CN107076894A

CN107076894A - Infrared ray shielding composition, cured film and solid camera head

Info

Publication number: CN107076894A
Application number: CN201580053503.8A
Authority: CN
Inventors: 畠山耕治; 嶋田遵生子; 河合孝广; 若林隆太郎
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2014-12-26
Filing date: 2015-12-22
Publication date: 2017-08-18
Anticipated expiration: 2035-12-22
Also published as: CN107076894B; WO2016104491A1; KR20220146660A; JP6702197B2; TWI701304B; JPWO2016104491A1; TW201631058A; KR20170099845A

Abstract

A kind of infrared ray shielding composition, there is the infrared absorbent and (B) siloxane polymer of maximum absorption wavelength containing (A) in the range of 700~2000nm of wavelength, (B) siloxane polymer has the construction unit α represented by following formula (1) and the construction unit β, construction unit α and construction unit β that are represented by following formula (3) content ratio [α/β] using molar ratio computing as 100/0~5/95.[in formula, R¹Represent aromatic hydrocarbyl, R³Chain alkyl is represented, m and n represent 1~3 integer independently of each other.]

Description

Infrared ray shielding composition, cured film and solid camera head

Technical field

Related to the present invention relates to infrared ray shielding composition, cured film and solid camera head, more specifically, the present invention And suitable for forming the infrared ray shielding composition of cured film used in infrared ray cut off filter etc., using the infrared ray Cured film that shielding composition is formed and the solid camera head for possessing the cured film.

Background technology

The semiconducting solids such as ccd image sensor, cmos image sensor are equipped with the camera devices such as digital camera to take the photograph Element.The sensitivity of these solid-state imagers, due to spanning to infrared spectral range from visibility region, therefore in camera device In, it is provided between pick-up lens and solid-state imager for blocking ultrared infrared ray cut off filter.By this Infrared ray cut off filter, can be by the sensitivity amendment of solid-state imager to the visibility close to the mankind.

As infrared ray cut off filter, such as it is known have make containing metal oxide, diimmonium pigment infrared ray inhale Receive the infrared ray-absorbable combination of the polymerizable compounds such as agent, the resin glue of alkali-soluble and (methyl) acrylic monomer Thing be solidified into it is membranaceous obtained from infrared ray cut off filter (patent document 1,2).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2013-137337 publications

Patent document 2：Japanese Unexamined Patent Publication 2013-151675 publications

The content of the invention

Now, as described in above-mentioned prior art, infrared ray cut off filter using using hydrocarbon system polymer as material as Main flow.The present inventor etc. is conceived to siloxane polymer as new material, and research and inquirement exploitation uses its infrared ray Cut-off filter, so that finding that the infrared ray cut off filter of siloxane-containing copolymer is present easily produces the poly- containing hydrocarbon system of cracking The non-existent peculiar problem of infrared ray cut off filter institute of compound.

Therefore, problem of the invention is to provide a kind of silicone-containing polymerization for forming the excellent cured film of crack resistance The infrared ray shielding composition of thing.In addition, the present invention provide formed using the infrared ray shielding composition cured film, And possess the solid camera head of the cured film.Here, " infrared ray masking " refers to absorb or reflects infrared in this specification Line.

The present inventor etc. dedicates oneself to research and inquirement, as a result finds by making in the range of 700~2000nm of wavelength Infrared ray smoke agent for shielding with maximum absorption wavelength contains the siloxane polymer of tool specific structure, you can solve above-mentioned problem.

That is, the present invention provides a kind of infrared ray shielding composition, containing (A) in the range of 700~2000nm of wavelength Infrared ray smoke agent for shielding and (B) siloxane polymer with maximum absorption wavelength,

(B) siloxane polymer has aromatic hydrocarbyl.

In addition, the present invention provides a kind of infrared ray shielding composition, containing (A) 700~2000nm of wavelength scope Interior infrared ray smoke agent for shielding and (B) siloxane polymer with maximum absorption wavelength,

(B) siloxane polymer has the construction unit α represented by following formula (1) and the structure represented by following formula (3) Unit β, construction unit α and construction unit β content ratio [α/β] are using molar ratio computing as 100/0~5/95.

[in formula, R¹Represent aromatic hydrocarbyl, R³Chain alkyl is represented, m and n represent 1~3 integer independently of each other.]

In addition, the present invention is provided using cured film formed by above-mentioned infrared ray shielding composition；Possesses the cured film Solid camera head.

Furthermore, the present invention provides a kind of solid camera head, wherein, possess：Transmit visible ray and at least a portion is infrared 1st optical layer of light, the 2nd optical layer with absorbing at least a portion infrared light,

Above-mentioned 2nd optical layer has the opening portion of transmission visible ray and infrared light, and by using above-mentioned infrared ray shielding The cured film that composition is formed is constituted.

As preferred mode, the present invention provides a kind of solid camera head, wherein, possess the 1st optical layer, the 2nd light Layer and pel array are learned, above-mentioned 1st optical layer transmission visible ray and at least a portion infrared light, above-mentioned 2nd optical layer are absorbed into Few a part of infrared light, above-mentioned pel array includes the 1st photo detector and the 2nd photo detector, and above-mentioned 1st photo detector detection is saturating Penetrate the above-mentioned visible ray of above-mentioned 1st optical layer and above-mentioned 2nd optical layer, above-mentioned 1st optics of above-mentioned 2nd photo detector detection transmission The above-mentioned infrared light of layer,

Above-mentioned 2nd optical layer has opening portion in the part corresponding to above-mentioned 2nd photo detector, above-mentioned 2nd optical layer by The cured film formed using above-mentioned infrared ray shielding composition is constituted.

Furthermore, the present invention provides a kind of solid camera head, possess transmission visible ray and at least a portion infrared light the 1st Optical layer and the 2nd optical layer for absorbing at least a portion infrared light,

2nd optical layer has the opening portion of transmission visible ray and infrared light, and contains following compositions (A) and (B) by using The cured film that is formed of infrared ray shielding composition constitute.

(A) there is the infrared ray smoke agent for shielding of maximum absorption wavelength in the range of 700~2000nm of wavelength,

(B) there is the siloxane polymer of aromatic hydrocarbyl.

The infrared ray shielding composition of the present invention, even if using siloxane polymer as raw material, crack resistance is also excellent It is different, and the optical shielding property in infrared spectral range is high.Therefore, using consolidating that the infrared ray shielding composition of the present invention is formed Change film can be work perfectly well as infrared ray cut off filter and use, and the making for solid camera head is extremely useful.

Brief description of the drawings

Fig. 1 is the schematic diagram of the solid camera head of one embodiment of the present invention.

Fig. 2 is the top view of the solid camera head of one embodiment of the present invention.

Fig. 3 is the sectional view of the summary for the solid camera head for representing one embodiment of the present invention.

Fig. 4 is the transmitted spectrum of the 1st optical layer used in the solid camera head for represent one embodiment of the present invention Figure.

Fig. 5 is the transmitted spectrum of the 2nd optical layer used in the solid camera head for represent one embodiment of the present invention Figure.

Fig. 6 is the transmission of the infrared light bandpass filter used in the solid camera head for represent one embodiment of the present invention The figure of spectrum.

Fig. 7 is to represent the cured film (infrared ray that the infrared ray shielding composition obtained by using in embodiment 5 is formed Cut-off filter) transmitted spectrum figure.

Fig. 8 is the sectional view of the summary for the solid camera head for representing the 2nd embodiment of the present invention.

Fig. 9 is the sectional view of the summary for the solid camera head for representing the 3rd embodiment of the present invention.

Embodiment

Infrared ray shielding composition

The infrared ray shielding composition of the present invention contains (A) composition and (B) composition, below for the infrared ray of the present invention The constituent of shielding composition is described in detail.

- (A) infrared ray smoke agent for shielding-

(A) composition is the infrared ray smoke agent for shielding with maximum absorption wavelength in the range of 700~2000nm of wavelength.

It is as long as having maximum absorption wavelength in the range of 700~2000nm of wavelength, then not special as (A) composition Restriction, can for example enumerate diimmonium based compound, sour cyanines (squarylium) based compound in side, flower cyanines based compound, phthalocyanine Based compound, naphthalene phthalocyanine based compound, quaterrylene (quaterrylene) based compound, ammonium based compound, imonium (imonium) based compound, Azo, anthraquinone based compound, porphyrin based compound, pyrrolopyrrole (pyrrolopyrrole) based compound, oxonols (oxonol) based compound, crocic acid (croconium) based compound, six First porphyrin (hexaphyrin) based compound, metal dithionite alcohol based compound, copper compound, tungsten compound, metal boride etc.. (A) composition can be used alone or in combination of two kinds or more.

Wherein, preferably comprise selected from diimmonium based compound, the sour cyanines based compound in side, flower cyanines based compound, phthalocyanine system Compound, naphthalene phthalocyanine based compound, quaterrylene based compound, ammonium based compound, imonium based compound, pyrrolopyrrole system It is at least one kind of in compound, crocic acid based compound, metal dithionite alcohol based compound, copper compound and tungsten compound.More preferably contain Have selected from diimmonium based compound, the sour cyanines based compound in side, flower cyanines based compound, phthalocyanine based compound, naphthalene phthalocyanine based compound, Quaterrylene based compound, ammonium based compound, imonium based compound, pyrrolopyrrole based compound, crocic acid based compound, The combination of at least one kind of and tungsten compound in metal dithionite alcohol based compound and copper compound；Or preferably comprise sub- selected from two Ammonium based compound, the sour cyanines based compound in side, flower cyanines based compound, phthalocyanine based compound, naphthalene phthalocyanine based compound, quaterrylene Based compound, ammonium based compound, imonium based compound, pyrrolopyrrole based compound, crocic acid based compound, metal dithionite alcohol Two or more in based compound and copper compound.By such mode, it can efficiently block and be injected into photo detector Infrared ray.

The compound illustrated below that may be used as (A) composition.

As the concrete example of diimmonium (diiminium, diimonium) based compound, for example, it can enumerate Japanese Unexamined Patent Publication 1-113482 publications, Japanese Unexamined Patent Publication 10-180922 publications, International Publication No. 2003/5076, International Publication No. No. 2004/48480, International Publication No. 2005/44782, International Publication No. 2006/120888, Japanese Unexamined Patent Publication 2007- No. 246464 publications, International Publication No. 2007/148595, Japanese Unexamined Patent Publication 2011-038007 publications, International Publication No. Compound described in No. 2011/118171 [0118] paragraph etc. etc..As commercially available product, for example, it can enumerate The CIR-108X such as the EPOLIGHT such as EPOLIGHT1178 series (Epolin company systems), CIR-1085 series and CIR-96X series (Japan Carlit company systems), IRG022, IRG023, PDC-220 (Japanese chemical drug company system) etc..

As the concrete example of the sour cyanines based compound in side, for example, it can enumerate No. 3094037 specifications of Japanese Patent No., Japan spy Open clear 60-228448 publications, Japanese Unexamined Patent Publication 1-146846 specifications, Japanese Unexamined Patent Publication 1-228960 publications, Japan Compound described in [0178] paragraph of JP 2012-215806 publications etc..

As the concrete example of flower cyanines based compound, for example, it can enumerate the of Japanese Unexamined Patent Publication 2007-271745 publications [0041]~[0042] [0016]~[0018] paragraph, the Japanese Unexamined Patent Publication of paragraph, Japanese Unexamined Patent Publication 2007-334325 publications 2009-108267 publications, Japanese Unexamined Patent Publication 2009-185161 publications, Japanese Unexamined Patent Publication 2009-191213 publications, Japan are special Open [0160] paragraph, [0047]~[0049] of Japanese Unexamined Patent Publication 2013-155353 publications of 2012-215806 publications Compound described in paragraph etc..As commercially available product, for example, it can enumerate Daito chmix 1371F (DAITO CHEMIX companies System), the NK such as NK-3212, NK-5060 serial (woods protobiochemistry research is made) etc..

As the concrete example of phthalocyanine based compound, for example, it can enumerate Japanese Unexamined Patent Application 60-224589 publications, Japanese Unexamined Patent Application Publication 2005-537319 publications, Japanese Unexamined Patent Publication 4-23868 publications, Japanese Unexamined Patent Publication 4-39361 publications, Japanese Unexamined Patent Publication 5-78364 publications, Japanese Unexamined Patent Publication 5-222047 publications, Japanese Unexamined Patent Publication 5-222301 publications, Japanese Unexamined Patent Publication 5- No. 222302 publications, Japanese Unexamined Patent Publication 5-345861 publications, Japanese Unexamined Patent Publication 6-25548 publications, Japanese Unexamined Patent Publication 6- No. 107663 publications, Japanese Unexamined Patent Publication 6-192584 publications, Japanese Unexamined Patent Publication 6-228533 publications, Japanese Unexamined Patent Publication 7- No. 118551 publications, Japanese Unexamined Patent Publication 7-118552 publications, Japanese Unexamined Patent Publication 8-120186 publications, Japanese Unexamined Patent Publication 8- No. 225751 publications, Japanese Unexamined Patent Publication 9-202860 publications, Japanese Unexamined Patent Publication 10-120927 publications, Japanese Unexamined Patent Publication 10- No. 182995 publications, Japanese Unexamined Patent Publication 11-35838 publications, Japanese Unexamined Patent Publication 2000-26748 publications, Japanese Unexamined Patent Publication 2000- No. 63691 publications, Japanese Unexamined Patent Publication 2001-106689 publications, Japanese Unexamined Patent Publication 2004-18561 publications, Japanese Unexamined Patent Publication 2005- No. 220060 publications, Japanese Unexamined Patent Publication 2007-169343 publications, Japanese Unexamined Patent Publication 2013-195480 publications [0026]~ [0027] compound described in paragraph etc. etc..As commercially available product, (the hillside plot chemistry work of the FB series such as can enumerate FB-22,24 Industry company system), Excolor series, Excolor TX-EX 720, Excolor TX-EX 708K (Japanese catalyst system), Lumogen IR788 (BASF systems), ABS643, ABS654, ABS667, ABS670T, IRA693N, IRA735 (Exciton systems), SDA3598、SDA6075、SDA8030、SDA8303、SDA8470、SDA3039、SDA3040、SDA3922、SDA7257 (H.W.SANDS systems), TAP-15, IR-706 (hillside plot chemical industry system) etc..

As the concrete example of naphthalene phthalocyanine based compound, for example, it can enumerate Japanese Unexamined Patent Publication 11-152413 publications, Japan spy Open flat 11-152414 publications, Japanese Unexamined Patent Publication 11-152415 publications, the of Japanese Unexamined Patent Publication 2009-215542 publications [0046]~[0049] compound described in paragraph etc..

As the concrete example of quaterrylene based compound, for example, it can enumerate Japanese Unexamined Patent Publication 2008-009206 publications Compound described in [0021] paragraph etc. etc..As commercially available product, for example, it can enumerate Lumogen IR765 (BASF AG's system) Deng.

As the concrete example of ammonium based compound, for example, it can enumerate [0018] of Japanese Unexamined Patent Publication 08-027371 publications Compound described in paragraph, Japanese Unexamined Patent Publication 2007-039343 publications etc..As commercially available product, can for example enumerate IRG002, IRG003 (Japanese chemical drug company system) etc..

As the concrete example of imonium based compound, for example, it can enumerate [0116] of International Publication No. 2011/118171 Compound described in paragraph etc..

As the concrete example of Azo, for example, it can enumerate the of Japanese Unexamined Patent Publication 2012-215806 publications [0114]~[0117] compound described in paragraph etc..

As the concrete example of anthraquinone based compound, for example, it can enumerate the of Japanese Unexamined Patent Publication 2012-215806 publications [0128] and the compound described in [0129] paragraph etc..

As the concrete example of porphyrin based compound, can for example enumerate No. 3834479 specifications of Japanese Patent No. with formula (1) The compound of expression.

As the concrete example of pyrrolopyrrole based compound, for example, it can enumerate Japanese Unexamined Patent Publication 2011-068731 publications, day Compound described in [0014]~[0027] paragraph of this JP 2014-130343 publications etc..

As the concrete example of oxonols based compound, for example, it can enumerate the of Japanese Unexamined Patent Publication 2007-271745 publications [0046] compound described in paragraph etc..

As the concrete example of crocic acid based compound, for example, it can enumerate the of Japanese Unexamined Patent Publication 2007-271745 publications [0049] chemical combination described in paragraph, Japanese Unexamined Patent Publication 2007-31644 publications, Japanese Unexamined Patent Publication 2007-169315 publications etc. Thing.

As the concrete example of hexa-atomic porphyrin based compound, can for example enumerate International Publication No. 2002/016144 with formula (1) compound represented.

As the concrete example of metal dithionite alcohol based compound, for example, it can enumerate Japanese Unexamined Patent Publication 1-114801 publications, day This JP 64-74272 publications, Japanese Unexamined Patent Application 62-39682 publications, Japanese Unexamined Patent Application 61-80106 publications, Japan Compound described in JP 61-42585 publications, Japanese Unexamined Patent Application 61-32003 publications etc..

As copper compound, preferably copper complex, as concrete example, for example, Japanese Unexamined Patent Publication 2013-253224 can be enumerated Number publication, Japanese Unexamined Patent Publication 2014-032380 publications, Japanese Unexamined Patent Publication 2014-026070 publications, Japanese Unexamined Patent Publication 2014- Change described in No. 026178 publication, Japanese Unexamined Patent Publication 2014-139616 publications, Japanese Unexamined Patent Publication 2014-139617 publications etc. Compound.

As tungsten compound, tungsten compound, more preferably cesium tungsten oxide, more preferably rubidium oxide tungsten, oxygen are preferably aoxidized Change caesium tungsten.As the composition formula of cesium tungsten oxide, Cs can be enumerated_0.33WO₃Deng additionally as the composition formula of rubidium oxide tungsten, can enumerating Rb_0.33WO₃Deng.Tungsten oxide based compound such as also can as the YMF-02A of Sumitomo Metal Mining Co., Ltd tungsten particulate Dispersion and obtain.

As the concrete example of metal boride, for example, it can enumerate [0049] of Japanese Unexamined Patent Publication 2012-068418 publications Compound described in paragraph etc..Wherein, preferably lanthanum boride.

It should illustrate, can also be by it in the case where above-mentioned (A) composition dissolves in disclosed (F) organic solvent below Color lake and as infrared ray smoke agent for shielding insoluble in (F) organic solvent.The method in color lake can use known method, for example It is referred to Japanese Unexamined Patent Publication 2007-271745 publications etc..

In addition, in the case where (A) composition does not dissolve in organic solvent, can also be with the dispersed, scattered of raising (A) composition The purpose of stability and contain dispersant.

As dispersant, for example, it can enumerate carbamic acid ester system dispersant, polyethyleneimine amine system dispersant, polyoxyethylene alkane Base ether system dispersant, polyoxyethylene alkyl phenyl ether system dispersant, polyethylene glycol di system dispersant, sorbitan fatty acids Ester system dispersant, Polyester dispersant, (methyl) dispersant containing acrylic etc..As commercially available product, for example, it can be used Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (are above BYK Chemie (BYK) company system) etc. (methyl) dispersant containing acrylic；Disperbyk-161、Disperbyk-162、 Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (are above BYK Chemie (BYK) Company system), the carbamic acid ester system dispersant such as SOLSPERSE 76500 (Lubrizol Co. Ltd. systems)；SOLSPERSE The polyethyleneimine amine system dispersants such as 24000 (Lubrizol Co. Ltd. systems)；AJISPER PB821、AJISPER PB822、 The Polyesters such as AJISPER PB880, AJISPER PB881 (being above Ajinomoto Fine-Techno Co. Ltd. systems) point Beyond powder, BYK-LPN21324 (BYK Chemie (BYK) company system) can also be used.Dispersant can alone or in combination 2 kinds Use above.

The content of dispersant can be properly selected according to the species of dispersant, but relative to (A) infrared ray smoke agent for shielding 100 mass parts, preferably 5~300 mass parts, more preferably 10~200 mass parts.

(A) content of composition is preferably 0.1~80 matter in the solid constituent of the infrared ray shielding composition of the present invention Measure %, more preferably more preferably 1~70 mass %, 3~60 mass %.

By such mode, infrared ray can be fully covered.Here, " solid constituent " is described later in this specification Composition beyond organic solvent.

- (B) siloxane polymers-

(B) siloxane polymer in the present invention has aromatic hydrocarbyl.Here, " aromatic hydrocarbyl " is in this specification In ring structure have aromatic ring structure alkyl, be condensed each other comprising monocyclic aromatic alkyl, phenyl ring or phenyl ring and its More than 2 in the condensed type aromatic hydrocarbyl and phenyl ring and condensed ring of the condensation of his hydrocarbon ring are with singly-bound bond The concept of polycycle aromatic hydrocarbyl.It should illustrate, aromatic hydrocarbyl only need not be made up of ring structure, a part for ring structure Also it can be replaced by chain alkyl.As chain alkyl, for example, alkyl, alkenyl, alkynyl can be enumerated, the carbon number of chain alkyl is excellent Elect 1~6, more preferably 1~4 as.

The carbon number of aromatic hydrocarbyl does not have special restriction, but preferably 6~20, and more preferably 6~14, enter one Step is preferably 6~10.

As the concrete example of aromatic hydrocarbyl, for example, it can enumerate phenyl, tolyl, xylyl, trimethylphenyl, styrene Base, indenyl, naphthyl, anthryl, phenanthryl, fluorenyl, pyrenyl, ethyl benzo anthryl (naphthacenaphthenyl), xenyl, three Xenyl etc..Wherein, the preferably aryl of the aromatic hydrocarbyl of carbon number 6~14, more preferably carbon number 6~14, enters One step is preferably phenyl, tolyl, naphthyl.Here, " aryl " refers to monocyclic to the aromatic hydrocarbon of 3 ring types in this specification Base.

In addition, aromatic hydrocarbyl can also have substituent, as substituent, for example, halogen atom, hydroxyl, mercapto can be enumerated Base, alkoxy, alkyloxy-alkoxy, alkylthio group, amino, dialkyl amido, amide groups, alkylamidoalkyl, acylamino-, carboxyl, Alkoxy carbonyl, cyano group, group with heterocyclic radical etc..Here, " heterocyclic radical " refers to oxygen atom, nitrogen original in this specification Son, sulphur atom etc., as the heteroatomic heterocyclic radical for constituting heterocycle, can be saturated heterocyclyl or unsaturated heterocycle Base.It should illustrate, the position of substituent and quantity are any, in the case of with more than 2 substituents, the substituent can be with It is identical, can also be different.

As halogen atom, fluorine atom, bromine atoms, chlorine atom, iodine atom can be enumerated, in addition, as alkoxy, such as may be used Enumerate the C such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy_1-6Alkoxy.As alkyloxy-alkoxy, for example, it can enumerate first The C such as Oxymethoxy, methoxy ethoxy, ethoxy ethoxy_2-6Alkyloxy-alkoxy, additionally as alkylthio group, for example, can be lifted Go out the C such as methyl mercapto, ethylmercapto group_1-6Alkylthio group.As dialkyl amido, two such as can enumerate dimethylamino, diethylamino (C_1-6Alkyl) amino, additionally as alkylamidoalkyl, the C such as can enumerate methyl acylamino, ethyl acylamino_1-6Alkylamide Base.As acylamino-, the C such as can enumerate acetyl-amino, propanoylamino_2-6Acylamino- etc., additionally as alkoxy carbonyl Base, the C such as can enumerate methoxycarbonyl, ethoxy carbonyl_2-6Alkoxy carbonyl.It is used as containing in the group with heterocyclic radical Oxa- ring group, the atomicity for preferably constituting ring is 3~7 cyclic ether group, as cyclic ether group, for example, can enumerate epoxy second Base, oxetanyl, 3,4- expoxycyclohexyls, tetrahydrofuran base etc..As the group with oxygen-containing heterocycle, for example may be used Enumerate glycidyl, glycidoxy, epoxy radicals alkoxy, 3,4- expoxycyclohexyls etc..As epoxy radicals alkoxy, for example Epoxy radicals (the C such as epoxy ylmethoxy, epoxy base oxethyl can be enumerated_1-6Alcoxyl) base.

From the viewpoint of crack resistance is improved, (B) siloxane polymer in the present invention, optimization aromatic alkyl contains It is 5 moles of more than %, more preferably 20 moles more than %, more preferably 60 moles more than % relative to Si atoms to have rate. It should illustrate, even if even the containing ratio of the aromatic hydrocarbyl is 100 moles of % relative to Si atoms, but it is also possible to rubbed for 95 You are below %.

In addition, as (B) siloxane polymer, from the viewpoint of crack resistance is improved, preferably with by following formula (1) The construction unit of expression.

[in formula (1), R¹Aromatic hydrocarbyl is represented, m represents 1~3 integer.]

R¹In aromatic hydrocarbyl can also have substituent.It should illustrate, the concrete mode of aromatic hydrocarbyl and substituent As explained above.

(B) siloxane polymer with the construction unit represented by above-mentioned formula (1), which can make to be selected from, has aromatic hydrocarbon At least one kind of hydrolytic condensation in base and the silane compound of hydrolization group and its partial hydrolystate and obtain.Here, this explanation In book " hydrolization group " refer to can be by room temperature (about 25 DEG C)~about generally under without catalyst, the coexisting of excessive water Heated within the temperature range of 100 DEG C and the group that is hydrolyzed to generate silanol group or silicone condensation thing can be formed Group.As hydrolization group, for example, it can enumerate halogen atom, alkoxy.In addition, " partial hydrolystate " refers in this specification The hydrolytic condensate that the part hydrolysis of silane compound and silanol group are condensed each other.More specifically, it is to divide (silicon atom number is 2~100, preferably to the remaining silicone compounds of at least one, the hydrolization group of preferably more than 2 in son Siloxane oligomer for 2~30).

Wherein, it is preferably to be represented by following formula (2) as the silane compound with aromatic hydrocarbyl and hydrolization group Compound.

[in formula (2), R²Represent the alkyl of carbon number 1~6, R¹With m with it is above-mentioned synonymous.]

It is used as R²In carbon number be 1~6 alkyl, methyl, ethyl, n-propyl, isopropyl, normal-butyl can be enumerated Deng.Wherein, from the viewpoint of the easiness of hydrolysis, preferably methyl, ethyl.

There are silane compound, m that silane compound, m that m is 1 are 2 to be 3 in the silane compound represented by above-mentioned formula (2) Silane compound or their mixture of more than two kinds.

As concrete examples of the m for 1 silane compound, for example, it can enumerate phenyltrimethoxysila,e, phenyl triethoxy Silane, tolyl trimethoxy silane, tolyl triethoxysilane, xylyl trimethoxy silane, the second of xylyl three TMOS, trimethylphenyl trimethoxy silane, trimethylphenyl triethoxysilane, ethylphenyl trimethoxy silane, ethyl Phenyl triethoxysilane, ethenylphenyl trimethoxy silane, ethenylphenyl triethoxysilane, hydroxyphenyl trimethoxy Silane, hydroxyphenyl triethoxysilane, methoxyphenyl trimethoxy silane, methoxyphenyl triethoxysilane, ethyoxyl Phenyltrimethoxysila,e, ethoxyl phenenyl triethoxysilane, Dimethoxyphenyl trimethoxy silane, Dimethoxyphenyl Triethoxysilane, trimethoxyphenyl trimethoxy silane, (2- methoxyl groups) ethoxyl phenenyl trimethoxy silane, aminobenzene Base trimethoxy silane, aminophenyl triethoxysilane, diamino-phenyl trimethoxy silane, dimethylaminophenyl front three TMOS, acetylamino phenyl trimethoxy silane, carboxyl phenyl trimethoxy silane, methoxycarbonyl-phenyl trimethoxy Silane, amidophenyl trimethoxy silane, mercaptophenyl trimethoxy silane, methyl mercapto phenyltrimethoxysila,e, epoxy Propyl group phenyltrimethoxysila,e, glycidoxyphenyl trimethoxy silane, glycidoxyphenyl triethoxysilane, (2- rings Epoxide) ethoxyl phenenyl trimethoxy silane, (2- epoxy radicals) ethoxyl phenenyl triethoxysilane, cyano-phenyl trimethoxy Silane, naphthyl trimethoxy silane, naphthyl-triethyoxy silicane alkane, methyl naphthyl trimethoxy silane, methoxyl group naphthyl trimethoxy Base silane, the positive propoxy silane of naphthyl three, anthryl trimethoxy silane, anthryl triethoxysilane, phenanthryl trimethoxy silane, Phenanthryl triethoxysilane, fluorenyl trimethoxy silane, fluorenyl triethoxysilane, pyrenyl trimethoxy silane, the second of pyrenyl three TMOS, indenyl trimethoxy silane, indenyl triethoxysilane, ethyl benzo anthryl trimethoxy silane, ethyl benzo Anthryl triethoxysilane etc..These silane compounds can be used alone or in combination of two kinds or more.

As concrete examples of the m for 2 silane compound, for example, it can enumerate dimethoxydiphenylsilane, phenyl methyl two Methoxy silane, phenyl methyl diethoxy silane, tolylmethyl dimethoxysilane, tolylmethyl diethoxy silicon Alkane, naphthyl methyl dimethoxysilane, naphthyl methyl diethoxy silane, methylphenylmethyl dimethoxysilane, methylbenzene Ylmethyl diethoxy silane, methoxyphenyl methyl dimethoxysilane, methoxyphenyl methyl diethoxy silane etc..This A little silane compounds can be used alone or in combination of two kinds or more.

As concrete examples of the m for 3 silane compound, for example, it can enumerate pheiiyldimetliyl methoxy silane, phenyl diformazan Base oxethyl silane, tolyl dimethyl methoxy silane, tolyl dimethylethoxysilane, methoxyphenyl dimethyl methyl TMOS, methoxyphenyl dimethylethoxysilane, naphthyl dimethyl methoxy silane, naphthyl dimethylethyloxy silicon Alkane.These silane compounds can be used alone or in combination of two kinds or more.

Wherein, as the silane compound represented by above-mentioned formula (2), the solidification obtained by promoting hydrolytic condensation, improving From the viewpoint of the crack resistance of film, the silane compound that the m in more preferably above-mentioned formula (2) is 1.It should illustrate, by inciting somebody to action The silane compound hydrolytic condensation that m in above-mentioned formula (2) is 1, so as to obtain with the structure that the m in above-mentioned formula (1) is 1 (B) siloxane polymer of unit.

In addition, (B) is even if siloxane polymer has other silicon come beyond the construction unit that freely above-mentioned formula (1) represents The construction unit of hydride compounds can also, but from the viewpoint of the crack resistance of the cured film obtained by raising, be preferably by The content ratio for the construction unit that above-mentioned formula (1) represents is 5 moles of more than %, more preferably 20 in (B) siloxane polymer Mole more than %, more preferably 60 moles more than %.Should illustrate, in (B) siloxane polymer by above-mentioned formula (1) table The content ratio of the construction unit shown can be 100 moles of %, or 95 moles of below %.

(B) silica with the construction unit represented by above-mentioned formula (1) with the other structures unit beyond the construction unit Alkane polymer, for example, can pass through the silanization beyond silane compound and the silane compound that will be represented by above-mentioned formula (2) Compound cohydrolysis is condensed and obtained.It should illustrate, silane compound used in cohydrolysis condensation can be partial hydrolystate.

The silane compound of other structures unit beyond the construction unit represented as assigning by above-mentioned formula (1), for example The silane compound with 4 hydrolization groups, the disiloxane compound with 6 hydrolization groups can be enumerated, with chain Silane compound of shape alkyl or alicyclic type hydrocarbon and hydrolization group etc..For hydrolization group, for example, it can enumerate halogen Atom, alkoxy.Chain alkyl and alicyclic type hydrocarbon can also have substituent.As substituent, for example, except in aromatic hydrocarbon Beyond being illustrated in the substituent of base, (methyl) acryloyl group, (methyl) acryloxy, (methyl) acryloxy can be enumerated Propyl group etc..It should illustrate, the position of substituent and quantity are any, in the case of with more than 2 substituents, the substituent Can be with identical, can also be different.

Chain alkyl can be that straight chain can also be side chain, and can be that saturation can also be unsaturated.It is used as chain Alkyl, for example, can enumerate alkyl, alkenyl, alkynyl, wherein preferably alkyl, alkenyl.The carbon number of chain alkyl is preferably 1~ 30, more preferably 1~20, more preferably 1~10.

As alkyl, can for example enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, oneself Base, heptyl, octyl group, nonyl, decyl, undecyl, 1- methyldecyls, dodecyl, 1- methylundecyls, the 1- ethyl last of the ten Heavenly stems Base, tridecyl, myristyl, tertiary dodecyl, pentadecyl, 1- heptyl octyl group, cetyl, octadecyl, 21 Alkane -1- bases, docosane -1- bases, tricosane -1- bases, lignocerane -1- bases etc..In addition, as alkenyl, such as can enumerate Vinyl, 1- acrylic, 2- acrylic, 1- cyclobutenyls, 2- cyclobutenyls, 1,3- butadienyls, 1- pentenyls, 2- pentenyls, 1- Hexenyl, 2- ethyl -2- cyclobutenyls, 2- octenyls, (4- vinyl) -5- hexenyls, 2- decene bases etc..Furthermore, as alkynyl, Acetenyl, 1- propinyls, 1- butynyls, 1- pentynyls, 3- pentynyls, 1- hexin bases, 2- ethyl -2- butine can for example be enumerated Base, 2- octynyls, (4- acetenyls) -5- hexin bases, 2- decynyls etc..

Alicyclic type hydrocarbon can be that saturation can also be unsaturated, such as can enumerate cycloalkyl, cycloalkenyl group.Ester ring type hydrocarbon The carbon number of base is preferably 3~30, more preferably 3~20, more preferably 6~10.

As cycloalkyl, such as can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl.Separately Outside, as cycloalkenyl group, cyclohexenyl group etc. can be enumerated.It should illustrate, " alicyclic type hydrocarbon " is including not having cyclic structure The concept of aliphatic alkyl.

As the other structures unit beyond the construction unit represented by above-mentioned formula (1), from the viewpoint for improving crack resistance Consider, be preferably the construction unit represented by following formula (3).

[in formula (3), R³Chain alkyl is represented, n represents 0~3 integer.]

R³In chain alkyl also can have substituent, should illustrate, the concrete mode of chain alkyl and substituent is as above State illustrated.

The silane compound of the construction unit represented as assigning by above-mentioned formula (3), is preferably to be represented by following formula (4) Silane compound.

[in formula (4), R⁴Represent the alkyl of carbon number 1~6, R³With n with it is above-mentioned synonymous.]

It is used as R⁴In carbon number be 1~6 alkyl, methyl, ethyl, n-propyl, isopropyl, normal-butyl can be enumerated Deng.Wherein, from the viewpoint of the easiness of hydrolysis, preferably methyl, ethyl.

There are silane compound, n that silane compound, n that n is 0 are 1 to be 2 in the silane compound represented by above-mentioned formula (4) Silane compound, n be 3 silane compound or their mixture of more than two kinds.

As concrete examples of the n for 0 silane compound, for example, it can enumerate tetramethoxy-silicane, tetraethoxysilane, four fourths TMOS, tetraphenoxy-silicane alkane, benzyloxy-4 silane, four positive propoxy silane, tetraisopropoxysilan etc..These silanizations Compound can be used alone or in combination of two kinds or more.

As concrete examples of the n for 1 silane compound, for example, it can enumerate MTMS, methyl triethoxy Silane, the isopropoxy silane of methyl three, the butoxy silane of methyl three, ethyl trimethoxy silane, ethyl triethoxysilane, second The isopropoxy silane of base three, the butoxy silane of ethyl three, butyl trimethoxy silane, vinyltrimethoxy silane, vinyl Triethoxysilane, the positive propoxy silane of vinyl three, 3- methacryloxypropyl trimethoxy silanes, 3- metering systems Acryloxypropylethoxysilane triethoxysilane, 3- acryloxypropyls trimethoxy silane, 3- acryloxypropyl triethoxies Silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxysilane, β-(3,4- epoxies Butylcyclohexyl) ethyl trimethoxy silane etc..These silane compounds can be used alone or in combination of two kinds or more.

As concrete examples of the n for 2 silane compound, for example, it can enumerate dimethyldimethoxysil,ne, dibutyl diformazan TMOS etc..These silane compounds can be used alone or in combination of two kinds or more.

As concrete examples of the n for 3 silane compound, for example, it can enumerate tributyl methoxy silane, trimethyl methoxy Silane, trimethylethoxysilane, tributyl Ethoxysilane etc..These silane compounds can come alone or in combination of two kinds or more Use.

In the silane compound represented by above-mentioned formula (4), the silane chemical combination that silane compound that preferably n is 0, n are 1 Thing, more preferably n are 1 silane compound.

Wherein, for the present invention (B) siloxane polymer preferably have by above-mentioned formula (1) represent construction unit α with By above-mentioned formula (3) represent construction unit β, and construction unit α and construction unit β content ratio [α/β] using molar ratio computing as 100/0~5/95.By such mode, not only crack resistance is excellent, it is possibility to have the light of effect ground masking infrared spectral range, together When reduce mist degree, suppress the generation of development residue.

In addition, from further raising crack resistance, infrared ray shielding, suppressing aobvious with reducing mist degree and higher level From the viewpoint of the generation of shadow residue, (B) siloxane polymer is preferably the construction unit α and knot in (B) siloxane polymer Structure unit β content ratio [α/β] be 100/0~10/90, more preferably 85/15~20/80, more preferably 75/25~ 25/75, it is still more preferably 75/25~30/70.

Such (B) siloxane polymer can be manufactured by appropriate method.The condition of hydrolytic condensation, as long as By the silane compound represented by above-mentioned formula (2), as needed and use by above-mentioned formula (4) represent silane compound extremely A few part is hydrolyzed, and hydrolization group is transformed into silanol group and makes condensation reaction, then without any special Restriction, can for example enumerate following condition.

Water used in hydrolytic condensation is preferably used by the methods such as reverse osmosis membrane processing, ion-exchange treatment, distillation institute The water of purifying.By using such purified water, side reaction can be suppressed, make the reactivity raising of hydrolysis.Relative to by above-mentioned Formula (2) represent silane compound hydrolization group, as needed and use by above-mentioned formula (4) represent silane compound Hydrolization group 1 mole of total amount, the usage amount of water is preferably 0.1~3 mole, more preferably 0.3~2 mole, further Preferably 0.5~1.5 mole.By using the water of this tittle, the reaction speed of hydrolytic condensation can be optimized.

Solvent can also be used in hydrolytic condensation, as solvent, as long as without prejudice to hydrolytic condensation, just without special restriction, But it can for example enumerate ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene-glycol monoalky lether, propanediol monoalkyl Ether acetic acid ester, propionic ester etc..Wherein, preferably diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl, propylene glycol monomethyl ether, 3- methoxy methyl propionates.

Hydrolysis-condensation reaction can be carried out in the presence of a catalyst, and the catalyst is preferably acid catalyst (such as hydrochloric acid, sulphur Acid, nitric acid, formic acid, oxalic acid, maleic acid, maleic anhydride, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acid ion are exchanged Resin, various lewis acids), the base catalyst (nitrogen-containing compound such as ammonia, primary amine class, secondary amine class, tertiary amines, pyridine；Alkalescence Ion exchange resin；The hydroxide such as sodium hydroxide；The carbonate such as potassium carbonate；The carboxylates such as sodium acetate；Various lewis bases), Or alkoxide (such as zirconium alkoxide, alkoxytitanium, aluminum alkoxide).For example, triethylamine can be used as tertiary amine, alkoxy is used as Tetraisopropoxide aluminium can be used in aluminium.Wherein, the preferably binary acid such as oxalic acid, maleic acid, maleic anhydride or its acid anhydride.It is used as catalyst Usage amount, from promote hydrolysis-condensation reaction from the viewpoint of, relative to the silane compound, basis represented by above-mentioned formula (2) 1 mole of the total for the silane compound represented by above-mentioned formula (4) for needing and using, preferably less than 0.2 mole, more preferably 0.00001~0.1 mole.

Reaction temperature and reaction time in hydrolytic condensation can be properly selected according to the species of silane compound, but example Following conditions can such as be used.Reaction temperature is preferably 40~200 DEG C, more preferably 50~150 DEG C.Reaction time is preferably 30 minutes~24 hours, more preferably 1~12 hour., can be with most effective by being set to such reaction temperature and reaction time / condensation reaction is hydrolyzed to rate.In this hydrolyzing/condensing, hydrolysable silanes can be disposably added in reaction system Compound, water and catalyst and reacted with a step, or also can be by the way that hydrolysable silanes compound, water and catalyst be divided into It is added in reaction system and is hydrolyzed with multistep and condensation reaction for several times.It should illustrate, after hydrolysis-condensation reaction, root Dehydrating agent is added according to needs, the alcohol of water and generation can be removed by being evaporated to outside reaction system.Dehydrating agent leads to Often it can adsorb or include excessive water and water separation capability can be wholly absent, or be removed by evaporation.

(B) composition in the present invention, preferably weight average molecular weight (Mw) are 500~10000, more preferably 700~5000. In addition, the ratio (Mw/Mn) of the weight average molecular weight (Mw) of (B) composition and number-average molecular weight (Mn) is preferably 1.0~5.0, more preferably For 1.0~3.0.By such mode, curability, crack resistance can be further improved.It should illustrate, it is described herein Mw, Mn are respectively with gel permeation chromatography (hereinafter referred to as GPC) (dissolution solvent：Tetrahydrofuran) determine polystyrene change Weight average molecular weight, the number-average molecular weight of calculation.

In the present invention, (B) composition can be used alone or in combination of two kinds or more.

From the viewpoint of curability, crack resistance is improved, content the consolidating in infrared ray shielding composition of (B) composition It is preferably 10~98 mass %, more preferably more preferably 10~95 mass %, 15~95 mass % in body composition. This, solid constituent is the composition beyond aftermentioned organic solvent.

- (C) sensitising agents-

The infrared ray shielding composition of the present invention can contain (C) sensitising agent.Here, " sensitising agent " is in this specification Finger makes what the dissolving to solvent was sexually revised by light irradiation by having for the cured film obtained by infrared ray shielding composition The compound of property.As such compound, such as can enumerate Photoepolymerizationinitiater initiater, photoacid generator.(C) composition can be independent Or combine two or more to use.

As Photoepolymerizationinitiater initiater, as long as free radical can be produced by light, then without special restriction, but it can such as lift Go out thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, O- acyl groups oxime compound, Benzoin based compound, benzophenone based compound, α-diketone based compound, multinuclear quinone based compound, two Azos, Acid imide sulfonate based compound etc..Photoepolymerizationinitiater initiater can be used alone or in combination of two kinds or more.

Wherein, as Photoepolymerizationinitiater initiater, bisglyoxaline based compound, thioxanthones based compound, acetophenone system are preferably selected from It is at least one kind of in compound, triazine based compound, O- acyl group oxime compounds.It should illustrate, use bisglyoxaline based compound In the case of, also can and with hydrogen donors such as 2-mercaptobenzothiazoles.Herein described " hydrogen donor " refer to can to by expose Light and from bisglyoxaline based compound produce free radical provide hydrogen atom compound.In addition, using bisglyoxaline based compound In the case of Photoepolymerizationinitiater initiater in addition, also can and with sensitizers such as EDMABs.

As photoacid generator, as long as producing the compound of acid by light, then without special restriction, but sulfonium can be enumerated Salt, benzothiazoleSalt (benzothiazolium salt), ammonium salt,Salt etc.Salt；N- hydroxy imide sulfonates Compound, oxime sulfonate, adjacent nitro benzyl sulfonate, quinone di-azido compound etc..Acid agent can make alone or in combination of two kinds or more With.Wherein, preferably sulfonium salt, benzothiazoleSalt, oxime sulfonate, quinone di-azido compound.It is used as sulfonium salt, benzothiazole The concrete example of salt, for example, can enumerate hexafluoroarsenate -4- acetoxyl group phenyl dimethyl sulfonium, hexafluoro-antimonic acid -4- hydroxyphenyl benzyls Ylmethyl sulfonium, hexafluoro-antimonic acid -4- acetoxyl group phenyl benzyl methyls sulfonium, hexafluoro-antimonic acid -4- hydroxyphenyl dibenzyl sulfonium, six Fluorine metaantimmonic acid -4- acetoxyl group phenyl dibenzyl sulfonium, hexafluoro-antimonic acid -3- benzyl benzothiazoles, 1- (4,7- dibutoxy -1- naphthalenes Base) thiophaneTrifluoro-methanyl sulfonate etc..As the concrete example of oxime sulfonate, for example, it can enumerate Japanese Unexamined Patent Publication 2014- Compound described in [0122] of No. 115438 publications~[0131] paragraph.

As the concrete example of quinone di-azido compound, for example, it can enumerate the of Japanese Unexamined Patent Publication 2008-156393 publications [0040]~[0048] compound described in paragraph, [0172]~[0186] of Japanese Unexamined Patent Publication 2014-174406 publications Compound described in paragraph.

(C) content of composition is preferably 0.03~10 mass % in the solid constituent of infrared ray shielding composition, more Preferably 0.1~8 mass %, more preferably 0.5~6 mass %.By such mode, curability, resistance to tortoise can be made Fragility is more good.

- (D) polymerizable compounds-

The infrared ray shielding composition of the present invention can contain (D) polymerizable compound.It is possible thereby to improve infrared ray The curability of shielding composition, and further improve crack resistance.Here, " polymerizable compound " refers to tool in this specification There is the compound of more than 2 polymerizable groups.As polymerizable group, for example, it can enumerate ethene unsaturated group, ring Oxygen ethyl, oxetanyl, N- alkoxy methyl amino etc..(D) composition individually or can mix two or more to use.Its In, as (D) composition, compound preferably with more than 2 (methyl) acryloyl group, with the N- alkoxies of more than 2 The compound of methylamino.

As the concrete example of the compound with more than 2 (methyl) acryloyl group, it can enumerate as aliphatic polyhydroxy Multifunctional (methyl) acrylate of the based compound with the reactant of (methyl) acrylic acid, the multifunctional (first through caprolactone modification Base) acrylate, be modified through alkylene oxide multifunctional (methyl) acrylate, as (methyl) acrylate with hydroxyl with Polyfunctional carbamate (methyl) acrylate of the reactant of polyfunctional isocyanate, it is used as (methyl) third with hydroxyl Multifunctional (methyl) acrylate with carboxyl of the reactant of olefin(e) acid ester and acid anhydrides etc..

As aliphatic polyhydroxy compound, can for example enumerate as ethylene glycol, propane diols, polyethylene glycol, polypropylene glycol 2 The aliphatic polyhydroxy compound of valency；Such as fat more than glycerine, trimethylolpropane, pentaerythrite, the trivalent of dipentaerythritol Race's polyol.

As (methyl) acrylate with hydroxyl, for example, it can enumerate (methyl) acrylic acid -2- hydroxyl ethyl esters, three hydroxyl first third Alkane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine Dimethylacrylate etc..

As polyfunctional isocyanate, for example, it can enumerate toluene di-isocyanate(TDI), six methylene diisocyanate, diphenyl sub- Methyl diisocyanate, IPDI etc..As acid anhydrides, for example, it can enumerate such as succinic anhydride, maleic anhydride, penta Dicarboxylic anhydride, itaconic anhydride, anhydride phthalic acid, the dibasic acid anhydride of hexahydro anhydride phthalic acid；Such as benzenetetrahydride, biphenyl tetracarboxylic dianhydride, hexichol The quaternary acid dianhydride of ketone tetracarboxylic dianhydride.

In addition, as multifunctional (methyl) acrylate through caprolactone modification, such as Japanese Unexamined Patent Publication 11- can be enumerated Compound described in [0015] of No. 44955 publications~[0018] paragraph.

As multifunctional (methyl) acrylate being modified through alkylene oxide, it can enumerate through selected from oxirane and expoxy propane In at least one kind of bisphenol-A two (methyl) acrylate being modified, through at least 1 in oxirane and expoxy propane Cyamelide three (methyl) acrylate for kind being modified, through in oxirane and expoxy propane it is at least one kind of enter Modified trimethylol propane three (methyl) acrylate of row, changed through at least one kind of in oxirane and expoxy propane Pentaerythrite three (methyl) acrylate of property, through at least one kind of season being modified in oxirane and expoxy propane Penta tetrol four (methyl) acrylate, through at least one kind of two seasons penta 4 being modified in oxirane and expoxy propane Alcohol five (methyl) acrylate, through at least one kind of dipentaerythritol six being modified in oxirane and expoxy propane (methyl) acrylate etc..

In addition, as the compound with the N- alkoxy methyl amino of more than 2, such as can enumerate with melamine Structure, benzoguanamine structure, compound of urea structure etc..It should illustrate, melamine structure, benzoguanamine structure refer to have The triazine ring of more than 1 or the triazine ring that replaces through phenyl, as the chemical constitution of basic framework, are also to include melamine, benzene And the concept of guanamines or their condensation product.As the concrete example of the compound with the N- alkoxy methyl amino of more than 2, N, N, N can be enumerated ', N ', N ", N "-six (alkoxy methyl) melamine, N, N, N ', N '-four (alkoxy methyl) benzocarbamidine Amine, N, N, N ', N '-four (alkoxy methyl) glycoluril etc..

In these polymerizable compound, preferably as aliphatic polyhydroxy compound more than trivalent and (methyl) third It is multifunctional (methyl) acrylate of the reactant of olefin(e) acid, multifunctional (methyl) acrylate through caprolactone modification, multifunctional Carbamate (methyl) acrylate, multifunctional (methyl) acrylate, N, N, N with carboxyl ', N ', N ", (alkane of N "-six Epoxide methyl) melamine, N, N, N ', N '-four (alkoxy methyl) benzoguanamine.Aliphatic polyhydroxy more than as trivalent In multifunctional (methyl) acrylate of the reactant of based compound and (methyl) acrylic acid, the preferably propylene of trimethylol propane three Acid esters, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate；With carboxyl Multifunctional (methyl) acrylate in, preferably as pentaerythritol triacrylate and the chemical combination of the reactant of succinic anhydride Thing, the compound as Dipentaerythritol Pentaacrylate and the reactant of succinic anhydride.

(D) content of composition is preferably 0.1~90 mass % in the solid constituent of infrared ray shielding composition, more excellent Elect 1~80 mass %, more preferably 2~70 mass % as.By such mode, curability, crack resistance can be made It is more good.

- (E) resin glues-

The infrared ray shielding composition of the present invention can be (poly- not including above-mentioned (B) siloxanes containing (E) resin glue Compound).(E) composition is preferably soluble in alkali, for example, can enumerate the resin with acidic-group.As acidic-group, for example, it can lift Go out carboxyl, phenolic hydroxyl group, sulfo group etc..For the resin with acidic-group, as long as there is more than 1 in 1 molecule The polymer of acidic-group, then without special restriction, but as preferred mode, for example, be preferably the polymer with carboxyl (hereinafter also referred to " carboxylic polymer "), can for example enumerate with the carboxyl of more than 1 ethylene unsaturated monomer (with It is lower also referred to as " unsaturated monomer (e1) ") ethylene unsaturated monomer that can carry out copolymerization with other is (hereinafter also referred to " unsaturated Monomer (e2) ") copolymer.(E) composition can be used alone or in combination of two kinds or more.

As unsaturated monomer (e1), for example, it can enumerate (methyl) acrylic acid, maleic acid, maleic anhydride, mono succinate [2- (methyl) acryloyl-oxy ethyl ester], ω-carboxy-polycaprolactone list (methyl) acrylate, to vinyl benzoic acid etc..

Unsaturated monomer (e1) can be used alone or in combination of two kinds or more.

In addition, as unsaturated monomer (e2), such as can enumerate：

Such as N- phenylmaleimides, the N- substitution maleimides of N- cyclohexylmaleimides； As styrene, α-methylstyrene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, to vinylbenzyl glycidyl The aromatic ethylene compound of ether, acenaphthylene；

Such as (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) Acrylic acid -2- hydroxyl ethyl esters, (methyl) allyl acrylate, (methyl) benzyl acrylate, polyethylene glycol (degree of polymerization 2~10) methyl Ether (methyl) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (methyl) acrylate, polyethylene glycol (degree of polymerization 2~ 10) single (methyl) acrylate of single (methyl) acrylate, polypropylene glycol (degree of polymerization 2~10), (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decyl- 8- base esters, the ring penta of (methyl) acrylic acid two Alkene ester (dicyclopentanyl (meth) acrylate), glycerine list (methyl) acrylate, (methyl) acrylic acid -4- hydroxyls Phenyl ester, ethylene-oxide-modified (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) third to cumenyl phenol Olefin(e) acid -3,4- expoxycyclohexyls methyl esters, 3- [(methyl) acryloyloxymethyl] oxetanes, 3- [(methyl) acryloyls Epoxide methyl] -3- Ethyloxetanes (methyl) acrylate；

Such as cyclohexyl vinyl ether, isobornyl vinyl ethers, three ring [5.2.1.0^2,6] decyl- 8- bases vinyl ethers, five rings The vinyl ethers of pentadecyl vinyl ethers, 3- (ethene yloxymethyl) -3- Ethyloxetanes；Such as polystyrene, poly- (first Base) methyl acrylate, poly- (methyl) n-butyl acrylate, the end in polymer molecular chain of polysiloxanes have single (methyl) Polymeric monomer of acryloyl group etc..

Unsaturated monomer (e2) can be used alone or in combination of two kinds or more.

In the copolymer of unsaturated monomer (e1) and unsaturated monomer (e2), the unsaturated monomer (e1) in the copolymer Copolymerization ratios, preferably 5~50 mass %, more preferably 10~40 mass %.It is unsaturated single by being made with such scope Body (e1) copolymerization, can be made the excellent infrared ray shielding composition of curability, crack resistance.

As unsaturated monomer (e1) and the concrete example of the copolymer of unsaturated monomer (e2), for example, it can enumerate Japanese Unexamined Patent Publication Flat 7-140654 publications, Japanese Unexamined Patent Publication 8-259876 publications, Japanese Unexamined Patent Publication 10-31308 publications, Japanese Unexamined Patent Publication 10-300922 publications, Japanese Unexamined Patent Publication 11-174224 publications, Japanese Unexamined Patent Publication 11-258415 publications, Japanese Unexamined Patent Publication Copolymer disclosed in 2000-56118 publications, Japanese Unexamined Patent Publication 2004-101728 publications etc..

In addition, can also be used in the present invention such as such as Japanese Unexamined Patent Publication 5-19467 publications, Japanese Unexamined Patent Publication 6- No. 230212 publications, Japanese Unexamined Patent Publication 7-207211 publications, Japanese Unexamined Patent Publication 9-325494 publications, Japanese Unexamined Patent Publication 11- Have (methyl) acryloyl group etc. poly- in side chain disclosed in No. 140144 publications, Japanese Unexamined Patent Publication 2008-181095 publications etc. The carboxylic polymer of conjunction property unsaturated bond.

The weight average molecular weight (Mw) of (E) composition in the present invention is usually 1000~100000, preferably 3000~ 50000.In addition, the ratio (Mw/Mn) of the weight average molecular weight (Mw) of (E) composition and number-average molecular weight (Mn), preferably 1.0~5.0, More preferably 1.0~3.0.By such mode, curability, crack resistance can be further improved.It should illustrate, herein Described Mw, Mn is respectively with GPC (dissolution solvents：Tetrahydrofuran) be measured polystyrene conversion weight average molecular weight, Number-average molecular weight.

Known method can be used to manufacture for (E) composition in the present invention, but such as Japanese Unexamined Patent Publication 2003- can also be used Method disclosed in No. 222717 publications, Japanese Unexamined Patent Publication 2006-259680 publications, International Publication No. 2007/029871 etc. To control its structure or Mw, Mw/Mn.

(E) content of composition is preferably 1~40 mass % in the solid constituent of infrared ray shielding composition, more preferably For 2~30 mass %, more preferably 3~25 mass %.In addition, relative to the mass parts of (B) siloxane polymer 100 (E) content of composition, preferably 10~1000 mass parts, more preferably 20~500 mass parts, more preferably 30~200 Mass parts.By such mode, alkali-soluble can be made more good, the excellent cured film of crack resistance can be formed.

- (F) organic solvents-

The infrared ray shielding composition of the present invention contain (A) composition and (B) composition and arbitrarily add other into Point, but be generally mated organic solvent and be prepared into liquid composition.

As (F) composition, as long as (A) composition and (B) composition, the others composition that infrared ray shielding composition will be constituted Disperse or dissolve and do not reacted with these compositions, with appropriate volatility, it is possible to properly select and use.(F) composition can Use alone or in combination of two kinds or more.

As (F) organic solvent, for example, it can enumerate：

Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-propyl ether, ethylene glycol list n-butyl ether, diethyl Glycol monomethyl ether, TC, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propane diols list n-propyl ether, the third two Alcohol list n-butyl ether, DPGME, dihydroxypropane single-ethyl ether, DPG list n-propyl ether, DPG list (poly-) alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ethylether；

The lactic acid alkyl esters such as methyl lactate, ethyl lactate；

Methanol, ethanol, propyl alcohol, butanol, isopropanol, isobutanol, the tert-butyl alcohol, octanol, 2-Ethylhexyl Alcohol, cyclohexanol etc. (ring) Alkylol；

The keto-alcohols such as DAA；

Ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethyl Glycol list monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, DPGME (poly-) the alkylene glycol monoalkyl ether acetic acid such as acetic acid esters, acetic acid -3- methoxybutyls, acetic acid -3- methyl -3- methoxybutyls Ester；

The glycol such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran Ether；

The ketone such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-HEPTANONE, 3- heptanone；

The diacetate esters such as propylene-glycol diacetate, 1,3 butylene glycol diacetate esters, 1,6-HD diacetate esters；

3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, The alkoxyl carboxylates such as ethoxy ethyl acetate, propionic acid -3- methyl -3- methoxybutyls；

Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, acetic acid Isopentyl ester, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyric acid N-butyl, methyl pyruvate, pyruvic acid The fatty acid alkyl esters such as ethyl ester, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester；

The aromatic hydrocarbons such as toluene, dimethylbenzene；

The halogenated hydrocarbons such as carbon tetrachloride, trichloro ethylene, chloroform, 1,1,1- trichloroethanes, dichloromethane, monochlorobenzene；

The acid amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE or lactams etc..

In these organic solvent, consider from viewpoints such as dissolubility, dispersiveness, coatings, preferably (poly-) alkylidene Glycol monoalkyl ether, lactic acid alkyl ester, (poly-) alkylene glycol monoalkyl ethers acetic acid esters, glycol ethers, ketone, diacetate esters, alcoxyl Yl carboxylic acid ester, fatty acid alkyl esters.

(F) content of composition does not have beyond the organic solvent in special restriction, but infrared ray shielding composition Total concentration of each composition preferably turns into 5~50 mass % amount, the more preferably amount as 10~30 mass %.By such Mode, so as to which the infrared ray shielding composition that dispersiveness, stability, coating are good is made.

- additive-

The infrared ray shielding composition of the present invention can contain various additives as needed.

As additive, the filler such as can enumerate silica, aluminum oxide, acrylic acid series particulate；It is polyvinyl alcohol, poly- The high-molecular compounds such as (fluoroalkyl base ester) class；Nonionic surfactants, fluorine system surfactant, silicone-based surface The surfactants such as activating agent；Vinyltrimethoxy silane, VTES, (the 2- methoxyl group second of vinyl three Epoxide) silane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, N- (2- amino-ethyls) -3- aminopropyls Trimethoxy silane, APTES, 3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxies Hydroxypropyl methyl dimethoxysilane, 2- (3,4- expoxycyclohexyls) ethyl trimethoxy silane, 3- chloropropyl dimethoxies Base silane, 3- r-chloropropyl trimethoxyl silanes, 3- methacryloxypropyl trimethoxy silanes, 3- mercaptopropyi trimethoxies The closely sealed accelerator such as base silane；2,2- sulphur double (4- methyl-6-tert-butylphenols), 2,6 di t butyl phenol, pentaerythrites four Double [2- [the 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls)-the third of [3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester], 3,9- Acyloxy] -1,1- dimethyl ethyls] -2,4,8,10- four oxaspiro [55] hendecane, the double [3- (uncles of 3,5- bis- of sulphur divinyl Butyl -4- hydroxyphenyls) propionic ester] etc. antioxidant；2- (the 3- tert-butyl group -5- methyl -2- hydroxyphenyls) -5- chlorobenzotriazoles, alkane The ultra-violet absorbers such as epoxide benzophenone；The aggregation inhibitors such as Sodium Polyacrylate；Malonic acid, adipic acid, itaconic acid, lemon health Acid, fumaric acid, mesaconic acid, 2- ethylaminoethanols, 3- amino -1- propyl alcohol, 5- amino -1- amylalcohols, 3- amido-1,2-propanediols, 2- The residue improvers such as amino -1,3- propane diols, 4- amino -1,2- butanediols；Mono succinate [2- (methyl) acryloyl-oxies ethyl ester], The developability improvers such as phthalandione list [2- (methyl) acryloyl-oxies ethyl ester], ω-carboxy-polycaprolactone list (methyl) acrylate；1- (4,7- dibutoxy -1- naphthyls) thiophaneDouble (the 2,4- diformazans of the thermal acid generators such as trifluoro-methanyl sulfonate, 2,2 '-azo Base valeronitrile) etc. hot radical producing agent heat sensitizer.

The content of these additives can be properly selected in the range of the purpose of the present invention is not damaged.

The infrared ray shielding composition of the present invention can be prepared by appropriate method, for example can be by having at (F) (A) composition and (B) composition and the other compositions arbitrarily added are mixed together in machine solvent and prepared.

Cured film and its forming method

The cured film of the present invention is due to being formed using the infrared ray shielding composition of the present invention, therefore in infrared ray Light-proofness (infrared ray shielding) in region (also comprising the near infrared range near wavelength 700nm) is high, and crack resistance Also it is excellent.Therefore, cured film of the invention can function properly as infrared ray shielding cured film, and such as infrared ray cut is filtered Device.

In addition, the cured film of the present invention preferably has following characteristic：When thickness is 0.5 μm, in 500~600nm of wavelength Wave band in the minimum transmittance of light be more than 90%, and the transmissivity of light wavelength 850nm at is less than 40%.Pass through Such mode, in the transmitted spectrum that spectrophotometer is determined, in the low wavelength side of visibility region, it is seen that light also can be abundant Ground is transmitted, and can fully cover the light of infrared spectral range, therefore, it is possible to the transmission for the light that visibility region is realized with high level With the masking of the light of infrared spectral range.From the viewpoint, the minimum of the light in 500~600nm of wavelength wave band is saturating The rate of penetrating is preferably more than 92%, and more preferably more than 95%, in addition, the transmissivity of the light at wavelength 850nm is preferably 35% Hereinafter, more preferably less than 30%.Here, " the minimum transmission of the light in 500~600nm of wavelength wave band in this specification Rate " refers in the transmitted spectrum that spectrophotometer is determined, the minimum value of the transmissivity of the light in 500~600nm of wavelength. In addition, " transmissivity of the light at wavelength 850nm is by less than 40% " refers in the transmitted spectrum that spectrophotometer is determined, The transmissivity of light at wavelength 850nm shows less than 40% value.

The cured film of the present invention can use appropriate method to be formed, for example, can use the infrared ray shielding combination of the present invention Thing is simultaneously formed by the process comprising following process (1) and (2).

(1) the infrared ray shielding composition of the present invention is coated on substrate, the process to form film is dried,

(2) process of above-mentioned curing of coating is made.

- process (1)-

Process (1) for be coated with substrate the present invention infrared ray shielding composition and be dried to form film Process.For substrate, not special restriction can enumerate glass, quartz, silicone, resin etc., can properly select. As the material of resin, for example, it can enumerate makrolon, polyester, aromatic polyamide, polyamidoimide, polyimides, ring Olefin polymer.It should illustrate, substrate can also in advance implement to handle using the medicine of silane coupler etc. according to required, etc. The appropriate pretreatments such as gas ions processing, ion plating, sputtering, gas-phase reaction method, vacuum evaporation.It should illustrate, be sent out by this In the case that bright infrared ray shielding composition is applied to solid camera head described later, visible ray pass filter can be also coated on The smooth surface of the photo detectors such as device (colour filter), photodiode.By the way that the infrared ray shielding composition of the present invention is coated with It can efficiently cover and be incident upon in the smooth surface of the photo detectors such as visible ray bandpass filter (colour filter), photodiode The infrared ray of photodiode, considers that it is preferred from the viewpoint.

For the coating method of infrared ray shielding composition, not special restriction can be used and for example sprayed The appropriate methods such as method, rolling method, method of spin coating (spin-coating method), slit mould rubbing method, rod coating method.Wherein, it is especially excellent Select spin-coating method.

When being dried, it can be heated as needed.Heat and can be used known to baking oven, heating plate etc. Heater meanses, also can be combined and are dried under reduced pressure with heat drying to carry out.Heating condition also can be with each composition species, match ratio Example is waited and different, but for example can be for 30 seconds~15 minutes or so at 60~250 DEG C of temperature.

The thickness of dried film is usually 0.1~30 μm, preferably 0.2~10 μm, more preferably 0.3~5 μm.

- process (2)-

Process (2) is to make the process of the curing of coating of formation in process (1).There is this to improve the machinery of cured film strong Degree, crack resistance.

Curing process is not particularly limited, and can be properly selected according to purpose, but can for example be enumerated at exposure Reason, heating etc..Here, " exposure " is not only to include the light of various wavelength in this specification, also comprising electron beam, X-ray The concept irradiated Deng radioactive ray.

For the method for exposure-processed, part or all that can for example enumerate the film coated surface that will be formed is exposed The method of light.

Exposure carried out preferably by the irradiation of radioactive ray, as radioactive ray, can enumerate electron beam, KrF, ArF, g line, Ultraviolet, the visible rays such as h lines, i lines, wherein preferably KrF, g line, h lines, i lines.

As Exposure mode, step printing (stepper exposure), contraposition exposure (aligner can be enumerated Exposure) etc..

Light exposure is preferably 5~3000mJ/cm², more preferably 10~2000mJ/cm², more preferably 50~ 1000mJ/cm²。

As exposure device, it is not particularly limited, known device can be properly selected, but can for example enumerates superelevation The UV exposure machines such as pressure mercury lamp.

In addition, as heating, part or all of side heated for the film coated surface that will be formed can be enumerated Method.

Heating-up temperature is preferably 120~250 DEG C, more preferably 160~230 DEG C.

Heat time is preferably 3 minutes~180 minutes, more preferably 5 minutes~120 minutes.

Heat up for device, be not particularly limited, known device can be properly selected, but can for example enumerate dry Dry baking oven, heating plate, IR heaters etc..

The thickness of the cured film formed like this is preferably 0.1~10 μm, more preferably 0.3~5 μm, more preferably 0.5~3 μm.

Furthermore, also can be as needed and including the part of cured film that will be obtained in process (2) or in process (1) The process (hereinafter also referred to " process (3) ") that a part for obtained film is removed., can be aftermentioned by process (3) The 1st embodiment of the invention in, corresponding to infrared light detection pixel part set opening portion.

Specifically, there are etching method, alkaline development method, solvent development method etc..

This photoresist layer is removed into pattern-like by etching method by forming photoresist layer in the cured film that is obtained in process (2) After form corrosion-resisting pattern, this corrosion-resisting pattern is etched as etching mask and with dry-etching, will be remaining anti-after etching Corrosion figure case is removed, so as to remove a part for the cured film obtained in process (2).On more specifically method, for example Japanese Unexamined Patent Publication 2008-241744 publications are referred to, its content is merged in present specification.

Alkaline development method after photomask is exposed, is shown by the film to being obtained in process (1) using alkalescence Shadow liquid is developed, and the unexposed portion of film is dissolved and removed, so as to remove the one of the film obtained in process (1) Part.Bakeed after can also being carried out after alkaline development.

As alkaline-based developer, for example, it is preferable to be sodium carbonate, sodium acid carbonate, sodium hydroxide, potassium hydroxide, hydroxide four First ammonium, choline, 1,8- diazabicyclos-[5.4.0] -7- hendecenes, 1,5- diazabicyclos-[4.3.0] -5- nonenes etc. are water-soluble Liquid.

Water-miscible organic solvent or surfactant such as methanol, ethanol can also be added in right amount in alkaline-based developer Deng.It should illustrate, generally be washed after alkaline development.

As development treatment method, spray development method, spray development method can be applicable, (dip) development method is impregnated, soaks to put and (cover Liquid) development method etc..Development conditions preferably at normal temperatures 5~300 seconds.

By the way that by process as above, the cured film of the present invention can be formed.

Solid camera head

The solid camera head of the present invention possesses the cured film of the present invention, and solid camera head of the invention can be using suitable When construction.For example, for an embodiment, by using the infrared ray shielding composition of the present invention in CMOS substrate It is special so as to the accuracy of detection that makes visible ray Deng by operation similar to the above forming cured film on semiconductor substrate Excellent solid camera head.

Below for the solid camera head of one embodiment of the present invention, it is described in detail with reference to the accompanying drawings.Below Shown embodiment is an example of embodiments of the present invention, and the present invention is not limited to the embodiment party illustrated herein Formula.

It should illustrate, in the accompanying drawing of present embodiment reference, with a part or the part emblem with said function Remember identical symbol or similar symbol (symbol that a, b etc. are marked only after numeral), its explanation repeated is omitted sometimes. In addition, illustrating for convenience, the dimension scale of accompanying drawing not necessarily can be consistent with actual ratio, sometimes by a part for composition from Accompanying drawing is omitted.

In addition, in this manual, " on " refer to be with the principal plane of supporting substrate (face of configuration solid-state imager) The relative position of benchmark, away from supporting substrate principal plane direction for " on ".In illustrations, towards paper and top For " on ".In addition, " on " comprising the situation (the namely situation of " on ") connected with the upper surface of object and positioned at object The situation (the namely situation of " over ") of top.Conversely, " under " refer to relative position on the basis of the principal plane of supporting substrate Put, close to supporting substrate principal plane direction for " under ".In illustrations, towards paper and lower section for " under ".

(the 1st embodiment)

Fig. 1 is the application examples of the solid camera head of one embodiment of the present invention.Specifically, represent this embodiment party The solid camera head of formula is applied to camera device (such as range image camera of TOF (Time Of Flight) mode (distance image camera)) example.It should illustrate, the camera device illustrated herein only schematic diagram, and Without prejudice to adds or deleted other key elements.

In Fig. 1, picture pick-up device (camera) 10 possesses light source 11, solid camera head (imaging sensor) 12, signal Processing unit 13, master control part 14 are used as basic inscape.Master control part 14 and light source 11, solid camera head 12 and signal Processing unit 13 is connected, for controlling respective operation.Solid camera head 12 is also further connected with signal processing part 13, will be solid The electric signal generated in body camera device 12 is sent to signal processing part 13.

As light source 11, the known LED (Light Emmiting Diode) of output infrared light can be used.From light source The Infrared irradiation of 11 outputs can reflect to after imaging object 15, and its reflected light can be injected into solid camera head 12.Now, Between the infrared light exported from light source 11 and the infrared light returned from shooting object 15, it can produce according to shooting object 15 Three-dimensional shape phase difference.

As solid camera head 12, cmos image sensor, ccd image sensor can be used.It is used as cmos image Sensor, it is possible to use any of surface irradiation type and rear surface irradiation type, but in the present embodiment, use high sensitivity Rear surface irradiation type cmos image sensor.

The extraneous visible ray reflected by shooting object 15 can be injected into solid with the infrared light exported from light source 11 and take the photograph As the solid-state imager (also referred to as photo-electric conversion element or sensing element) in device 12, so as to be converted into according to light quantity Fixed electric signal.Converted electric signal is digitized by the A/D converter circuit being arranged in solid camera head 12, is made Signal processing part 13 is output into data signal.On the specific configuration of solid camera head 12, it will be explained below.

Signal processing part 13 receives the data signal exported from solid camera head 12 and carries out signal transacting, and formation is based on Image the image of object 15.Now, the data signal based on visible ray is used as color, shape representation by object 15 is imaged Information, the data signal based on infrared light as recognize shooting object 15 distance information and use.Pass through These data signals, can three-dimensionally grasp shooting object 15.

Master control part 14 is the calculation processing unit centered on CPU, in control light source 11, solid camera head 12 and signal While processing unit 13, other processing units (not shown) can be also controlled based on the information obtained from signal processing part 13.

Fig. 2 is the top view for illustrating the summary of solid camera head 12.Encapsulation 16 is configured with pixel portion 17 and terminal Portion 18.A/D converter circuit is may also set up between pixel portion 17 and portion of terminal 18.Enlarging section 19 is represented one of pixel portion 17 Divide the apperance of amplification.As shown in enlarging section 19, in pixel portion 17, multiple pixels 20 are configured to rectangular.

Fig. 2 only represents to construct merely as pixel portion 17 with portion of terminal 18, but the solid-state image pickup dress of present embodiment Put and be not limited to this.For example, for the solid camera head 12 shown in Fig. 2, can also include shown in Fig. 1 as signal processing part 13 function.Furthermore, the calculation disposal ability equal with master control part 14 shown in Fig. 1 can be also included, and as with single-chip Possess the system IC circuits of camera function and calculation function.

Fig. 3 is the sectional view for cutting off the pixel 20 shown in Fig. 2 with III-III '.In figure 3, one injected from exterior light Side rise, it is illustrated that the 1st optical layer 21, the 1st gap 22, microlens array 23, the 2nd gap 24, the 2nd optical layer 25, the 3rd gap 26, Visible ray bandpass filter (colour filter) 27a~27c, infrared light bandpass filter 27d, insulator 28, photodiode 29a~29d, And supporting substrate 30.1st gap 22, the 2nd gap 24 and the 3rd gap 26 can be ensured that as with air, non-active gas institute The space of filling, can also be ensured that as the insulator constituted with organic insulating film, inorganic insulating membrane.In addition, can not have yet 1st gap 22, the 2nd gap 24 or the 3rd gap 26, for example, the 2nd optical layer 25 can be with visible ray bandpass filter 27a~27c phases Connect, or microlens array 23 can connect with the 2nd optical layer 25.

In this manual, the photodiode that will be configured by visible ray bandpass filter 27a~27c and corresponding to them The pixel that 29a~29c is constituted is referred to as " visible detection pixel ", will be by infrared light bandpass filter 27d and photodiode 29d The pixel of composition is referred to as " infrared light detection pixel ".

Here, optical layer of the 1st optical layer 21 for transmission visible ray and at least a portion infrared light, such as transmission peak wavelength The infrared light of 400~700nm visible ray and 750~2500nm of wavelength (being 750~950nm on typical case) of at least some. Certainly, the wavelength region of transmission is not limited by scope described herein, as long as energy TEM investigation is in R (red), G (green) and B The visible ray of the light of (indigo plant) with can be with the infrared light of the wavelength region of infrared light detection pixel detection described later.Possesses picture So transmit the wave filter of the optical characteristics of 2 different wavelength regions, commonly referred to as 2 wavelength bandpass filters.

It should illustrate, in the present embodiment, as the 1st optical layer 21, using (there is translucency with transparent resin Resin) base material of layer is provided with the optical layer of multilayer dielectric film, the transparent resin (resin with translucency) layer includes tool There is the compound of certain optical properties.As the compound with certain optical properties, for example, it can enumerate absorption a part of infrared The compound (hereinafter referred to as " compound (Z) ") of light.Specifically, as compound (Z), the infrared ray with the present invention can be enumerated (A) composition identical compound that shielding composition contains, wherein can preferably use selected from the sour cyanines based compound in side, phthalocyanine In based compound, naphthalene phthalocyanine based compound, crocic acid based compound, hexa-atomic porphyrin based compound and Hua Jing based compounds at least 1 kind of compound.

Like this, by the way that multilayer dielectric film is arranged at into the base material with transparent resin layer, and the transparent resin layer bag Containing the compound (Z) for absorbing a part of infrared light, so as to which 2 wavelength of transmission visible ray and at least a part of infrared light are made Bandpass filter.Now, base material can be individual layer, or multilayer.If individual layer, then transparent resin layer composition can be made Flexible substrate.In the case of multiple layers, it is laminated with and contains on transparency carrier such as can use in glass substrate, resin substrate There is the base material of the transparent resin layer of compound (Z) and curable resin or on the transparency carrier upper strata containing compound (Z) It is laminated with the base material of the resin beds such as the protective layer containing curable resin.

In microlens array 23, the position of each lenticule corresponds respectively to the position of each pixel, is gathered with each lenticule The incident light of collection is received by corresponding each pixel (specifically, by each photodiode) respectively.Microlens array 23 due to Resin material can be used to be formed, therefore can also be formed with single-chip.For example, insulator can be used as the 2nd gap 24, will It is coated on resin material processing thereon and forms microlens array 23.In addition, it is possible to use the base material (film) that resin is constituted As the 2nd gap 24, the resin material being coated on thereon is processed and formed after microlens array 23, to attach the shape of this base material Formula is incorporated in solid-state imager 12.

2nd optical layer 25 can use the infrared ray masking of the present invention to absorb the optical layer of at least a portion infrared light Property composition is manufactured well.Specifically, by containing in the range of 700~2000nm of wavelength have maximum absorption ripple Long infrared ray smoke agent for shielding, can play the function of the infrared cut of light wave filter as masking at least a portion infrared light.Should Explanation is given, the solid camera head of the 1st embodiment for the present invention, preferably the 1st optical layer 21 are with transparent tree The optical layer (2 wavelength bandpass filter) of multilayer dielectric film is set on the base material of fat (resin with translucency) layer, and this is saturating Ming tree fat (resin with translucency) layer contains the compound with certain optical properties, and the 2nd optical layer 25 is to use this hair The cured film that bright infrared ray shielding composition is formed.

In the 1st embodiment, the 2nd optical layer 25 (specifically, is being photoelectricity two corresponding to infrared light detection with pixel Pole pipe 29d) part there is opening portion.That is, in order that infrared light directly reaches photodiode 29d, so that in the pole of photoelectricity two Pipe 29d top sets opening portion, the construction of the injection as without prejudice to infrared light.In other words, in the 2nd optical layer 25 " part for corresponding to photodiode 29d " refers to photodiode 29d top, that is, refers to towards photodiode 29d Infrared light the part intersected with the 2nd optical layer 25 of light path.Opening portion can for example pass through above-mentioned etching method, alkaline development method To be formed.The infrared ray shielding composition of the present invention by etching, alkaline development method due to that can form opening portion, therefore spy The formation of the 2nd optical layer 25 that Shi Yu be in the 1st embodiment.

Like this, in the 1st embodiment, the 2nd optical layer 25 is to cover the part beyond infrared light detection pixel The mode of the top of (i.e., it is seen that light is detected with pixel) is configured.It is possible thereby to which strongly suppressing infrared light reaches visible ray inspection Survey pixel.It as a result, noise contribution can be reduced in visible detection pixel, can put forward the accuracy of detection of visible ray It is high.

In the lower section of the 2nd optical layer 25, configure it is above-mentioned containing visible detection with pixel and infrared light detection pixel Pixel groups.As described above, in the present embodiment, each photodiode 29a~29c and visible ray bandpass filter 27a~27c It is each corresponding and constitute visible detection pixel.In addition, photodiode 29d is corresponding with infrared light bandpass filter 27d And constitute infrared light detection pixel.In this manual, photodiode 29a~29c is referred to as " the 1st photo detector ", will Photodiode 29d is referred to as " the 2nd photo detector ".

It should illustrate, in fact, visible ray bandpass filter 27a~27c is by transmiting the filter of the visible ray of each different wave length Logical device is constituted, for example, visible ray bandpass filter can include the logical device 27a of filter of transmission green light, transmit the logical device 27b of filter of red light Device 27c is led in filter with transmitting blue light.Therefore, also the pixel corresponding to their other colors can be referred to as green light inspection respectively Survey is with pixel, red light detection with pixel, blue light detection pixel.

In addition, visible ray bandpass filter 27a~27c and infrared light bandpass filter 27d can be used containing in specific wavelength The known resin material of pigment (pigment or dyestuff) with absorption.For example, infrared light bandpass filter 27d can be used and is included in There is the wavelength region of visible ray the pigment absorbed and the solidification compound of curability composition to be formed.As long as containing 1 with On the wavelength region in visible ray have absorb pigment, but also can be combined multiple pigments.Specifically, for example can be with Infrared light bandpass filter is formed using the photo-sensitive composition described in Japanese Unexamined Patent Publication 2014-130332 publications.

Above-mentioned photodiode 29a~29d can use silicone substrate as supporting substrate 30, and in silicone substrate Surface is formed using known semiconductor technology.It is of course also possible to be used as branch support group using substrates such as glass, ceramics, resins Plate 30, and form photodiode 29a~29d using known film formation technology.

In the present embodiment, the green light for receiving 520~560nm of wavelength is used as using photodiode 29a Photo detector, using photodiode 29b as the photo detector of the red light for receiving 580~620nm of wavelength, uses light Electric diode 29c as the blue light for receiving 430~470nm of wavelength photo detector.Like this, in present embodiment In solid camera head 12, the visible ray injected from outside is detected using these photodiodes 29a~29c.

On the other hand, photodiode 29d play for receive 750~2500nm of wavelength (on typical case be wavelength 750~ The function of the photo detector of infrared light 950nm), by photodiode 29d, can detect the infrared light injected from outside.

Herein by the 1st optical layer 21 used in the solid camera head 12 of present embodiment, the 2nd optical layer 25 and red Outer smooth bandpass filter 27d optical characteristics is shown in Fig. 4~6.

Fig. 4 is the figure of the transmitted spectrum for the 1st optical layer 21 for representing the solid camera head 12 for present embodiment. In Fig. 4, transverse axis represents the wavelength of incident light, the transmission when longitudinal axis represents to be measured from the direction perpendicular to the 1st optical layer 21 Rate.As shown in figure 4, the 1st optical layer 21 used in present embodiment has 400~700nm of transmission peak wavelength visible ray and ripple The optical characteristics of long 750~950nm infrared light.Certainly, the optical characteristics represented in Fig. 4 is an example, is used as this implementation The 1st optical layer 21 used in mode, if the optical characteristics with transmission visible ray and at least a portion infrared light, even thoroughly 2 wavelength bandpass filters of other wavelength regions are penetrated, can also be used.

Fig. 5 is the 2nd optical layer (infrared ray cut off filter) for representing the solid camera head 12 for present embodiment The figure of 25 transmitted spectrum.In Figure 5, transverse axis represents the wavelength of incident light, and the longitudinal axis is represented from the side perpendicular to the 2nd optical layer 25 To transmissivity when being measured.It should illustrate, the 2nd optical layer (A) and the 2nd two kinds of optical layer (B), but two are shown in Fig. 5 The difference of the transmitted spectrum of person by containing (A) infrared ray smoke agent for shielding difference caused by.Specifically, the 2nd optical layer (A) contains There is the flower cyanines based compound for absorbing a length of 865nm of maximum wave of maximum as (A) composition, the 2nd optical layer (B) contains maximum suction Receive a length of 865nm of maximum wave flower cyanines based compound and the maximum flower cyanines based compound conduct for absorbing a length of 810nm of maximum wave (A) composition.

As shown in figure 5, the infrared ray cut off filter 25 used in present embodiment have by wavelength about 600~950nm, The function that preferably 700~900nm of wavelength incident light is blocked.Certainly, the optical characteristics represented in Fig. 5 is an example, is made For the 2nd optical layer 25 used in present embodiment, there is the red of maximum absorption in 700~2000nm of wavelength as long as using and containing The optical layer of outside line smoke agent for shielding.

Fig. 6 is the transmitted spectrum for the infrared light bandpass filter 27d for representing the solid camera head 12 for present embodiment Figure.In figure 6, transverse axis represents the wavelength of incident light, and the longitudinal axis represents to carry out from perpendicular to infrared light bandpass filter 27d direction Transmissivity during measure.As shown in fig. 6, the infrared light bandpass filter 27d used in present embodiment shows transmittance wavelength The characteristic of the light of wavelength side also long near 800nm.Certainly, workable infrared light bandpass filter 27d is not in present embodiment It is limited to the transmitted spectrum characteristic shown in Fig. 6, absorption edge can be in longer wavelength side or shorter wavelength side.

Solid camera head 12 in present embodiment, first, passes through the 1st light with optical characteristics as shown in Figure 4 Learn the filtering external of layer 21 light and 400~700nm of transmission peak wavelength visible ray with least a part of 750~2500nm's of wavelength Infrared light (specifically 750~950nm of wavelength infrared light).Then, the visible ray and infrared light of the 1st optical layer 21 are transmitted A part can be incident upon the 2nd optical layer 25.

Now, because the 2nd optical layer 25 above photodiode 29d is provided with opening portion, the 1st optical layer 21 is transmitted Visible ray and the part of infrared light can be emitted directly toward infrared light bandpass filter 27d.In infrared light bandpass filter 27d, such as Shown in Fig. 6, (blocking) wavelength about below 750nm visible ray is absorbed, 750~950nm of wavelength infrared light injects the pole of photoelectricity two Pipe 29d.Thus, do not influenceed by noise that visible ray is caused etc., grasp shooting object 15 well so as to precision Untill distance.

On the other hand, due in photodiode 29a~29c top (visible ray bandpass filter 27a~27c top) The 2nd optical layer 25 is provided with, a part for the visible ray and infrared light that transmit the 1st optical layer 21 injects the 2nd optical layer 25. In 2 optical layers 25, as shown in figure 5, absorb (blocking) wavelength about 800~900nm infrared light, each containing RGB is into light splitting Visible ray injects photodiode 29a~29c by visible ray bandpass filter 27a~27c.Thus, it is possible to which injection is greatly reduced The light quantity of photodiode 29a~29c infrared light, therefore will not be influenceed by noise caused by infrared light etc., so that Energy precision grasps colourity, the shape of shooting thing 15 well.

Like this, in solid camera head 12 in the present embodiment, with by suitably adjusting the 1st optical layer 21 With the optical characteristics of the 2nd optical layer 25 and suppress the feature of the final infrared light for injecting visible detection pixel.

In contrast, in the case that only the 1st optical layer 21 is set, because the infrared light for transmiting the 1st optical layer 21 can be direct Visible detection pixel is injected, thus there is the possibility of color reprodubility deterioration.

In addition, in the case of only setting the 2nd optical layer 25, it is impossible to fully block visible detection pixel, photoelectricity two The unwanted infrared light of pole pipe 29d institutes, so as to have color reprodubility, the possibility of infrared ray sensing penalty.For example, general For, red colour filter can inject infrared light due to the optical characteristics of the light with more than transmission peak wavelength 600nm Red light detection pixel.In addition, in general, the colour filter of green, the colour filter of blueness are due to slow with transmissivity Slow optical characteristics increased near wavelength 750nm, therefore infrared light is injected green light detection pixel, blue light inspection Survey pixel.

(the 2nd embodiment)

Then, the solid camera head of the 2nd embodiment of the present invention is illustrated.

Fig. 8 is the solid camera head along III-III ' the 2nd embodiments for cutting off the pixel 20 shown in Fig. 2 Summary sectional view.The solid camera head of 2nd embodiment has the solid camera head identical base with the 1st embodiment This composition, but in the following areas, it is different from the solid camera head of the 1st embodiment.That is, the solid-state image pickup of the 2nd embodiment The 1st optical layer 21, photodiode 29d and infrared light bandpass filter 27d are not present in device, and with regard to the quilt of the 2nd optical layer 25 It is arranged on for the point of the lower section of microlens array 23, with the solid camera head of the 1st embodiment and differing.2nd optics Layer 25 can absorb at least a portion infrared light in the same manner as the 2nd optical layer of the 1st embodiment, and to possess detection transmission the 2nd The solid camera head of 1st photo detector of the transmitted light of optical layer 25, the 2nd optical layer using the infrared ray of the present invention by being covered Property the cured film that is formed of composition constitute.

1st photo detector refers to be arranged at photodiode 29a~29c below visible ray bandpass filter 27a~c, the 2nd Optical layer is configured in the top of the photodiode.In addition, visible ray bandpass filter 27a~c can include transmission green light Device is led in the logical device of filter, the filter of the logical device of filter and transmitting blue light of transmission red light.Like this, because the solid of the 2nd embodiment is taken the photograph As the 2nd optical layer 25 is arranged at the top of visible detection pixel by device, therefore incident light can be greatly reduced in visible ray The light quantity of electric diode 29a~c infrared light.In addition, in the solid camera head of the 1st embodiment, relative to must be A part for 2nd optical layer 25 forms opening portion, need not be in the 2nd optical layer in the solid camera head of the 2nd embodiment 25 form opening portion, therefore also the manufacture with solid camera head becomes simple such advantage.

(the 3rd embodiment)

Then, the solid camera head of the 3rd embodiment of the present invention is illustrated.

Fig. 9 is the solid camera head along III-III ' the 3rd embodiments for cutting off the pixel 20 shown in Fig. 2 Summary sectional view.The solid camera head of 3rd embodiment has the solid camera head identical base with the 2nd embodiment This composition, but in the following areas, it is different from the solid camera head of the 2nd embodiment.That is, the solid-state image pickup of the 3rd embodiment Device, this point of the top of microlens array 23 is arranged in the 2nd optical layer 25, the solid-state image pickup with the 2nd embodiment Device is different.Like this, the solid camera head of the 3rd embodiment, is used due to the 2nd optical layer 25 is arranged at into visible detection The top of pixel, therefore the light quantity for the infrared light for injecting photodiode 29a~c can be greatly reduced in visible ray.

The solid camera head of the embodiment of 1st, the 2nd and the 3rd injects the red of the 1st photo detector due to that can be greatly reduced The light quantity of outer light, therefore will not be influenceed by noise caused by infrared light etc., grasp and take the photograph well so as to precision As the distance of thing.Therefore, its remote control, 3-dimensional shape measuring apparatus, vapour for being applied to the remote control or automatically-controlled door of television set etc. Range image sensor, biography used in motor vehicle equipment, the gesture input controllers such as the separation between vehicles detection sensor of car etc. The true or imaging sensor in duplicator, the color monitoring of liquid crystal display are used or simple color detection is sensed with used color The appropriate OPTICAL SENSORS such as device, infrared-ray detecting element.Moreover, being also applied for the colour recognition sensor such as camera.

Embodiment

Embodiment is enumerated below, further illustrates embodiments of the present invention, but the invention is not restricted to following embodiments.

Synthesis example 1

Maleic anhydride 10.00g is dissolved by heating in propylene glycol monomethyl ether (hereinafter also referred to " PGME ") 90.00g, make The PGME solution of standby 10% maleic anhydride.Then, the PGME solution 1.8g of 10% maleic anhydride is mixed with water 72.41g, Prepare acid catalyst solutions.

Then, in flask add 182.66g MTMS and 43.13g PGME, set cooling tube and Dropping funel equipped with previously prepared acid catalyst solutions.Next, above-mentioned flask is heated to after 50 DEG C with oil bath, delay Above-mentioned acid catalyst solutions are slowly added dropwise, are reacted 3 hours at 60 DEG C after completion of dropwise addition.After reaction terminates, reaction solution will be equipped with Flask cooling.

Next, reaction solution is moved into another flask, untill solid constituent amount is concentrated into 50% by evaporator after, Solid constituent amount is diluted to as 30% using PGME again.Next, carrying out being concentrated into after solid constituent amount 50% again, entered with PGME The operation of row dilution so that solid component concentration turns into 35 mass %, by removing the water and methanol of residual, so as to obtain solid The mass % of constituent concentration 35 siloxane polymer (B-1) solution.The Mw of siloxane polymer (B-1) be 2480, Mn be 1200, Mw/Mn is 2.1.

Synthesis example 2

Except be altered in synthesis example 1 mixing 10% maleic anhydride PGME solution 1.80g and water 69.21g and obtain Acid catalyst solutions, the MTMS 165.86g as silane compound, the phenyltrimethoxysila,e arrived Beyond 12.71g, 50.43g PGME as solvent, carried out in the same manner as synthesis example 1, obtain the matter of solid component concentration 35 Measure % siloxane polymer (B-2) solution.

Synthesis example 3

Except be altered in synthesis example 1 mixing 10% maleic anhydride PGME solution 1.80g and water 63.59g and obtain Acid catalyst solutions, the MTMS 136.35g as silane compound, the phenyltrimethoxysila,e arrived Beyond 35.03g, 63.23g PGME as solvent, carried out in the same manner as synthesis example 1, obtain the matter of solid component concentration 35 Measure % siloxane polymer (B-3) solution.

Synthesis example 4

Except be altered in synthesis example 1 mixing 10% maleic anhydride PGME solution 1.80g and water 58.81g and obtain Acid catalyst solutions, the MTMS 111.27g as silane compound, the phenyltrimethoxysila,e arrived Beyond 53.99g, 74.13g PGME as solvent, carried out in the same manner as synthesis example 1, obtain the matter of solid component concentration 35 Measure % siloxane polymer (B-4) solution.

Synthesis example 5

Except be altered in synthesis example 1 mixing 10% maleic anhydride PGME solution 1.80g and water 49.51g and obtain Acid catalyst solutions, the MTMS 62.45g as silane compound, the phenyltrimethoxysila,e arrived 90.91g, 95.32g as solvent PGME and by container turn into backflow in the way of change beyond reaction temperature, with synthesis Example 1 is similarly carried out, and obtains the mass % of solid component concentration 35 siloxane polymer (B-5) solution.

Synthesis example 6

Except be altered in synthesis example 1 mixing 10% maleic anhydride PGME solution 1.80g and water 43.95g and obtain Acid catalyst solutions, the MTMS 33.26g as silane compound, the phenyltrimethoxysila,e arrived Beyond 112.98g, 108.00g PGME as solvent, carried out in the same manner as synthesis example 1, obtain the matter of solid component concentration 35 Measure % siloxane polymer (B-6) solution.

Synthesis example 7

Except be altered in synthesis example 5 mixing 10% maleic anhydride PGME solution 1.80g and water 37.62g and obtain The acid catalyst solutions that arrive, as silane compound phenyltrimethoxysila,e 138.14g, 122.44g as solvent Beyond PGME, carried out in the same manner as synthesis example 5, obtain the mass % of solid component concentration 35 siloxane polymer (B-7) solution.

Synthesis example 8

Except be altered in synthesis example 1 mixing 10% maleic anhydride PGME solution 1.80g and water 40.37g and obtain The acid catalyst solutions that arrive, the MTMS 30.55g as silane compound, tolyl trimethoxy silane Beyond 111.11g, 116.17g PGME as solvent, carried out in the same manner as synthesis example 1, obtain the matter of solid component concentration 35 Measure % siloxane polymer (B-8) solution.

Synthesis example 9

Except be altered in synthesis example 1 mixing 10% maleic anhydride PGME solution 1.80g and water 43.95g and obtain Acid catalyst solutions, MTMS 27.72g, 3- methacryloxypropyl as silane compound arrived Trimethoxy silane (trade name Sila-Ace S710, CHISSO Co. Ltd. system) 10.11g, phenyltrimethoxysila,e Beyond 112.98g, 108.00g PGME as solvent, carried out in the same manner as synthesis example 1, obtain the matter of solid component concentration 35 Measure % siloxane polymer (B-9) solution.

For siloxane polymer (B-2)~(B-9) resulting in above-mentioned synthesis example, pass through GPC (dissolution solvents：Four Hydrogen furans) molecular weight that polystyrene converts is determined, it the results are shown in table 1.

[table 1]

In table 1, MTMS refers to MTMS, and S710 refers to 3- methacryloxypropyl trimethoxies Silane (trade name Sila-Ace S710, CHISSO Co. Ltd. system), PTMS refers to phenyltrimethoxysila,e, and TTMS refers to Tolyl trimethoxy silane.

The synthesis ＞ of ＜ (E) resin glue

Synthesis example 10

Load the mass parts of propylene glycol monomethyl ether 100 in possessing the flask of cooling tube and mixer and with nitrogen Displacement.It is heated to after 80 DEG C, the mass parts of propylene glycol monomethyl ether 100, methyl-prop was added dropwise with 1 hour at the same temperature The mass parts of olefin(e) acid 20, the mass parts of styrene 10, the mass parts of benzyl methacrylate 5, the mass of 2-hydroxyethyl methacry-late 15 Part, the mass parts of methacrylic acid -2- ethylhexyls 23, the mass parts of N- phenylmaleimides 12, mono succinate (2- propylene Acyloxy ethyl ester) 15 mass parts and 2, the mixed solution of double (2,4- methyl pentane nitrile) 6 mass parts of 2 '-azo keeps the temperature Carry out polymerization 2 hours.Afterwards, by the way that the temperature of reaction solution is warming up into 100 DEG C, then the polymerization of 1 hour is carried out, is bonded Agent resin solution (the mass % of solid component concentration 33).The Mw of resulting resin glue is that 12200, Mn is 6500, by this Resin glue is set to " resin glue (E-1) ".

The preparation ＞ of ＜ basilar memebranes (base film) formation composition

Preparation example 1

It will be carried out in flask after nitrogen displacement, loading is dissolved with the 2 of 0.6 mass parts, the propionic acid first of 2 '-azodiisobutyronitrile The mass parts of base -3- methoxyl groups ester solution 200.Then the Tert-butyl Methacrylates of 37.5 mass parts, 62.5 mass parts are loaded After GMA, it is stirred, is heated 6 hours at 70 DEG C.After cooling, the resin containing polymer is obtained molten Liquid.

Then, with the propionic acid of 31.9 mass parts of the resin solution of 33.3 mass parts (polymer containing 10 mass parts) After methyl -3- methoxies base ester, the dilution of the propylene glycol monomethyl ether of 3.4 mass parts, by the trihemellitic acid of 0.3 mass parts, 0.5 mass 3- glycidoxypropyltrime,hoxysilanes, the trade name " FC-4432 " of 0.005 mass parts (3M plants of formulas of Sumitomo of part Commercial firm's system) dissolving, prepare basilar memebrane formation composition.

The preparation ＞ of ＜ infrared ray shielding compositions

Embodiment 1

By the flower cyanines based compound NK-5060 (Hayashibara Co., Ltd. as (A) composition for adding 2.53 mass parts of mixing System, maximum absorption wavelength 865nm (film)), 100.00 mass parts as (B) composition siloxane polymer (B-2) solution (Gu The mass % of body constituent concentration 35), the acid agent 1- (4,7- dibutoxy -1- naphthyls) as (C) sensitising agent of 1.63 mass parts ThiophaneTrifluoro-methanyl sulfonate, fluorine system surfactant Ftergent FTX-218 (Co., Ltd. as additive Neos systems) 0.07 mass parts and the mass parts of N- tert-butoxycarbonyls dicyclohexyl amine 0.16 and 289.55 mass parts conduct (F) The cyclohexanone of organic solvent, so as to obtain the infrared ray shielding composition (S-1) that solid component concentration is 10 mass %.

The formation of ＜ cured films and evaluation ＞

On the glass substrate using automatic coating developing apparatus (Tokyo Electron Co. Ltd. system CLEAN TRACK, Trade name " MARK-Vz "), it is coated with spin-coating method after above-mentioned basilar memebrane formation composition, baking 2 minutes, shape is carried out at 250 DEG C Into 0.6 μm of basilar memebrane of thickness.

It is coated with spin-coating method on the basilar memebrane after infrared ray shielding composition (S-1), it is enterprising in 100 DEG C of heating plates Row prebake 2 minutes, forms the film of 0.5 μm of thickness.Afterwards, by being bakeed 5 minutes after being carried out with 200 DEG C of heating plate, from And make the glass substrate with cured film.

With the substrate obtained by observation by light microscope, situation about not being cracked completely is evaluated as " ◎ ", will have 1~3 The situation of individual cracking is evaluated as "○", and the situation for having 4~10 crackings is evaluated as into " △ ", the situation of more than 11 is evaluated as "×", shows the result in table 2.

Then, using Suga Test Instruments company systems haze meter and according to JIS K7136 come determine gained The mist degree of the substrate arrived, " ◎ " is evaluated as by the situation that mist degree is less than 0.3%, will be greater than being equal to 0.3% and the feelings less than 0.5% Condition is evaluated as "○", will be greater than being equal to 0.5% and the situation less than 1.0% is evaluated as " △ ", by more than 1.0% situation evaluation For "×", table 2 is shown the result in.It should illustrate, the measure of mist degree is entered under the contrast of the glass substrate with not forming cured film OK.

Embodiment 2~8

In addition in embodiment 1 into siloxane polymer being made to (B-3)~(B-9), enter similarly to Example 1 OK, infrared ray shielding composition (S-2)~(S-8) is prepared, the formation and evaluation of cured film is carried out.It the results are shown in table 2.

In addition, the transmitted spectrum of cured film resulting in embodiment 5 is shown in into Fig. 7.But Fig. 7 be with the glass substrate Only form the contrast of the substrate of basilar memebrane.

Comparative example 1

In addition in embodiment 1 into siloxane polymer being made to (B-1), carry out, prepare infrared similarly to Example 1 Line shielding composition (S-9), carries out the formation and evaluation of cured film.It the results are shown in table 2.

[table 2]

It should illustrate, in table 2, " A-1 " is NK-5060 (Hayashibara Co., Ltd.'s system, maximum absorption wavelength 865nm (film)).

Embodiment 9

Except using siloxane polymer (B-2) solution (the mass % of solid component concentration 35) 50 mass in embodiment 1 Part replace siloxane polymer (B-2) solution (the mass % of solid component concentration 35) 100.00 mass parts, and further chase after Beyond adding additives resin (E-1) solution (the mass % of solid component concentration 33) 50 mass parts are as (E) composition, with embodiment 1 Similarly carry out, prepare infrared ray shielding composition (S-10), carry out the formation and evaluation of cured film.It the results are shown in table 3。

Embodiment 10~16

In addition to making the species of siloxane polymer into (B-3)~(B-9) in embodiment 9, similarly to Example 9 Ground is carried out, and prepares infrared ray shielding composition (S-11)~(S-17), carries out the formation and evaluation of cured film.Its result is shown In table 3.

Comparative example 2

In addition to making the species of siloxane polymer into (B-1) in embodiment 9, carry out similarly to Example 9, Infrared ray shielding composition (S-18) is prepared, the formation and evaluation of cured film is carried out.It the results are shown in table 3.

[table 3]

Embodiment 17~33

Except in example 4 using (A) composition described in table 4 come in addition to replacing NK-5060, similarly to Example 4 Ground is carried out, and prepares infrared ray shielding composition (S-19)~(S-35), carries out the formation and evaluation of cured film.Its result is shown In table 4.It should illustrate, in embodiment 25~33, so that the mass ratio described in table 4 mixes 2 kinds of (A) compositions and uses.

Embodiment 34~45

Except in embodiment 12 using (A) composition described in table 4 come in addition to replacing NK-5060, it is same with embodiment 12 Carry out sample, prepare infrared ray shielding composition (S-36)~(S-47), the formation and evaluation of cured film are carried out, by its result It is shown in table 4.It should illustrate, in embodiment 39~45, so that the mass ratio described in table 4 mixes 2 kinds of (A) compositions and uses.

[table 4]

It should illustrate, in table 4, " A-1 "~" A-9 " is as described below.

A-1：NK-5060 (woods original Co. Ltd. systems.Flower cyanines based compound.Maximum absorption wavelength 865nm (film))

A-2：Excolor TX-EX 708K (Nippon Shokubai Co., Ltd's systems.Phthalocyanine based compound.Maximum absorption wavelength 755nm (film))

A-3：(greatly inhaled according to the phthalocyanine based compound synthesized by the embodiment 1 of No. 5046515 specifications of Japanese Patent No. Receive wavelength 990nm (film))

A-4：Lumogen IR765 (BASF AG's systems.Quaterrylene based compound.Maximum absorption wavelength 705nm (film))

A-5：According to the phosphorus synthesized by the method described in [0263] paragraph of Japanese Unexamined Patent Publication 2014-139617 publications Acid esters copper complex (copper compound.Maximum absorption wavelength 868nm (film))

A-6：According to the pyrrolopyrrole based compound synthesized by the synthesis example 2 of Japanese Unexamined Patent Publication 2011-68731 publications (maximum absorption wavelength 780nm (film))

A-7：Compound (1) (the metal dithionite alcohol based compound of Japanese Unexamined Patent Application 61-42585 publications.Maximum absorption ripple Long 908nm (film))

A-8：According to double { double (the fluoroform sulphonyl) synthesized by the embodiment 3 of No. 4168031 specifications of Japanese Patent No. Acid imide acid } N, N, N ', N '-four (to dibenzyl amino phenyl)-to benzene diimmonium (diimmonium based compound.Maximum absorption ripple Long 1060nm (film))

A-9：YMF-02 (Sumitomo Metal Mining Co., Ltd's systems.For cesium tungsten oxide compound Cs_0.33WO₃(average dispersible granule Below footpath 800nm, 1550~1650nm of maximum absorption wavelength (film)) 18.5 mass % dispersion liquids)

Embodiment 46

Automatic coating developing apparatus (Tokyo Electron Co. Ltd. systems CLEAN is used on 2 sheet glass substrates TRACK, trade name " MARK-Vz "), it is coated with spin-coating method after above-mentioned basilar memebrane formation composition, baking 2 is carried out at 250 DEG C Minute, the basilar memebrane of 0.6 μm of thickness is formed respectively.

To the substrate of the 1st, with spin-coating method infrared ray shielding group resulting in coating Examples 12 on basilar memebrane After compound (S-13), prebake is carried out in 100 DEG C of heating plate 2 minutes, form the film of 0.5 μm of thickness.Then, using exposure Ray machine (" MPA-600FA " (mixing of ghi lines) of Canon Inc.), not across photomask with 1000J/m²Light exposure to film Exposure.Then, bakeed 5 minutes after 200 DEG C of heating plate is carried out, make the substrate with cured film.

For resulting substrate, after being evaluated similarly to Example 1, crack resistance is " ◎ ", and mist degree is " ◎ ".

To the substrate of the 2nd, with spin-coating method infrared ray shielding group resulting in coating Examples 12 on basilar memebrane After compound (S-13), prebake is carried out in 100 DEG C of heating plate 2 minutes, form the film of 0.5 μm of thickness.Then, using exposure Ray machine (" MPA-600FA " (mixing of ghi lines) of Canon Inc.), across the line width with 60 μm and spacing (line and Space) the mask of the pattern of (10 pair 1), with 1000J/m²Light exposure to film expose.Then, using 2.38 mass %'s Tetramethylammonium hydroxide aqueous solution, at 23 DEG C with covering liquid Faxian shadow 80 seconds.Cleaned with the flowing water that ultra-pure water is carried out 1 minute, in rotation Become a cadre it is dry after, after being bakeed 5 minutes after being carried out with 200 DEG C of heating plate, the substrate with line width and spacing can be made.

Symbol description

10 picture pick-up devices (camera)

11 light sources

12 solid camera heads (imaging sensor)

13 signal processing parts

14 master control parts

15 shooting objects

16 encapsulation

17 pixel portions

18 portion of terminal

19 enlarging sections

20 pixels

21 the 1st optical layers (2 wavelength bandpass filter)

22 the 1st gaps

23 microlens arrays

24 the 2nd gaps

25 the 2nd optical layers (infrared ray cut off filter)

26 the 3rd gaps

27a~27c visible rays bandpass filter (colour filter)

27d infrared light bandpass filters

28 insulators

29a~29d photodiodes

30 supporting substrates

Claims

1. a kind of infrared ray shielding composition, has maximum absorption wavelength containing (A) in the range of 700~2000nm of wavelength Infrared ray smoke agent for shielding and (B) siloxane polymer,

(B) siloxane polymer has the construction unit α represented by following formula (1) and the construction unit represented by following formula (3) β, construction unit α and construction unit β content ratio α/β using molar ratio computing as 100/0~5/95,

In formula,

R¹Represent aromatic hydrocarbyl,

R³Chain alkyl is represented,

M and n represent 1~3 integer independently of each other.

2. infrared ray shielding composition according to claim 1, wherein, m and n are 1.

3. infrared ray shielding composition according to claim 1 or 2, wherein, construction unit α contains with construction unit β's Proportional a/b is using molar ratio computing as 100/0~10/90.

4. according to infrared ray shielding composition according to any one of claims 1 to 3, wherein, (A) infrared absorbent is Selected from diimmonium based compound, the sour cyanines based compound in side, flower cyanines based compound, phthalocyanine based compound, naphthalene phthalocyanine based compound, four Embedding three benzene compounds of naphthalene, ammonium based compound, imonium based compound, Azo, anthraquinone based compound, porphyrin system chemical combination Thing, pyrrolopyrrole based compound, oxonols based compound, crocic acid based compound, hexa-atomic porphyrin based compound, metal dithionite It is at least one kind of in alcohol based compound, copper compound, tungsten compound and metal boride.

5. according to infrared ray shielding composition according to any one of claims 1 to 4, wherein, it is further photosensitive containing (C) Agent.

6. according to infrared ray shielding composition according to any one of claims 1 to 4, wherein, further contain heat sensitizer.

7. a kind of cured film, is formed by the infrared ray shielding composition any one of usage right requirement 1~6.

8. cured film according to claim 7, wherein, when thickness is 0.5 μm, in 500~600nm of wavelength wave band The minimum transmittance of light be more than 90%, and the transmissivity of light wavelength 850nm at is less than 40%.

9. the cured film according to claim 7 or 8, it is infrared ray cut off filter.

10. a kind of solid camera head, it possesses the cured film any one of claim 7~9.

11. a kind of solid camera head, possesses the 1st optical layer of transmission visible ray and at least a portion infrared light and absorbs 2nd optical layer of at least a portion infrared light,

2nd optical layer has the opening portion of transmission visible ray and infrared light, and contains following compositions (A) and (B) by using The cured film that is formed of infrared ray shielding composition constitute,

(B) there is the siloxane polymer of aromatic hydrocarbyl.

12. solid camera head according to claim 11, wherein, the containing ratio of the aromatic hydrocarbyl of siloxane polymer It is 5 moles of more than % relative to Si atoms.

13. the solid camera head according to claim 11 or 12, wherein, siloxane polymer has by following formula (1) The construction unit α of expression,

In formula (1),

R¹Represent aromatic hydrocarbyl,

M represents 1~3 integer.

14. solid camera head according to claim 13, wherein, the construction unit α of siloxane polymer contain than Example is 5 moles of more than %.

15. the solid camera head according to claim 13 or 14, wherein, siloxane polymer contains by following formula (1) The construction unit α of expression and the construction unit β, construction unit α and construction unit β that are represented by following formula (3) content ratio α/β Using molar ratio computing as 100/0~5/95,

In formula,

R¹Represent aromatic hydrocarbyl,

R³Chain alkyl is represented,

M and n represent 1~3 integer independently of each other.