present invention, by using a combination of a norbornene-based resin substrate and a near-infrared reflective film, it is possible to produce a near-infrared cut filter that is easy to cut during production and contains little foreign matter.

  According to the present invention, the solid-state imaging device can be reduced in thickness and size by including the near infrared cut filter.

Hereinafter, the present invention will be specifically described.
[Near-infrared cut filter]
The near-infrared cut filter according to the present invention has a norbornene-based resin substrate and a near-infrared reflective film.

<Norbornene resin>
The norbornene-based resin used in the present invention is a resin obtained by polymerizing a monomer composition containing at least one norbornene-based compound and, if necessary, further hydrogenating.

<Monomer composition>
As a norbornene-type compound used for the said monomer composition, the norbornene-type compound represented by following General formula (1) can be mentioned, for example.

[In the formula (1), R _{1 to} R ₄ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom that may have a linking group containing oxygen, nitrogen, sulfur or silicon, 1 Represents a hydrocarbon group of ˜15 or other monovalent organic group. Alternatively, R ₁ and R ₂ or R ₃ and R ₄ may be bonded to each other to form an alkylidene group, and R ₁ and R ₂ , R ₃ and R _4, or R ₂ and R ₃ are bonded to each other. Thus, a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure) may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X represents 0 or an integer of 1 to 3, and y represents 0 or 1. When x is 0, y is 0. ]
Specific examples of the norbornene-based monomer represented by the general formula (1) include, for example, the compounds shown below, 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-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-phenoxycarboni -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, 5,5-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 5-bromo-bicyclo [2.2.1] hept-2-ene5,6-difluoro-bicyclo [2.2.1] hept-2-ene5,6-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 ] Undec-3-ene.7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene.7-ethyl-tricyclo [4.3. 0.1 ^2,5] dec-3-ene-7-cyclohexyl - tricyclo [4.3.0.1 ^2,5] dec-3-ene-7-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 Methyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7,8,9- trimethyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-8- Methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene · 8-phenyl-tricyclo [4.4.0.1 ^2,5 ] undec-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-tricycl B [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] deca-3-ene-tetracyclo [4.4.0.1 ^2,5. 1 ^7,10 ] dodec-3-ene pentacyclo [7.4.0.1 ^2,5 . 1 ^8,11 . 0 ^7,12] pentadeca-3-ene-hexacyclo [8.4.0.1 ^2,5. 1 ^7,14 . 1 ^9,12 . 0 ^8,13] heptadec-3-en-8-methyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-ethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-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 ] Dodeca-3-
Ene-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodec-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 ] dodec-3-ene-8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-ethylidene - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,8-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-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] dodeca-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 ] dodec-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 compounds may be used alone or in combination of two or more.

The kind and amount of the norbornene-based compound used in the present invention are appropriately selected depending on the properties required for the obtained resin.
Of these, 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 “polar structure”) is used. In addition, it is excellent in adhesiveness and adhesion to other materials, and when used by containing a near infrared absorber, there are advantages such as excellent dispersibility of the near infrared absorber. In particular, in the formula (1), R ₁ and R ₃ are 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 compound having a polar structure and the other being a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable because the water absorption (wet) property of the resin is low. Furthermore, a norbornene compound in which the group having a polar structure is a group represented by the following general formula (2) is easy to balance the heat resistance and water absorption (wet) property of the resulting resin and can be preferably used.

_{- (CH 2) z COOR ...} (2)
(In formula (2), R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents 0 or an integer of 1 to 10)
In the general formula (2), the smaller the value of z, the higher the glass transition temperature of the resulting hydrogenated product and the better the heat resistance, so z is preferably an integer of 0 or 1 to 3, A monomer in which z is 0 is preferable in that its synthesis is easy. Further, R in the general formula (2) tends to decrease the water absorption (wet) property of the hydrogenated polymer obtained as the number of carbon atoms increases, but also tends to decrease the glass transition temperature. From the viewpoint of maintaining heat resistance, 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 general formula (1), when an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is bonded to the carbon atom to which the group represented by the general formula (2) is bonded, heat resistance and water absorption It is preferable in terms of (wet) balance. Further, in the general formula (1), a compound in which x is 0 or 1 and y is 0 has high reactivity, a polymer can be obtained in a high yield, and polymer hydrogen having high heat resistance. It is preferably used because an additive is obtained and it is industrially easily available.

In obtaining the norbornene-based resin used in the present invention, a monomer that can be copolymerized with the norbornene-based compound can be included in the monomer composition and polymerized as long as the effects of the present invention are not impaired.

  Examples of these copolymerizable monomers include cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and cyclododecene, and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatriene. Can be mentioned.

These copolymerizable monomers may be used alone or in combination of two or more.
<Polymerization method>
The method for polymerizing the monomer composition containing the norbornene-based compound is not particularly limited as long as the monomer composition can be polymerized. For example, the polymerization is performed by ring-opening polymerization or addition polymerization. be able to.

(A) Ring-opening polymerization Production of a polymer by ring-opening polymerization can be performed by a known ring-opening polymerization reaction for a norbornene-based compound, and a monomer composition containing the norbornene-based compound is used as a polymerization catalyst and a polymerization reaction. It can manufacture by carrying out ring-opening polymerization using the solvent for use, and a molecular weight regulator as needed.

(A) Polymerization catalyst In the present invention, when the polymerization of the monomer composition is performed by a ring-opening polymerization reaction, the polymerization is performed in the presence of a metathesis catalyst.

This metathesis catalyst is
(A) at least one compound selected from compounds having W, Mo and Re (hereinafter referred to as compound (A));
(B) Deming periodic table group IA elements (for example, Li, Na, K, etc.), group IIA elements (for example, Mg, Ca, etc.), group IIB elements (for example, Zn, Cd, Hg, etc.), group IIIA elements (For example, B, Al, etc.), a compound having a group IVA element (for example, Si, Sn, Pb, etc.), or a group IVB element (for example, Ti, Zr, etc.), The catalyst comprises a combination of at least one compound selected from compounds having at least one bond between this element and hydrogen (hereinafter referred to as compound (B)). Moreover, in order to improve the activity of a catalyst, what added the below-mentioned additive (C) may be used.

Examples of the compound (A) include W, Mo or Re halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, and derivatives thereof. Alternatively, a combination thereof may be mentioned, and W and Mo compounds, particularly their halides, oxyhalides and alkoxyhalides are preferred from the viewpoint of polymerization activity and practicality. Moreover, you may use the mixture of 2 or more types of compounds which produce | generate the said compound by reaction. Furthermore, these compounds may be complexed with a suitable complexing agent such as P (C ₆ H ₅ ) ₅ , C ₅ H ₅ N, and the like.

Specific examples of the compound (A) include WCl ₆ , WCl ₅ , WCl ₄ , WBr ₆ , WF ₆ , WI ₆ , MoCl ₅ , MoCl ₄ , MoCl ₃ , ReCl ₃ , WOCl ₄ , MoOCl ₃ , ReOCl _3. , ReOBr ₃ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , Mo (OC ₂ H ₅ ) ₅ , MoO ₂ (acac) ₂ , W (OCOR) ₅ , W (OC ₂ H ₅ ) ₂ Cl ₃ , W (CO) ₆ , Mo (CO) ₆ , Re ₂ (CO) ₁₀ , ReOBr ₃・ P (C ₆ H ₅ ) ₃ , WCl _{5 · P (C 6 H 5)} 3, WCl 6 · C 5 H 5 N, such as _{W (CO) 5 · P (} C 6 H 5) 3, W (CO) 3 · (CH 3 CN) 3 and the like . Among the above compounds, particularly preferred compounds include MoCl ₅ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , WCl ₆ , W (OC ₂ H ₅ ) ₂ Cl _{3 and the} like.

Specific examples of the compound _{(B), n-C 4 H 5 Li} , n-C 5 H 11 Na, C 5 H 5 Na, CH 3 MgI, C 2 H 5 MgBr, CH 3 MgBr, n- C ₃ H ₇ MgCl, (C ₆ H ₅ ) ₃ Al, t-C ₄ H ₉ MgCl, CH ₂ = CHCH ₂ MgCl, (C ₂ H ₅ ) ₂ Zn, (C ₂ H ₅ ) ₂ Cd, CaZn ( C ₂ H ₅ ) ₄ , (CH ₃ ) ₃ B, (C ₂ H ₅ ) ₃ B, (nC ₄ H ₉ ) ₃ B, (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, LiAl (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₃ Al-O (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ AlCl, C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (iso-C ₄ H ₉ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (iso-C ₄ H ₉ ) ₃ Al, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , (CH ₃ ) ₄ Ga, (CH ₃ ) ₄ Sn, (n−C ₄ H ₉ ) ₄ Sn, (C ₂ H ₅ ) ₃ SiH, (n-C ₆ H ₁₃ ) ₃ Al, (
_{n-C 4 H 17) 3} Al, LiH, NaH, B 2 H 6, NaBH 4, AlH 3, LiAlH 4, etc. BiH ₄ and TiH ₄ and the like. Moreover, the mixture of 2 or more types of compounds which produce | generate these compounds by reaction can also be used. Preferred examples of these include (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH
, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (C ₂ H ₅ ) ₂ AlCN, (C ₃ H ₇ ) ₃ Al, (iso−C ₄ H ₉ ) ₃ Al, (iso−C ₄ H ₉ ) ₂ AlH, (C ₆ H ₁₃ ) ₃ Al, (C ₈ H ₁₇ ) ₃ Al, (C ₆ H ₅ ) ₅ Al, and the like.

As the additive (C) that can be used together with the compound (A) and the compound (B), alcohols, aldehydes, ketones, amines and the like can be suitably used. For example, the following (1) to (1) to (9) can be exemplified.
(1) Non-organometallic compounds of boron such as simple boron, BF ₃ , BCl ₃ , B (OnC ₄ H ₉ ) ₃ , (C ₂ H ₅ O ₃ ) ₂ , BF, B ₂ O ₃ , H ₃ BO ₃ Silicon non-organometallic compounds such as Si (OC ₂ H ₅ ) ₄ ;
(2) alcohols, hydroperoxides and peroxides;
(3) water;
(4) oxygen;
(5) Carbonyl compounds such as aldehydes and ketones and polymers thereof;
(6) cyclic ethers such as ethylene oxide, epichlorohydrin, oxetane;
(7) Amides such as N, N-diethylformamide and N, N-dimethylacetamide, amines such as aniline, morpholine and piperidine, and azo compounds such as azobenzene;
(8) N-nitroso compounds such as N-nitrosodimethylamine and N-nitrosodiphenylamine;
(9) Compounds containing an S-Cl or N-Cl group such as trichloromelamine, N-chlorosuccinimide, phenylsulfenyl chloride and the like.

  The amount of the metathesis catalyst used is such that the molar ratio (compound: total monomer) of the compound (A) and all monomers used for polymerization is usually 1: 500 to 1: 50,000, preferably 1: An amount of 1,000 to 1: 10,000 is desirable.

The ratio of the compound (A) to the compound (B) (compound (A): compound (B)) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio.
The ratio of the compound (A) to the compound (C) (compound (C): compound (A)) is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1 in molar ratio. desirable.

(B) Polymerization solvent As the solvent used in the ring-opening polymerization reaction, the monomer composition or catalyst to be used for polymerization is not dissolved and the catalyst is not deactivated. Although it will not specifically limit if a compound melt | dissolves, For example, alkanes, such as pentane, hexane, heptane, octane, nonane, decane; Cycloalkanes, such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; benzene, Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene; halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chloroform, tetrachloroethylene; halogenated aryl compounds such as chlorobenzene; ethyl acetate, acetic acid n-butyl, Examples thereof include saturated carboxylic acid esters such as iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. These can be used alone or in admixture of two or more. Such a solvent is used as a solvent for dissolving the solvent constituting the molecular weight regulator solution, the norbornene compound, the copolymerizable monomer and / or the metathesis catalyst.

The amount of the solvent used is such that the weight ratio of the solvent to the monomer composition used for polymerization (solvent: monomer composition) is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. Is desirable.
(C) Molecular weight regulator The molecular weight of the resulting ring-opening polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent, but it can also be adjusted by allowing a molecular weight regulator to coexist in the reaction system. be able to.

  Suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene, 4 -Methylstyrene, 2-methylstyrene, 4-ethylstyrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more.

The usage-amount of a molecular weight modifier is 0.005-0.6 mol normally with respect to 1 mol of monomers with which a ring-opening polymerization reaction is provided, Preferably it is 0.01-0.5 mol.
(D) Other polymerization conditions The ring-opening polymer can be obtained by ring-opening polymerization of the norbornene compound alone or the norbornene compound and a copolymerizable monomer. Polybutadiene, polyisoprene. Presence of unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain, such as conjugated diene compounds such as styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene A monomer composition containing a norbornene compound may be subjected to ring-opening polymerization.

(B) Addition polymerization The production of a polymer by addition polymerization can be performed by a known addition polymerization reaction for a norbornene compound, and a monomer composition containing the norbornene compound is polymerized as a polymerization catalyst, if necessary. It can be produced by addition polymerization using a reaction solvent and, if necessary, a molecular weight regulator.

(A) Polymerization catalyst Examples of the polymerization catalyst include single catalysts and multicomponent catalysts such as palladium, nickel, cobalt, titanium and zirconium listed in the following (a-1) to (a-3). The polymerization catalyst used in the present invention is not limited to these.

(A-1) Single catalyst system [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ , [Pd (PhCN) ₄ ] [SbF ₆ ]
[(Η ³ -crotyl) Pd (cycloocta-1,5-diene)] [PF ₆ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [B (3
, 5- (CF ₃ ) ₂ C ₆ F ₃ ) ₄ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [PF ₆ ],
[(Η ³ -allyl) Ni (cycloclota-1,5-diene)] [B (C ₆ F ₅ ) ₄ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [SbF ₆ ],
Toluene · Ni (C ₆ F ₅ ) ₂ , Benzene · Ni (C ₆ F ₅ ) ₂ , Mestinene · Ni (C ₆ F ₅ ) ₂ , Ethylether · Ni (C ₆ F ₅ ) ₂
Etc.

(A-2) Multi-component catalyst system (1)
A combination of a palladium complex having a σ or σ, π bond and an organoaluminum or super strong acid salt.
Di-μ-chloro-bis (6-methoxybicyclo [2.2.1] hept-2-ene-endo-5σ, 2π) Pd, methylalumoxane (abbreviated as MAO), AgSbF6 or AgBF4 Combinations with different compounds,
A combination of [(η ³ -aryl) PdCl] ₂ and AgSbF ₆ or AgBF ₄ ;
A combination of [(cycloocta-1,5-diene) Pd (CH ₃ ) Cl], PPh ₃ and NaB [3,5- (CF ₃ ) ₂ C ₆ H ₃ ] ₄ may be mentioned.

(A-3) Multi-component catalyst system (2)
(I) transition metal compounds selected from nickel compounds, cobalt compounds, titanium compounds or zirconium compounds,
(II) a compound selected from super strong acids, Lewis acids and ionic boron compounds,
(III) A combination comprising three components of an organoaluminum compound.

(I) Examples of transition metal compounds (I-1) Examples of nickel compounds and cobalt compounds:
Compounds selected from nickel or cobalt organic carboxylates, organic phosphites, organic phosphates, organic sulfonates, β-diketone compounds,
For example, nickel 2-ethylhexanoate, nickel naphthenate, cobalt naphthenate, nickel oleate, nickel dodecanoate, cobalt dodecanoate, cobalt neodecanoate, nickel dibutyl phosphite, nickel dibutyl phosphate, nickel dioctyl phosphate, phosphoric acid Examples thereof include nickel salts of dibutyl ester, nickel dodecylbenzenesulfonate, nickel p-toluenesulfonate, nickel bis (acetylacetonate), and bis (ethylacetoacetate) nickel.

A compound obtained by modifying the organic carboxylate of nickel with a super strong acid such as hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid, hexafluoroacetone,
Nickel diene or triene coordination complexes,
For example, dichloro (1,5-cyclooctadiene) nickel, [(η ³ -crotyl) (
1,5-cyclooctadiene) nickel] hexafluorophosphate, and its tetrafluoroborate, tetrakis [3,5-bis (trifluoromethyl)] borate complex, (1,5,9-cyclododecatriene) nickel, bis Nickel complexes such as (norbornadiene) nickel and bis (1,5-cyclooctadiene) nickel,
A complex in which a ligand having an atom such as P, N, or O is coordinated to nickel.

For example, bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dibromide, bis (triphenylphosphine) cobalt dibromide, bis [tri (2-methylphenyl) phosphine] nickel dichloride, bis [tri (4 - methylphenyl) phosphine] nickel dichloride, bis [N- (3-t- butylsalicylidene) phenyl aminate] nickel, Ni [PhC (O) CH] (Ph), Ni (OC ( C 6 H 4) PPh) (H) (PCy ₃ ), Ni [OC (O) (C ₆ H ₄ ) P]
(H) (PPh ₃ ), bis (1,5-cyclooctadiene) nickel and PhC (O) CH
= Reaction product of PPh _{3, [2,6- (i-Pr) 2 C} 6 H 3 N = CHC 6 H 3 (O) (Anth) ] (Ph) (PPh ₃₎ nickel complex such as Ni (here And Anth is 9-anthr
acenyl and Ph are abbreviations for phenyl and Cy for cyclohexyl. ),
Is mentioned.

(I-2) Examples of titanium and zirconium compounds:
[T-BuNSiMe (Me ₄ Cp)] TiCl ₂ , (Me ₄ Cp) (O—iPr ₂ C ₆ H ₃ ) ₂ TiCl, (Me ₄ Cp) TiCl ₃ , (Me ₄ Cp) Ti (OBu) ₃ , [T-BuNS
iMe ₂ Flu] TiMe ₂ , [t-BuNSiMe ₂ Flu] TiCl ₂ , Et (Ind) ₂ ZrCl ₂ , Ph ₂ C (Ind) (Cp) ZrCl ₂ , iPr (Cp) (Flu) ZrCl ₂ , iPr (3 -tert-But-Cp) (Ind ) ZrCl 2, iPr (Cp) (Ind) ZrCl 2, Me 2 Si (Ind) 2 ZrCl 2, Cp 2 ZrCl 2, (Cp is Cyc
lotentadienl and Ind are abbreviations for Indenyl and Flu for Fluorenyl. )
Etc.

(II) Examples of super strong acids, Lewis acids and ionic boron compounds include:
Examples of super strong acids include hexafluoroantimonic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, trifluoroacetic acid, fluorosulfuric acid, trifluoromethanesulfonic acid, tetrafluoroboric acid, tetrakis (pentafluorophenyl) boric acid, tetrakis [3, 5-bis (trifluoromethyl) phenyl] boric acid, p-toluenesulfonic acid, pentafluoropropionic acid, etc.
Examples of Lewis acid compounds include complexes of boron trifluoride with ethers, amines, phenols, etc., aluminum trifluoride ethers, complexes of amines, phenols, tris (pentafluorophenyl) borane, tris [3,5 Boron compounds such as -bis (trifluoromethyl) phenyl] borane, aluminum compounds such as aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum fluoride, tri (pentafluorophenyl) aluminum , Organic halogen compounds exhibiting Lewis acidity such as hexafluoroacetone, hexachloroacetone, chloranil, hexafluoromethyl ethyl ketone, and other Lewis acidity such as titanium tetrachloride and pentafluoroantimony Such as the compounds,
Examples of the ionic boron compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylcarbeniumtetrakis (2,4 , 6-trifluorophenyl) borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-diphenylanilinium tetrakis (pentafluorophenyl) borate and the like.

As an example of the organoaluminum compound (III),
Alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, butylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, diethylaluminum fluoride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc. The alkylaluminum compound and the halogenated alkylaluminum compound, or a mixture of the alkylalumoxane compound and the alkylaluminum compound are preferably used.

These catalyst components are used, for example, in amounts used within the following ranges.
Transition metal compounds such as nickel compounds, palladium compounds, cobalt compounds, titanium compounds, and zirconium compounds are 0.02 to 100 millimole atoms per mole of monomer, and organoaluminum compounds are per mole of transition metal compound. The amount of non-conjugated diene, Lewis acid, and ionic boron compound is 0 to 100 mol with respect to 1 mol atom of the transition metal compound.

(B) Polymerization solvent As the solvent used in the addition polymerization reaction, the monomer composition or catalyst to be subjected to the polymerization is dissolved and the catalyst is not deactivated. Although it will not specifically limit if it melt | dissolves, For example, alicyclic hydrocarbon solvents, such as cyclohexane, cyclopentane, and methylcyclopentane, Aliphatic hydrocarbon solvents, such as hexane, heptane, and octane, toluene, benzene, xylene, mesitylene And an aromatic hydrocarbon solvent such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and other solvents selected from dichlorobenzene. These can be used alone or in admixture of two or more.

(C) Molecular Weight Modifier In the present invention, the molecular weight of the norbornene addition polymer to be produced can be adjusted by adding hydrogen or α-olefin as a molecular weight regulator in the polymerization system. The molecular weight of the norbornene-based addition polymer produced decreases as the molecular weight regulator added increases.

《Hydrogenation reaction》
The polymer obtained by the ring-opening polymerization reaction has an olefinically unsaturated bond in the molecule. Moreover, also in the said addition polymerization reaction, a polymer may have an olefinically unsaturated bond in the molecule | numerator. Thus, if an olefinically unsaturated bond is present in the polymer molecule, the olefinically unsaturated bond may cause deterioration over time such as coloring or gelation. It is preferable to carry out a hydrogenation reaction to convert to.

  In the hydrogenation reaction, a known hydrogenation catalyst is added to an ordinary method, that is, a polymer solution having an olefinically unsaturated bond, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added to the solution. The reaction can be carried out at -200 ° C, preferably 20-180 ° C.

The hydrogenation rate of the hydrogenated polymer is typically 50 MHz, as measured by ¹ H-NMR.
% Or more, preferably 70% or more, more preferably 90% or more, particularly preferably 98% or more, and most preferably 99% or more. The higher the hydrogenation rate, the better the stability to heat and light, and it is preferable because stable characteristics can be obtained over a long period when used as a molded product.

  In addition, when the polymer obtained by the above method has an aromatic group in the molecule, the aromatic group does not cause deterioration such as coloring over time or gelation, but rather, mechanical characteristics and optical characteristics. In some cases, such an aromatic group does not necessarily have to be hydrogenated.

  As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. Homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichloro Examples thereof include tris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts are usually used in a ratio such that the weight ratio of the ring-opening polymer to the hydrogenation catalyst (ring-opening polymer: hydrogenation catalyst) is 1: 1 × 10 ⁻⁶ to 1: 2. The
The norbornene resin used in the present invention preferably has an intrinsic viscosity [η] _inh of 0.2 to
2.0 dl / g, more preferably 0.35 to 1.0 dl / g, particularly preferably 0.4 to 0.85 dl / g, and a number average in terms of polystyrene measured by gel permeation chromatography (GPC). The molecular weight (Mn) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, particularly preferably 15,000 to 250,000, and the weight average molecular weight (Mw) is 10,000 to 2,000,000, more preferably Those of 20,000 to 1,000,000, particularly preferably 30,000 to 500,000 are suitable. When the intrinsic viscosity [η] _inh , the number average molecular weight, and the weight average molecular weight are in the above ranges, the norbornene resin has excellent mechanical strength, and a norbornene resin substrate that is not easily damaged can be obtained.

  The norbornene resin has a glass transition temperature (Tg) of usually 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 150 ° C. or higher. When Tg is within the above range, the adhesion strength of the dielectric multilayer film to the base material is improved, and a norbornene resin substrate having excellent solder reflow resistance is obtained.

  The saturated water absorption of the norbornene resin is 1% by weight or less, preferably 0.1 to 0.8% by weight. When the saturated water absorption exceeds 1% by weight, there may be a problem in durability such that the resin substrate obtained from the resin is subject to water absorption (wet) deformation over time depending on the environment in which it is used. On the other hand, when the amount is less than 0.1% by weight, there may be a problem in adhesiveness or a problem in dispersibility of the near infrared absorber. Further, since the saturated water absorption rate is within the above range, deterioration of the image sensor due to moisture can be prevented particularly when used for a translucent lid of a package for housing a solid-state image sensor. The saturated water absorption is a value obtained by immersing in 23 ° C. water for 1 week and measuring the increased weight according to ASTM D570.

《Near-infrared absorber》
The norbornene-based resin used in the present invention can be used by containing a near infrared absorber. As this near infrared absorber, for example, a metal complex compound that absorbs near infrared rays can be used. The near-infrared-absorbing metal complex compound (hereinafter referred to as “specific dye”) used in the present invention is a spectrum measured at an optical path length of 1 cm at a wavelength of 800 to 1000 nm when dissolved in a good solvent. A compound having a concentration range in which the transmittance is 60% or less, preferably 30% or less is desirable. Further, depending on applications such as a front plate for PDP, in the so-called visible light region having a wavelength of 400 to 700 nm, the total light transmittance measured under the above conditions may be required to be 50% or more, preferably 65% or more. is there.

As the compound, any metal complex compound that acts as a dye that absorbs near infrared rays can be used, and examples thereof include a phthalocyanine compound, a naphthalocyanine compound, and a dithiol metal complex compound. Specifically, for example, JP-A-8-225752, JP-A-8-253893, JP-A-9-111138, JP-A-9-157536, JP-A-9-176501, JP-A-9 -263658, JP-A 2000-212546, JP-A 2002-200711 and the like, and metal complex compounds whose structures and production methods are disclosed. Further, for example, CIR-1080, CIR-1081 (manufactured by Nippon Carlit), YKR-3080, YKR-3081 (manufactured by Yamamoto Kasei), eXcolor IR-10, IR-12, IR-14 (manufactured by Nippon Shokubai), Commercial products such as phthalocyanine compounds such as SIR-128, SIR-130, SIR-159, PA-1001, and PA-1005 (manufactured by Mitsui Chemicals Fine) can also be used.

  In the present invention, a metal ion and a chelate-forming compound are added independently, and the metal ion and the chelate-forming compound react to form a metal complex compound that absorbs near infrared rays, that is, a specific dye. May be. Examples of the specific dye include a reaction product of a phosphate ester compound and copper ions described in JP-A-6-118288.

  Furthermore, the compound in the present invention includes a compound in which the polar group in the norbornene-based resin used in the present invention and a metal ion form a complex and have infrared absorption ability. That is, in this invention, when it becomes a norbornene-type resin-made board | substrate, it can also contain the metal complex compound which has a function which absorbs near infrared rays.

  In the present invention, the near-infrared absorber is appropriately selected according to desired properties, but is usually 0.01 to 20.0 parts by weight, preferably 0, based on 100 parts by weight of the norbornene resin used in the present invention. 0.02 to 10.0 parts by weight, more preferably 0.05 to 5.0 parts by weight. When the amount used is within the above range, a near-infrared cut filter excellent in visible light transmittance can be obtained.

《Other ingredients》
In the present invention, additives such as an antioxidant and an ultraviolet absorber can be further added to the norbornene-based resin as long as the effects of the present invention are 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, tetrakis [ And methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. Moreover, when manufacturing a norbornene-type resin-made board | substrate by the solution casting method mentioned later, manufacture of a resin board | substrate can be made easy by adding a leveling agent and an antifoamer.

  These additives may be mixed together with a norbornene resin or the like when manufacturing the norbornene resin substrate used in the present invention, or may be added in advance when the norbornene resin is manufactured. May be. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2. parts by weight based on 100 parts by weight of the norbornene resin. 0 part by weight is desirable.

<< Manufacturing Method of Norbornene Resin Substrate >>
The norbornene-based resin substrate used in the present invention can be molded by directly melt-molding norbornene-based resin, or by dissolving in a solvent and casting (cast molding). In the case of a norbornene-based resin substrate containing an infrared absorber, for example, a method of melt-molding pellets obtained by melt-kneading a norbornene-based resin and an infrared absorber, a norbornene-based resin, an infrared absorber, And a method of melt-molding pellets obtained by removing the solvent from the liquid resin composition containing the solvent, or a method of casting (cast molding) the above-mentioned liquid resin composition.

(A) Melt Molding The norbornene resin substrate used in the present invention can be produced by melt molding a norbornene resin or a resin composition containing a norbornene resin and an infrared absorber. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

(B) Casting The norbornene-based resin substrate used in the present invention is a liquid resin composition obtained by dissolving a norbornene-based resin in a solvent, or a liquid resin composition containing a norbornene-based resin, a near infrared absorber, and a solvent. It can also be produced by casting on a substrate to remove the solvent. For example, a norbornene-based resin substrate is formed by applying the above-described 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. Can be obtained. Further, a norbornene resin substrate can be formed on the original optical component by coating the above-mentioned liquid composition on an optical component made of glass, quartz or transparent plastic and drying the solvent.

  The amount of residual solvent in the norbornene-based 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 residual solvent amount exceeds 3% by weight, the resin substrate may be deformed over time or the characteristics may be changed over time, and a desired function may not be exhibited.

<Near-infrared reflective film>
The near-infrared ray reflecting film used in the present invention is a film having the ability to reflect near-infrared rays. As such a near-infrared reflective film, an aluminum vapor-deposited film, a noble metal thin film, a resin film in which metal oxide fine particles mainly containing indium oxide and containing a small amount of tin oxide are dispersed, a high refractive index material layer and a low refractive index material A dielectric multilayer film in which layers are alternately stacked can be used.

Among these near-infrared reflective films, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated can be suitably used.
As a 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 1.7 to 2.5 is usually 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 small amounts of titanium oxide, tin oxide, cerium oxide, and the like. The thing etc. which were made to contain are mentioned.

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 1.2 to 1.6 is usually selected.
Examples of these materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and aluminum hexafluoride sodium.

The method for 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 stacked is formed. For example, CVD, sputtering, vacuum deposition A dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated is formed by a method or the like, and this is laminated on a norbornene resin substrate with an adhesive. In addition, it can be obtained by directly forming a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated by a CVD method, a sputtering method, a vacuum deposition method or the like.

  The thicknesses of the high refractive index material layer and the low refractive index material layer are generally 0.1λ to 0.5λ of the infrared wavelength λ (nm) to be blocked. When the thickness is out of the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by λ / 4, and the optical characteristics of reflection and refraction are different. The relationship is broken, and control for blocking / transmitting a specific wavelength tends to be impossible.

The number of laminated layers in the dielectric multilayer film is usually in the range of 10 to 80 layers, preferably in the range of 25 to 50 layers.
In particular, when a near-infrared absorber is contained in a norbornene-based resin substrate, the number of laminated layers in the dielectric multilayer film can be 5 to 40 layers, preferably 10 to 30 layers. The dielectric multilayer film is preferable in that it is difficult to break.

  In addition, if the substrate is warped when the dielectric multilayer film is deposited, in order to eliminate this, the dielectric multilayer film is deposited on both sides of the substrate. It is possible to take a method such as irradiation with ultraviolet rays or the like. In addition, when irradiating a radiation, you may irradiate while performing the vapor deposition of a dielectric multilayer, and you may irradiate separately after vapor deposition.

<Uses of near-infrared cut filter>
These near-infrared cut filters obtained by the present invention have excellent near-infrared cut ability and are difficult to break. Therefore, not only is it useful as a heat ray cut filter mounted on glass in automobiles and buildings, but it is especially useful for correcting the visibility of solid-state image sensors such as CCDs and CMOSs in digital still cameras and mobile phone cameras. Useful.

〔Example〕
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. “Parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

First, a method for measuring each physical property value and a method for evaluating the physical property will be described.
(1) Molecular weight:
Standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type) manufactured by WATERS, equipped with an H type column manufactured by Tosoh Corporation, under conditions of o-dichlorobenzene solvent and 120 ° C. The converted weight average molecular weight (Mw) and number average molecular weight (Mn) were measured.
(2) Hydrogenation rate:
The measurement was carried out using 500 MHz ¹ H-NMR (AVANCE 500) manufactured by Bruker.
(3) Glass transition temperature (Tg):
Using a differential scanning calorimeter (DSC6200) manufactured by Seiko Instruments Inc., the temperature was increased at a rate of temperature increase of 20 ° C. per minute under a nitrogen stream.
(4) Saturated water absorption:
In accordance with ASTM D570, the test piece was immersed in water at 23 ° C. for 1 week, and the water absorption was measured from the change in weight of the test piece.
(5) Spectral transmittance:
Measurement was performed using a spectrophotometer (U-3410) manufactured by Hitachi, Ltd.

<Example 1>
A transparent resin “Arton F” (hydrogenated norbornene ring-opening polymer: saturated water absorption 0.4%) manufactured by JSR Corporation was dissolved in toluene to obtain a 30% solution. Then, the solution is cast on a smooth glass plate and dried at 60 ° C. for 8 hours, 100 ° C. for 8 hours, and further under reduced pressure at 100 ° C. for 8 hours to obtain a substrate having a thickness of 0.2 mm and a side of 60 mm. Obtained. A multi-layer vapor deposition film [silica (SiO ₂ : film thickness 120) that reflects near infrared rays at a vapor deposition temperature of 150 ° C. on one surface of the substrate.
˜190 nm) layer and titania (TiO ₂ : film thickness 70-120 nm) ) Layers are alternately stacked, and the number of stacked layers is 50]. Next, an optical filter was manufactured by irradiating the surface of the substrate on which the multilayer deposited film was laminated with 1 J / cm ² of ultraviolet light in a nitrogen atmosphere using a metal halide lamp equipped with a cold mirror. The spectral transmittance curve of this optical filter was measured. The result is shown in FIG.

  The horizontal axis of the graph in FIG. 1 indicates the wavelength, and the vertical axis indicates the transmittance. As is apparent from this graph, the transmittance in the visible region of the wavelength 400 to 700 nm is about 90%, and the near red of the wavelength 750 to 1000 nm. The transmittance in the outer region was 5% or less.

This transmittance is measured using a spectrophotometer under the condition that the light source is perpendicularly incident on the resin substrate.
The degree of warping of the optical filter thus prepared at room temperature (20 ° C.) was measured by the Newton ring method using a laser beam having a wavelength of 633 nm. As a result, +5 Newton rings (λ = 633 nm, 60 mmΦ) in a region having a diameter of 60 mm. It was as follows and it was confirmed that almost no warping occurred. In addition, before the ultraviolet irradiation, +18 Newton rings were confirmed.

<Example 2>
A substrate having a thickness of 0.2 mm and a side of 60 mm was obtained in the same manner as in Example 1 except that 0.1% of a near infrared absorber “SIR-159” manufactured by Mitsui Chemicals, Inc. was added at the time of manufacturing the substrate. It was. On one surface of the substrate, a multilayer deposited film [silica (SiO ₂
: Film thickness 120-190 nm) and titania (TiO ₂ : film thickness 70-120 nm) ) Layers are alternately stacked, and the number of stacked layers is 25]. Next, an optical filter was manufactured by irradiating the surface of the substrate on which the multilayer deposited film was laminated with 1 J / cm ² of ultraviolet light in a nitrogen atmosphere using a metal halide lamp equipped with a cold mirror. The spectral transmittance curve of this optical filter was measured. The result is shown in FIG.

  As is apparent from this graph, even when the number of layers is 25, the transmittance in the visible range of 400 to 700 nm was about 85%, and the transmittance in the near infrared range of 750 to 1000 nm was 5% or less.

The warpage of the optical filter thus obtained was measured in the same manner as in Example 1. As a result, the number of Newton rings was +1.
<Synthesis Example 1> (Synthesis of Addition Polymer A)
Fully dried and nitrogen-substituted 1 liter stainless steel autoclave with 6 ppm water dehydrated cyclohexane; 420.4 g, p-xylene; 180.2 g, 5-trimethoxytoxylsilylbicyclo [2.2.1] hepta 2-ene; 48.75 mmol (10.43 g) and bicyclo [2.2.1] hept-2-ene; 1,425 mmol (134.1 g) were charged, and gaseous ethylene was charged with an internal pressure of 0 in the autoclave. It was charged to 1 MPa.

The autoclave is heated to 75 ° C., and palladium 2-ethylhexanoate as a catalyst component (as Pd atoms); 0.003 milligram atoms and tricyclohexylphosphine; 0.0
Polymerization was started by adding 015 mmol of toluene in the order of toluene; the total amount of the solution reacted at 25 ° C. for 1 hour, triphenylcarbenium pentafluorophenylborate; 0.00315 mmol.

  90 minutes after the start of polymerization 5-trimethoxytoxylsilylbicyclo [2.2.1] hept-2-ene; 11.25 mmol (2.41 g), then 7.5 mmol (1.61 g) every 30 minutes, 3.75 mmol (0.80 g) and 3.75 mmol were added a total of 4 times.

  After performing the polymerization reaction at 75 ° C. for 4 hours, 1 ml of tributylamine was added to terminate the polymerization to obtain a polymer A solution having a solid content of 19.9% by weight. A part of the polymer A solution was placed in isopropanol, solidified, and further dried to obtain polymer A.

As a result of 270 MHz-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) of this polymer A, polymer A
The proportion of structural units derived from 5-trimethoxyoxysilylbicyclo [2.2.1] hept-2-ene is 4.8 mol%, and the molecular weight is 74,000 in terms of number average molecular weight (Mn) and weight average. The molecular weight (Mw) was 185,000, the glass transition temperature (Tg) was 360 ° C., and the saturated water absorption was 0.35%.

<Example 3>
A substrate having a thickness of 0.2 mm and a side of 60 mm was prepared in the same manner as in Example 1 except that a 30% resin solution obtained by dissolving the addition polymer A obtained in Synthesis Example 1 in cyclohexane was used. Obtained. Further, an optical filter was produced in the same manner as in Example 1. The spectral transmittance of this optical filter was measured in the same manner as in Example 1. As a result, a transmittance curve almost the same as that in FIG. 1 was obtained, and near-infrared light having a wavelength of 750 to 1000 nm was cut.

  When the warpage of the optical filter thus obtained was measured in the same manner as in Example 1, it was 4 Newton rings.

FIG. 1 shows a spectral transmittance curve of the optical filter produced in Example 1. FIG. 2 shows a spectral transmittance curve of the optical filter produced in Example 2.

Claims (6)

  A near-infrared cut filter comprising a norbornene-based resin substrate and a near-infrared reflective film.   The near-infrared cut filter according to claim 1, wherein the near-infrared reflective film is a dielectric multilayer film.   The near-infrared cut filter according to claim 1, wherein the norbornene-based resin substrate contains a near-infrared absorber.   The near-infrared cut filter for solid-state imaging devices according to claim 1.   A solid-state imaging device comprising the near-infrared cut filter according to claim 1.   A method for producing a near-infrared cut filter comprising: laminating a near-infrared reflective film on one side of a norbornene-based resin substrate; and irradiating the surface with radiation.

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