JPH11231126A - Ir absorbing filter - Google Patents
Ir absorbing filterInfo
- Publication number
- JPH11231126A JPH11231126A JP10325287A JP32528798A JPH11231126A JP H11231126 A JPH11231126 A JP H11231126A JP 10325287 A JP10325287 A JP 10325287A JP 32528798 A JP32528798 A JP 32528798A JP H11231126 A JPH11231126 A JP H11231126A
- Authority
- JP
- Japan
- Prior art keywords
- infrared absorbing
- infrared
- compds
- antioxidant
- absorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Optical Filters (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光学フィルタに関
するもので、特に可視光線領域に透過率が高く、赤外線
を遮断する光学フィルタに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical filter, and more particularly to an optical filter having a high transmittance in a visible light region and blocking infrared rays.
【０００２】[0002]
【従来の技術】従来、熱線吸収フィルタや、ビデオカメ
ラ視感度補正用フィルター、等には次に示されるような
物が広く使われてきた。 燐酸系ガラスに、銅や鉄などの金属イオンを含有した
フィルター（特開昭６０−２３５７４０、特開昭６２−
１５３１４４など） 基板上に屈折率の異なる層を積層し、透過光を干渉さ
せることで特定の波長を透過させる干渉フィルター（特
開昭５５−２１０９１、特開昭５９−１８４７４５な
ど） 共重合体に銅イオンを含有するアクリル系樹脂フィル
ター（特開平６−３２４２１３） バインダー樹脂に色素を分散した構成のフィルター
（特開昭５７−２１４５８、特開昭５７−１９８４１
３、特開昭６０−４３６０５など）2. Description of the Related Art Conventionally, the following materials have been widely used as a heat ray absorption filter, a video camera visibility correction filter, and the like. Filters containing phosphoric acid glass and metal ions such as copper and iron (JP-A-60-235740, JP-A-62-1987)
153144) Interference filters that transmit specific wavelengths by laminating layers having different refractive indices on a substrate and causing transmitted light to interfere (for example, JP-A-55-21091 and JP-A-59-184745). Acrylic resin filter containing copper ions (JP-A-6-324213) Filters having a structure in which a pigment is dispersed in a binder resin (JP-A-57-21458, JP-A-57-19841)
3, JP-A-60-43605, etc.)
【０００３】[0003]
【発明が解決しようとする課題】上記の従来使用されて
きた赤外線吸収フィルタには、それぞれ以下に示すよう
な問題点がある。前述の方式では近赤外領域に急峻に
吸収が有り、赤外線遮断率は非常に良好であるが、可視
領域の赤色の一部も大きく吸収してしまい、透過色は青
色に見える。ディスプレー用途では色バランスを重視さ
れ、このような場合、使用するのに困難である。また、
ガラスであるために加工性にも問題がある。前述の方
式の場合、光学特性は自由に設計でき、ほぼ設計と同等
のフィルタを製造することが可能であるが、その為に
は、屈折率差のある層の積層枚数が非常に多くなり、製
造コストが高くなる欠点がある。また、大面積を必要と
する場合、全面積にわたって高い精度の膜厚均一性が要
求され、製造が困難である。前記の方式の場合、の
方式の加工性は改善される。しかし方式と同様に、急
峻な吸収特性が有るが、やはり、赤色部分にも吸収が有
りフィルタが青く見えてしまう問題点は変らない。前記
の方式は、赤外線吸収色素として、フタロシアニン
系、ニッケル錯体系、アゾ化合物、ポリメチン系、ジフ
ェニルメタン系、トリフェニルメタン系、キノン系、な
ど多くの色素が持ちいられている。しかし、それぞれ単
独では、吸収が不十分であったり、可視領域で特定の波
長の吸収が有るなどの問題点を有している。さらに、同
フィルターを高温下、や加湿下に長時間放置すると、色
素の分解や、酸化が起こり可視領域での吸収が発生した
り、赤外領域での吸収が無くなってしまうなどの問題が
ある。The above-mentioned conventionally used infrared absorption filters have the following problems. In the above-mentioned method, the absorption is sharp in the near-infrared region, and the infrared cutoff rate is very good. However, a part of red in the visible region is also largely absorbed, and the transmitted color looks blue. In display applications, color balance is emphasized, and in such a case, it is difficult to use. Also,
Since it is glass, it has a problem in workability. In the case of the above-mentioned method, the optical characteristics can be freely designed, and a filter almost equivalent to the design can be manufactured. However, for this purpose, the number of layers having a refractive index difference becomes extremely large, There is a disadvantage that the manufacturing cost is increased. In addition, when a large area is required, high-accuracy film thickness uniformity is required over the entire area, and manufacturing is difficult. In the case of the above method, the workability of the method is improved. However, as in the case of the system, although there is a steep absorption characteristic, the problem that the filter also looks blue because there is absorption in the red portion as well. In the above-mentioned method, many dyes such as phthalocyanine, nickel complex, azo compound, polymethine, diphenylmethane, triphenylmethane, and quinone are used as infrared absorbing dyes. However, each of them has problems such as insufficient absorption and absorption of a specific wavelength in the visible region. Furthermore, if the filter is left under high temperature or humidification for a long time, there is a problem that the decomposition and oxidation of the dye occur, absorption in the visible region occurs, and absorption in the infrared region disappears. .
【０００４】[0004]
【課題を解決するための手段】本発明は、近赤外領域に
急峻な吸収があり、可視領域の光透過性が高く、且つ、
可視領域に特定波長の大きな吸収を持つことがなく、更
に、加工性及び生産性が良好で、しかも、熱的に安定な
近赤外線吸収フィルタを提供する物である。即ち本発明
は、赤外線吸収色素として、少なくともジイモニウム化
合物、含フッ素フタロシアニン系化合物及び、ニッケル
錯体系化合物のいずれか２種類以上を含有し、さらに、
酸化防止剤としてヒンダードフェノール系１次酸化防止
剤及び、燐系２次酸化防止剤を含有するポリマー組成物
を基材上に積層してなることを特徴とする赤外線吸収フ
ィルタである。好ましい実施態様は、ポリマー組成物に
含有される赤外線吸収色素の配合比が、ジイモニウム化
合物１重量部当たり、含フッ素フタロシアニン系化合物
の場合０．５〜０．０１重量部、ニッケル錯体系化合物
の場合１〜０重量部である。また、基材は透明で、ポリ
エステルフィルムである。さらに、基材に積層するポリ
マーはポリエステル樹脂であり、比重が１．０５〜１．
３５の範囲にあり、ガラス転移温度が４５℃以上であ
り、かつ赤外線吸収色素の溶解度が１wt％以上である。SUMMARY OF THE INVENTION The present invention has a steep absorption in the near infrared region, a high light transmittance in the visible region, and
An object of the present invention is to provide a near-infrared absorption filter which does not have large absorption at a specific wavelength in the visible region, has good processability and productivity, and is thermally stable. That is, the present invention contains at least a diimmonium compound, a fluorine-containing phthalocyanine-based compound, and at least one of a nickel complex-based compound as an infrared absorbing dye,
An infrared absorption filter comprising a polymer composition containing a hindered phenol-based primary antioxidant and a phosphorus-based secondary antioxidant as antioxidants, laminated on a substrate. In a preferred embodiment, the compounding ratio of the infrared absorbing dye contained in the polymer composition is 0.5 to 0.01 parts by weight in the case of the fluorinated phthalocyanine-based compound and 1 in the case of the nickel complex-based compound per 1 part by weight of the diimmonium compound. 1 to 0 parts by weight. The substrate is a transparent, polyester film. Further, the polymer laminated on the base material is a polyester resin, and the specific gravity is 1.05 to 1.
35, the glass transition temperature is 45 ° C. or more, and the solubility of the infrared absorbing dye is 1% by weight or more.
【０００５】本発明では、少なくとも２種類以上の赤外
線吸収色素が混合されていることにより、近赤外線領域
に、広く吸収があり、また、可視光線領域でも、高い透
過率でかつフラットであるために、フィルターがある特
定の色に着色しているようなことはない。本発明に用い
られる、ジイモニウム化合物としては、次のような物が
挙げられる。日本化薬社製Kayasorb IRG −０２２、IR
G −０２３があげられ、好ましくはIRG −０２２がよ
い。また、本発明に用いられる、含フッ素フタロシアニ
ン系化合物としては、日本触媒社製 Excolor IR１、
IR2 、IR3 、IR4 などが挙げられるが、好ましくは、IR
1 がよい。さらに、本発明に用いられる、ニッケル錯体
系化合物としては、三井東圧染料社製SIR-128 、SIR-13
0 、SIR-132 、SIR-159 などが挙げられるが、好ましく
はSIR-159 がよい。上記赤外線吸収色素は一例であり、
特に限定される物ではない。In the present invention, since at least two or more kinds of infrared absorbing dyes are mixed, absorption is wide in the near infrared region, and high transmittance and flatness in the visible light region. There is no such thing as a filter being colored to a particular color. Examples of the diimonium compound used in the present invention include the following. Nippon Kayaku Kayasorb IRG-022, IR
G-023, and preferably IRG-022. The fluorinated phthalocyanine compound used in the present invention includes Excolor IR1 manufactured by Nippon Shokubai Co., Ltd.
IR2, IR3, IR4 and the like, preferably IR
1 is good. Further, as the nickel complex-based compound used in the present invention, Mitsui Toatsu Dye SIR-128, SIR-13
0, SIR-132, SIR-159 and the like, and preferably SIR-159. The infrared absorbing dye is an example,
There is no particular limitation.
【０００６】また、本発明において、赤外線吸収色素を
分散したバインダーを基材にコーティングする場合に用
いる、透明基材としても、特に限定される物ではない
が、ポリエステル系、アクリル系、セルロース系、ポリ
エチレン系、ポリプロピレン系、ポリオレフィン系、ポ
リ塩化ビニル系、ポリカーボネート、フェノール系、ウ
レタン系のフィルムなどが挙げられるが、特に好ましく
は、分散安定性、環境負荷などの観点から、ポリエステ
ルフィルムが好ましい。In the present invention, the transparent substrate used when coating the substrate with a binder in which an infrared absorbing dye is dispersed is not particularly limited, but may be polyester, acrylic, cellulose, or the like. Polyethylene-based, polypropylene-based, polyolefin-based, polyvinyl chloride-based, polycarbonate, phenol-based, urethane-based films and the like can be mentioned, and polyester films are particularly preferred in view of dispersion stability, environmental load and the like.
【０００７】本発明の赤外線吸収フィルタでは、環境安
定性を向上させる為に、酸化防止剤の含有が必須であ
る。酸化防止剤としては、１次酸化防止剤と２次酸化防
止剤を組合わせるのが好ましい。更に好ましくは1 次酸
化防止剤として、ヒンダードフェノール系酸化防止剤が
良く、2 次酸化防止剤としては燐系酸化防止剤が好まし
い。また、本発明赤外線吸収フィルターでは耐光性を向
上、させる目的で、UV吸収剤を添加したものが好まし
い。さらに、本発明赤外線吸収フィルタでは、必要に応
じて更に色素を混合しても良い。In the infrared absorbing filter of the present invention, it is essential to contain an antioxidant in order to improve environmental stability. As the antioxidant, it is preferable to combine a primary antioxidant and a secondary antioxidant. More preferably, a hindered phenol-based antioxidant is preferable as the primary antioxidant, and a phosphorus-based antioxidant is preferable as the secondary antioxidant. In the infrared absorbing filter of the present invention, a filter to which a UV absorber is added is preferable for the purpose of improving and improving light resistance. Further, in the infrared absorbing filter of the present invention, a dye may be further mixed as necessary.
【０００８】本発明に用いられる１次酸化防止剤として
は、例えば、２, ６- ジターシャルブチル4 メチルフェ
ノール、スチレン化フェノール、n-オクタデシル3-(3,5
- ジターシャルブチル4-ヒドロフェニル) プロピネー
ト、2,2'- メチレンビス(4- メチル-6- ターシャルブチ
ルフェノール) 、2-ターシャルブチル-6-(3-ターシャル
ブチル-2- ヒドロキシ-5- メチルベンジル)-4-メチルフ
ェニルアクリレート、2-[1-(2-ヒドロキシ-3,5- ジター
シャルブチルペンチルフェニル) エチル]-4,6-ジターシ
ャルペンチルフェニルアクリレート、4,4'- ブチリデン
ビス(3- メチル-6- ターシャルブチルフェノール) 、4,
4'- チオビス（3-メチル-6- ターシャルブチルフェノー
ル）、テトラキス（メチレン3-(3,5- ジターシャルブチ
ル-4- ヒドロキシフェニル) プロピオネート）メタン、
3,9-ビス（2-(3-(3-ターシャルブチル-4- ヒドロキシ-5
- メチルフェニル)-プロピオニルオキシ)-1,1-ジメチル
エチル）-2,4,8,10-テトラオキサスピロ(5・5) アンデカ
ンなどが挙げられる。前記最後の化合物としては、例え
ば、住友化学社製GA-80 が入手可能である。The primary antioxidant used in the present invention includes, for example, 2,6-di-tert-butyl 4-methylphenol, styrenated phenol, n-octadecyl 3- (3,5
-Di-tert-butyl 4-hydrophenyl) propinate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-) Methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-ditalbutylpentylphenyl) ethyl] -4,6-ditalpentylphenylacrylate, 4,4′-butylidenebis ( 3-methyl-6-tert-butylphenol), 4,
4'-thiobis (3-methyl-6-tert-butylphenol), tetrakis (methylene 3- (3,5-d-tert-butyl-4-hydroxyphenyl) propionate) methane,
3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5
-Methylphenyl) -propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) andecan. As the last compound, for example, GA-80 manufactured by Sumitomo Chemical Co., Ltd. is available.
【０００９】また本発明に用いられる２次酸化防止剤
は、例えばトリノニルフェニルフォスフェート、トリフ
ェニルフォスフェート、トリ(2,4- ジターシャルブチル
フェニル) フォスフェートなどが挙げられる。前記最後
の化合物としては、例えば、住友化学社製P-16が入手可
能である。The secondary antioxidant used in the present invention includes, for example, trinonylphenyl phosphate, triphenyl phosphate, tri (2,4-ditert-butylphenyl) phosphate and the like. As the last compound, for example, P-16 manufactured by Sumitomo Chemical Co., Ltd. is available.
【００１０】実施例１ ベースポリマーとして東洋紡績製バイロンRV200 （比重
１．２６、ガラス転移温度67℃）を用いて表1 に示すよ
うな組成で、赤外線吸収色素と酸化防止剤( 住友化学社
製 Sumilizer)、バインダー樹脂、溶剤を、フラスコに
いれ、約８０℃で加熱しながら攪拌し、色素及びバイン
ダー樹脂を溶解した。次に溶解した樹脂を厚さ１００μ
ｍの高透明性ポリエステルフィルム基材（東洋紡績製
コスモシャインＡ４１００）に、ギャップが１００μｍ
のアプリケーターを用いてコーティングし、乾燥温度約
90℃で1 時間乾燥させた。コーティング厚さは約２５μ
ｍであった。得られた赤外線吸収フィルムは、目視での
色目はダークグレーであった。また、図１にその分光特
性を示す。図1 に示すように、波長４００ｎｍから６５
０ｎｍまでの可視領域においては吸収が平らで、波長７
００ｎｍ以上では急峻に吸収があるフィルムが得られ
た。得られたフィルムを80℃乾燥雰囲気中に５００ｈｒ
放置し、再度分光特性を測定したところ図２のようにな
り、若干の色変化は見られるが、近赤外吸収特性を維持
していた。Example 1 An infrared-absorbing dye and an antioxidant (manufactured by Sumitomo Chemical Co., Ltd.) having the composition shown in Table 1 were obtained using Toyobo Byron RV200 (specific gravity 1.26, glass transition temperature 67 ° C.) as a base polymer. Sumilizer), the binder resin, and the solvent were placed in a flask and stirred while heating at about 80 ° C. to dissolve the dye and the binder resin. Next, melt the resin to a thickness of 100μ.
m high transparency polyester film substrate (manufactured by Toyobo
Cosmo Shine A4100) with a gap of 100 μm
Coating using an applicator and drying temperature
It was dried at 90 ° C. for 1 hour. Coating thickness is about 25μ
m. The color of the obtained infrared absorbing film was dark gray visually. FIG. 1 shows the spectral characteristics. As shown in FIG.
In the visible region up to 0 nm, the absorption is flat and the wavelength is 7
At a thickness of 00 nm or more, a film having sharp absorption was obtained. The obtained film is dried in an atmosphere at 80 ° C. for 500 hours.
When left to stand and the spectral characteristics were measured again, the results were as shown in FIG. 2. Although a slight color change was observed, the near-infrared absorption characteristics were maintained.
【００１１】[0011]
【表１】 [Table 1]
【００１２】実施例２ ベースポリマーとして東洋紡績製バイロンRV296 （比重
１．２６、ガラス転移温度71℃）を用いて表２に示すよ
うな組成で、実施例１と同様に、赤外線吸収色素と酸化
防止剤( 住友化学社製 Sumilizer)、バインダー樹脂、
溶剤を、フラスコにいれ、約８０℃で加熱しながら攪拌
し、色素及びバインダー樹脂を溶解した。次に溶解した
樹脂を厚さ１００μｍの高透明性ポリエステルフィルム
基材（東洋紡績製 コスモシャインＡ４１００）に、ギ
ャップが１００μｍのアプリケーターを用いてコーティ
ングし、乾燥温度約90℃で１時間乾燥させた。コーティ
ング厚さは約２５μｍであった。得られた赤外線吸収フ
ィルムは、目視での色目はダークグレーであった。ま
た、その分光特性は、実施例１とほぼ同じとなり、波長
４００ｎｍから６５０ｎｍまでの可視領域においては吸
収が平らで、波長７００ｎｍ以上では急峻に吸収がある
フィルムが得られた。得られたフィルムを80℃乾燥雰囲
気中に５００ｈｒ放置し、再度分光特性を測定したとこ
ろほとんど図２と同じようになり、若干の色変化は見ら
れるが、近赤外吸収特性を維持していた。Example 2 An infrared-absorbing dye and an oxidizing agent were used in the same manner as in Example 1 with the composition shown in Table 2 by using Toyobo Byron RV296 (specific gravity: 1.26, glass transition temperature: 71 ° C.) as a base polymer. Inhibitor (Sumitomo Chemical Sumilizer), binder resin,
The solvent was placed in a flask and stirred while heating at about 80 ° C. to dissolve the dye and the binder resin. Next, the melted resin was coated on a 100 μm thick highly transparent polyester film substrate (Cosmoshine A4100 manufactured by Toyobo Co., Ltd.) using an applicator having a gap of 100 μm, and dried at a drying temperature of about 90 ° C. for 1 hour. The coating thickness was about 25 μm. The color of the obtained infrared absorbing film was dark gray visually. Further, the spectral characteristics were almost the same as those of Example 1, and a film having a flat absorption in a visible region from a wavelength of 400 nm to 650 nm and a sharp absorption at a wavelength of 700 nm or more was obtained. The obtained film was left in a dry atmosphere at 80 ° C. for 500 hours, and the spectral characteristics were measured again. The result was almost the same as in FIG. 2, and although a slight color change was observed, the near-infrared absorption characteristics were maintained. .
【００１３】[0013]
【表２】 [Table 2]
【００１４】実施例３ ベースポリマーとして東洋紡績製バイロンRV200 （比重
１．２６、ガラス転移温度67℃）を用いて表３に示すよ
うな組成で、赤外線吸収色素と酸化防止剤( 住友化学社
製 Sumilizer)、バインダー樹脂、溶剤を、フラスコに
いれ、約８０℃で加熱しながら攪拌し、色素及びバイン
ダー樹脂を溶解した。次に溶解した樹脂を厚さ１００μ
ｍの高透明性ポリエステルフィルム基材（東洋紡績製
コスモシャインＡ４１００）に、ギャップが１００μｍ
のアプリケーターを用いてコーティングし、乾燥温度約
90℃で１時間乾燥させた。コーティング厚さは約２５μ
ｍであった。得られた赤外線吸収フィルムは、目視での
色目はダークグレーであった。また、図３にその分光特
性を示す。図３に示すように、波長４００ｎｍから６５
０ｎｍまでの可視領域においては若干の吸収は有るもの
の平らで、波長７００ｎｍ以上では急峻に吸収があるフ
ィルムが得られた。得られたフィルムを80℃乾燥雰囲気
中に５００ｈｒ放置し、再度分光特性を測定したところ
図４のようになり、若干の色変化は見られるが、近赤外
吸収特性を維持していた。Example 3 An infrared-absorbing dye and an antioxidant (manufactured by Sumitomo Chemical Co., Ltd.) were used in the composition shown in Table 3 by using Toyobo Byron RV200 (specific gravity 1.26, glass transition temperature 67 ° C.) as a base polymer. Sumilizer), the binder resin, and the solvent were placed in a flask and stirred while heating at about 80 ° C. to dissolve the dye and the binder resin. Next, melt the resin to a thickness of 100μ.
m high transparency polyester film substrate (manufactured by Toyobo
Cosmo Shine A4100) with a gap of 100 μm
Coating using an applicator and drying temperature
Dry at 90 ° C. for 1 hour. Coating thickness is about 25μ
m. The color of the obtained infrared absorbing film was dark gray visually. FIG. 3 shows the spectral characteristics. As shown in FIG.
In the visible region up to 0 nm, a film was obtained which was flat with some absorption, and had a sharp absorption at a wavelength of 700 nm or more. The obtained film was allowed to stand in a dry atmosphere at 80 ° C. for 500 hours, and the spectral characteristics were measured again. The results were as shown in FIG. 4. Although a slight color change was observed, the near-infrared absorption characteristics were maintained.
【００１５】[0015]
【表３】 [Table 3]
【００１６】比較例１ ベースポリマーとして東洋紡績製バイロンRV200 （比重
１．２６、ガラス転移温度67℃）を用いて表４に示すよ
うな組成で、赤外線吸収色素とバインダー樹脂、溶剤
を、フラスコにいれ、約８０℃で加熱しながら攪拌し、
色素及びバインダー樹脂を溶解した。次に溶解した樹脂
を厚さ１００μｍの高透明性ポリエステルフィルム基材
（東洋紡績製 コスモシャインＡ４１００）に、ギャッ
プが１００μｍのアプリケーターを用いてコーティング
し、乾燥温度約90℃で１時間乾燥させた。コーティング
厚さは約２５μｍであった。本比較例１は、酸化防止剤
を使用していない例である。得られた赤外線吸収フィル
ムは、目視での色目はダークグレーであった。また、図
５にその分光特性を示す。図５に示すように、波長４０
０ｎｍから６５０ｎｍまでの可視領域においては吸収が
平らで、波長７００ｎｍ以上では急峻に吸収があるフィ
ルムが得られた。得られたフィルムを80℃乾燥雰囲気中
に５００ｈｒ放置し、再度分光特性を測定したところ図
６のようになり、色変化が発生し、近赤外吸収特性は極
めて悪くなってしまっていた。Comparative Example 1 An infrared absorbing dye, a binder resin, and a solvent having a composition shown in Table 4 were used in a flask using Toyobo Byron RV200 (specific gravity: 1.26, glass transition temperature: 67 ° C.) as a base polymer. And stir while heating at about 80 ° C,
The dye and binder resin were dissolved. Next, the melted resin was coated on a 100 μm thick highly transparent polyester film substrate (Cosmoshine A4100 manufactured by Toyobo Co., Ltd.) using an applicator having a gap of 100 μm, and dried at a drying temperature of about 90 ° C. for 1 hour. The coating thickness was about 25 μm. Comparative Example 1 is an example in which an antioxidant was not used. The color of the obtained infrared absorbing film was dark gray visually. FIG. 5 shows the spectral characteristics. As shown in FIG.
Absorption was flat in the visible region from 0 nm to 650 nm, and a film with sharp absorption was obtained at a wavelength of 700 nm or more. The obtained film was allowed to stand in a dry atmosphere at 80 ° C. for 500 hours, and the spectral characteristics were measured again. The results were as shown in FIG. 6, a color change occurred, and the near-infrared absorption characteristics were extremely poor.
【００１７】[0017]
【表４】 [Table 4]
【００１８】比較例２ ベースポリマーとして東洋紡績製バイロンRV200 （比重
１．２６、ガラス転移温度67℃）を用いて表５に示すよ
うな組成で、赤外線吸収色素と一次酸化防止剤（住友化
学社製 Sumilizer)、バインダー樹脂、溶剤を、フラス
コにいれ、約８０℃で加熱しながら攪拌し、色素及びバ
インダー樹脂を溶解した。次に溶解した樹脂を厚さ１０
０μｍの高透明性ポリエステルフィルム基材（東洋紡績
製 コスモシャインＡ４１００）に、ギャップが１００
μｍのアプリケーターを用いてコーティングし、乾燥温
度約90℃で1 時間乾燥させた。コーティング厚さは約２
５μｍであった。本比較例２は、酸化防止剤として燐系
２次酸化防止剤を使用していない例である。得られた赤
外線吸収フィルムは、目視での色目はダークグレーであ
った。また、図７にその分光特性を示す。図７に示すよ
うに、波長４００ｎｍから６５０ｎｍまでの可視領域に
おいては吸収が平らで、波長７００ｎｍ以上では急峻に
吸収があるフィルムが得られた。得られたフィルムを80
℃乾燥雰囲気中に５００ｈｒ放置し、再度分光特性を測
定したところ図８のようになり、色変化が発生し、近赤
外吸収特性は極めて悪くなってしまっていた。COMPARATIVE EXAMPLE 2 An infrared absorbing dye and a primary antioxidant (Sumitomo Chemical Co., Ltd.) having a composition as shown in Table 5 using Toyobo Byron RV200 (specific gravity 1.26, glass transition temperature 67 ° C.) as a base polymer. Sumilizer, a binder resin and a solvent were placed in a flask and stirred while heating at about 80 ° C. to dissolve the dye and the binder resin. Next, melt the resin to a thickness of 10
A 0 μm high transparency polyester film substrate (Cosmoshine A4100 manufactured by Toyobo Co., Ltd.)
It was coated using a μm applicator and dried at a drying temperature of about 90 ° C. for 1 hour. About 2 coating thickness
It was 5 μm. Comparative Example 2 is an example in which a phosphorus-based secondary antioxidant was not used as an antioxidant. The color of the obtained infrared absorbing film was dark gray visually. FIG. 7 shows the spectral characteristics. As shown in FIG. 7, a film was obtained in which the absorption was flat in the visible region from a wavelength of 400 nm to 650 nm, and was sharply absorbed at a wavelength of 700 nm or more. 80 obtained film
When left in a dry atmosphere at 500 ° C. for 500 hours and the spectral characteristics were measured again, the results were as shown in FIG. 8, and a color change occurred, and the near-infrared absorption characteristics were extremely poor.
【００１９】[0019]
【表５】 [Table 5]
【００２０】比較例３ ベースポリマーとして東洋紡績製バイロンRV200 （比重
１．２６、ガラス転移温度67℃）を用いて表６に示すよ
うな組成で、赤外線吸収色素と酸化防止剤、バインダー
樹脂、溶剤を、フラスコにいれ、約８０℃で加熱しなが
ら攪拌し、色素及びバインダー樹脂を溶解した。次に溶
解した樹脂を厚さ１００μｍの高透明性ポリエステルフ
ィルム基材（東洋紡績製 コスモシャインＡ４１００）
に、ギャップが１００μｍのアプリケーターを用いてコ
ーティングし、乾燥温度約90℃で1 時間乾燥させた。コ
ーティング厚さは約２５μｍであった。本比較例は、１
次酸化防止剤としてアミン系酸化防止剤を使用した例で
ある。得られた赤外線吸収フィルムは、目視での色目は
ダークグレーであった。また、図９にその分光特性を示
す。図９に示すように、波長４５０ｎｍから６５０ｎｍ
までの可視領域においては吸収が平らであるが、４５０
ｎｍ以下で吸収が有り、波長７００ｎｍ以上では急峻に
吸収があるフィルムが得られた。得られたフィルムを80
℃乾燥雰囲気中に５００ｈｒ放置し、再度分光特性を測
定したところ図１０のようになり、色変化が発生し、近
赤外吸収特性は極めて悪くなってしまっていたComparative Example 3 An infrared absorbing dye, an antioxidant, a binder resin, a solvent having a composition as shown in Table 6 using Toyobo Byron RV200 (specific gravity 1.26, glass transition temperature 67 ° C.) as a base polymer. Was placed in a flask and stirred while heating at about 80 ° C. to dissolve the dye and the binder resin. Next, a 100 μm-thick highly transparent polyester film base material (Cosmoshine A4100 manufactured by Toyobo Co., Ltd.)
Was coated using an applicator having a gap of 100 μm and dried at a drying temperature of about 90 ° C. for 1 hour. The coating thickness was about 25 μm. This comparative example is 1
This is an example in which an amine antioxidant is used as a secondary antioxidant. The color of the obtained infrared absorbing film was dark gray visually. FIG. 9 shows the spectral characteristics. As shown in FIG. 9, the wavelength is from 450 nm to 650 nm.
Absorption is flat in the visible range up to
A film having absorption at nm or less and having sharp absorption at a wavelength of 700 nm or more was obtained. 80 obtained film
When left in a dry atmosphere at 500 ° C. for 500 hours, and the spectral characteristics were measured again, the results were as shown in FIG. 10, a color change occurred, and the near-infrared absorption characteristics were extremely poor.
【００２１】[0021]
【表６】 [Table 6]
【００２２】比較例４ 分散媒となるベースポリエステルを以下の要領で製作し
た。温度計、撹拌機を備えたオ−トクレ−ブ中に、 ダイマー酸 （ヴァーサダイム２８８、平均分子量５７６） １７３重量部、 フマル酸 ２３重量部、 エチレングリコ−ル ３４．１重量部、 ジメチロールヘプタン ８８重量部、 ターシャルブチルカテコール ０．３重量部 テトラブトキシチタネ−ト ０．１重量部、 を仕込み１５０〜２２０℃で１８０分間加熱してエステ
ル化反応を行った。次いで、系の温度を２２０℃に保
ち、圧力を徐々に減じて３０分後に１０ｍｍＨｇとし、
１２０分間反応を続け、共重合ポリエステル樹脂（Ａ
１）を得た。Comparative Example 4 A base polyester as a dispersion medium was produced in the following manner. In an autoclave equipped with a thermometer and a stirrer, 173 parts by weight of dimer acid (versa dime 288, average molecular weight 576), 23 parts by weight of fumaric acid, 34.1 parts by weight of ethylene glycol, dimethylol heptane 88 parts by weight, tert-butyl catechol 0.3 parts by weight, and tetrabutoxy titanate 0.1 parts by weight were charged and heated at 150 to 220 ° C. for 180 minutes to perform an esterification reaction. Then, the temperature of the system was maintained at 220 ° C., and the pressure was gradually reduced to 10 mmHg after 30 minutes.
The reaction was continued for 120 minutes, and the copolymerized polyester resin (A
1) was obtained.
【００２３】得られた共重合ポリエステル樹脂（Ａ１）
は分析の結果以下のようであった。 組成比（ＮＭＲ分析） 酸成分 ダイマー酸 ６０ mol％、 フマル酸 ４０ mol％、 アルコール成分 エチレングリコール ５０ mol％、 ジメチロールヘプタン ５０ mol％、 平均分子量 ３３００、 比重 １．０２The obtained copolyester resin (A1)
Was as follows as a result of the analysis. Composition ratio (NMR analysis) Acid component Dimer acid 60 mol%, fumaric acid 40 mol%, alcohol component Ethylene glycol 50 mol%, dimethylolheptane 50 mol%, average molecular weight 3300, specific gravity 1.02
【００２４】次にこの樹脂を用いて、表７に示すような
組成で、赤外線吸収色素とバインダー樹脂、溶剤を、フ
ラスコにいれ、約８０℃で加熱しながら攪拌し、色素及
びバインダー樹脂を溶解した。次に溶解した樹脂を厚さ
１００μｍの高透明性ポリエステルフィルム基材（東洋
紡績製 コスモシャインＡ４１００）に、ギャップが１
００μｍのアプリケーターを用いてコーティングし、乾
燥温度約90℃で１時間乾燥させた。コーティング厚さは
約２５μｍであった。本比較例４は、酸化防止剤を使用
しておらず、かつ共重合ポリエステル樹脂の比重が請求
項６の範囲より小さい例である。得られた赤外線吸収フ
ィルムは、目視での色目はダークグレーであった。ま
た、実施例１とほぼ同様の分光特性を示すが、色素の析
出が発生し、耐候性に問題があった。Next, using this resin, an infrared absorbing dye, a binder resin, and a solvent having the composition shown in Table 7 were placed in a flask and stirred while heating at about 80 ° C. to dissolve the dye and the binder resin. did. Next, the melted resin was applied to a 100 μm thick highly transparent polyester film substrate (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) with a gap of 1 μm.
It was coated using a 00 μm applicator and dried at a drying temperature of about 90 ° C. for 1 hour. The coating thickness was about 25 μm. Comparative Example 4 is an example in which an antioxidant was not used and the specific gravity of the copolymerized polyester resin was smaller than the scope of Claim 6. The color of the obtained infrared absorbing film was dark gray visually. In addition, it shows almost the same spectral characteristics as in Example 1, but has a problem in weather resistance due to precipitation of a dye.
【００２５】[0025]
【表７】 [Table 7]
【００２６】比較例５ 分散媒となるベースポリエステルを以下の要領で製作し
た。温度計、撹拌機を備えたオ−トクレ−ブ中に、 ジメチルテレフタレート １５５ 重量部、 ジメチルイソフタレート ３９ 重量部、 エチレングリコール １３６ 重量部、 テトラブトキシチタネート ０．１ 重量部 を仕込み１５０〜２２０℃で１８０分間加熱してエステ
ル化反応を行った。次いで、系の温度を２２０℃に保
ち、圧力を徐々に減じて３０分後に１０ｍｍＨｇとし、
１２０分間反応を続け、共重合ポリエステル樹脂（Ａ
２）を得た。Comparative Example 5 A base polyester as a dispersion medium was produced in the following manner. In an autoclave equipped with a thermometer and a stirrer, 155 parts by weight of dimethyl terephthalate, 39 parts by weight of dimethyl isophthalate, 136 parts by weight of ethylene glycol, and 0.1 part by weight of tetrabutoxytitanate were charged at 150 to 220 ° C. The esterification reaction was performed by heating for 180 minutes. Then, the temperature of the system was maintained at 220 ° C., and the pressure was gradually reduced to 10 mmHg after 30 minutes.
The reaction was continued for 120 minutes, and the copolymerized polyester resin (A
2) was obtained.
【００２７】得られた共重合ポリエステル樹脂（Ａ２）
は分析の結果以下のようであった。 組成比（ＮＭＲ分析） 酸成分として、 テレフタル酸 ８０mol ％、 イソフタル酸 ２０mol ％、 アルコール成分として、 エチレングリコール １００mol ％、 であった。 また、比重は１．３５５ 次にこの樹脂をメチルエチルケトンとトルエンの混合溶
媒に溶解しようとしたが溶解しなかった。そこで、溶剤
としてN −メチルピロリドンを用いて、表８に示すよう
な組成で、赤外線吸収色素とバインダー樹脂、溶剤を、
フラスコにいれ、加熱しながら攪拌し、色素及びバイン
ダー樹脂を溶解した。しかし、赤外線吸収色素の一部が
溶解せず沈殿し、コーティングすることが出来なかっ
た。The obtained copolyester resin (A2)
Was as follows as a result of the analysis. Composition ratio (NMR analysis) As an acid component, terephthalic acid was 80 mol%, isophthalic acid was 20 mol%, and as an alcohol component, ethylene glycol was 100 mol%. The specific gravity was 1.355. Next, the resin was dissolved in a mixed solvent of methyl ethyl ketone and toluene, but was not dissolved. Thus, using N-methylpyrrolidone as a solvent, the composition shown in Table 8 was used to form an infrared absorbing dye, a binder resin, and a solvent,
The mixture was placed in a flask and stirred while heating to dissolve the dye and the binder resin. However, a part of the infrared absorbing dye did not dissolve but precipitated and could not be coated.
【００２８】[0028]
【表８】 [Table 8]
【００２９】[0029]
【発明の効果】近赤外線領域に広く吸収を持ち、かつ可
視領域の透過率が高く、特定の可視領域波長を大きく吸
収することのない赤外線吸収フィルタが得られ、ビデオ
カメラ、ディスプレーなどに使用しても色ずれが少な
い。また、環境安定性に優れ、長い期間での試用に耐え
ることがわかる。According to the present invention, an infrared absorption filter which has a wide absorption in the near-infrared region and a high transmittance in the visible region and does not significantly absorb a specific visible region wavelength can be obtained. Even with little color shift. In addition, it is found that it has excellent environmental stability and can withstand a long-term trial.
【図１】図１は実施例１で得られた赤外線吸収フィルタ
の分光特性である。FIG. 1 shows the spectral characteristics of an infrared absorption filter obtained in Example 1.
【図２】図２は実施例１で得られた赤外線吸収フィルタ
の耐熱テスト後の分光特性である。FIG. 2 shows spectral characteristics of the infrared absorption filter obtained in Example 1 after a heat test.
【図３】図３は実施例３で得られた赤外線吸収フィルタ
の分光特性である。FIG. 3 shows spectral characteristics of the infrared absorption filter obtained in Example 3.
【図４】図４は実施例３で得られた赤外線吸収フィルタ
の耐熱テスト後の分光特性である。FIG. 4 shows the spectral characteristics of the infrared absorption filter obtained in Example 3 after a heat resistance test.
【図５】図５は比較例１で得られた赤外線吸収フィルタ
の分光特性である。FIG. 5 shows the spectral characteristics of the infrared absorption filter obtained in Comparative Example 1.
【図６】図６は比較例１において耐熱テスト後の分光特
性である。FIG. 6 shows spectral characteristics after a heat resistance test in Comparative Example 1.
【図７】図７は比較例２で得られた赤外線吸収フィルタ
の分光特性である。FIG. 7 shows the spectral characteristics of the infrared absorption filter obtained in Comparative Example 2.
【図８】図８は比較例２において耐熱テスト後の分光特
性である。FIG. 8 shows spectral characteristics after a heat resistance test in Comparative Example 2.
【図９】図９は比較例３で得られた赤外線吸収フィルタ
の分光特性である。FIG. 9 shows spectral characteristics of the infrared absorption filter obtained in Comparative Example 3.
【図１０】図１０は比較例３において耐熱テスト後の分
光特性である。FIG. 10 shows spectral characteristics after a heat resistance test in Comparative Example 3.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山田 陽三 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yozo Yamada 2-1-1 Katada, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Research Laboratory
Claims (6)
ニウム化合物、含フッ素フタロシアニン系化合物及び、
ニッケル錯体系化合物のいずれか２種類以上の色素を含
有し、さらに、酸化防止剤としてヒンダードフェノール
系１次酸化防止剤及び、燐系２次酸化防止剤を含有する
ポリマー組成物を基材上に積層してなることを特徴とす
る赤外線吸収フィルタ。1. An infrared absorbing dye comprising at least a diimonium compound, a fluorine-containing phthalocyanine compound, and
A polymer composition containing any two or more kinds of nickel complex compounds and further containing a hindered phenol-based primary antioxidant and a phosphorus-based secondary antioxidant as an antioxidant is provided on a substrate. An infrared absorption filter characterized by being laminated on a substrate.
れる赤外線吸収色素の配合比が、ジイモニウム化合物１
重量部当たり、含フッ素フタロシアニン系化合物の場合
０．５〜０．０１重量部、ニッケル錯体系化合物の場合
１〜０重量部であることを特徴とする赤外線吸収フィル
タ。2. The compound ratio of the infrared absorbing dye contained in the polymer composition according to claim 1 is diimonium compound 1.
An infrared absorption filter characterized by being 0.5 to 0.01 parts by weight in the case of a fluorine-containing phthalocyanine compound and 1 to 0 parts by weight in the case of a nickel complex compound per part by weight.
ことを特徴とする請求項１、２記載の赤外線吸収フィル
タ。3. The infrared absorbing filter according to claim 1, wherein the substrate according to claim 1 is a transparent substrate.
樹脂であることを特徴とする請求項１〜３に記載の赤外
線吸収フィルタ。4. The infrared absorbing filter according to claim 1, wherein the polymer according to claim 1 is a polyester resin.
フィルムであることを特徴とする請求項３、４に記載の
赤外線吸収フィルタ。5. The infrared absorbing filter according to claim 3, wherein the transparent substrate according to claim 3 is a polyester film.
が１．０５〜１．３５の範囲にあり、該ポリエステル樹
脂のガラス転移温度が４５℃以上であり、かつ請求項１
に記載の赤外線吸収色素の溶解度が１wt％以上であるこ
とを特徴とする請求項４、５に記載の赤外線吸収フィル
タ。6. The polyester resin according to claim 4, wherein the specific gravity is in the range of 1.05 to 1.35, the glass transition temperature of the polyester resin is 45 ° C. or more, and
6. The infrared absorbing filter according to claim 4, wherein the solubility of the infrared absorbing dye described in (1) is 1 wt% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32528798A JP4232062B2 (en) | 1997-11-18 | 1998-11-16 | Infrared absorption filter |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31712597 | 1997-11-18 | ||
| JP9-317125 | 1997-11-18 | ||
| JP32528798A JP4232062B2 (en) | 1997-11-18 | 1998-11-16 | Infrared absorption filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11231126A true JPH11231126A (en) | 1999-08-27 |
| JP4232062B2 JP4232062B2 (en) | 2009-03-04 |
Family
ID=26568925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32528798A Expired - Fee Related JP4232062B2 (en) | 1997-11-18 | 1998-11-16 | Infrared absorption filter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4232062B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1001282A2 (en) * | 1998-11-11 | 2000-05-17 | Nisshinbo Industries, Inc. | Near infrared absorption filter |
| EP1111410A2 (en) * | 1999-12-20 | 2001-06-27 | Toyo Boseki Kabushiki Kaisha | Infrared absorption filter |
| CN1299134C (en) * | 2001-05-14 | 2007-02-07 | 住友化学工业株式会社 | Filter for image display equipment |
| WO2007032325A1 (en) | 2005-09-14 | 2007-03-22 | Toyo Boseki Kabushiki Kaisha | Polyester, process for production of polyester, and polyester molded article |
| WO2007111155A1 (en) * | 2006-03-27 | 2007-10-04 | Fujifilm Corporation | Near-infrared-absorbing material |
| WO2007111157A1 (en) * | 2006-03-29 | 2007-10-04 | Fujifilm Corporation | Near infrared absorbing material |
| WO2007111154A1 (en) * | 2006-03-29 | 2007-10-04 | Fujifilm Corporation | Near-infrared absorbing material |
| JP2009122650A (en) * | 2007-10-23 | 2009-06-04 | Jsr Corp | Radiation-sensitive composition for blue color filter, color filter and liquid crystal display element |
| US8603370B2 (en) | 2008-10-09 | 2013-12-10 | Fujifilm Corporation | Near-infrared absorptive composition, near-infrared absorptive coated material, near-infrared absorptive liquid dispersion, near-infrared absorptive ink, printed material, and near-infrared absorptive image-forming composition |
| WO2014050582A1 (en) * | 2012-09-28 | 2014-04-03 | 富士フイルム株式会社 | Metal particle dispersion and heat ray shielding material |
| CN103838081A (en) * | 2012-11-23 | 2014-06-04 | 奇美实业股份有限公司 | Photosensitive resin composition for color filter and application thereof |
| WO2017047215A1 (en) * | 2015-09-14 | 2017-03-23 | 富士フイルム株式会社 | Near-infrared absorbing composition, film, near-infrared blocking filter and solid-state imaging element |
| KR20190077078A (en) | 2017-01-11 | 2019-07-02 | 후지필름 가부시키가이샤 | Composition, film, optical filter, pattern forming method, solid-state image sensor, image display device and infrared sensor |
-
1998
- 1998-11-16 JP JP32528798A patent/JP4232062B2/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1001282A2 (en) * | 1998-11-11 | 2000-05-17 | Nisshinbo Industries, Inc. | Near infrared absorption filter |
| EP1001282A3 (en) * | 1998-11-11 | 2001-07-11 | Nisshinbo Industries, Inc. | Near infrared absorption filter |
| EP1111410A2 (en) * | 1999-12-20 | 2001-06-27 | Toyo Boseki Kabushiki Kaisha | Infrared absorption filter |
| EP1111410A3 (en) * | 1999-12-20 | 2001-12-05 | Toyo Boseki Kabushiki Kaisha | Infrared absorption filter |
| US6542292B2 (en) | 1999-12-20 | 2003-04-01 | Toyo Boseki Kabushiki Kaisha | Infrared absorption filter |
| CN1299134C (en) * | 2001-05-14 | 2007-02-07 | 住友化学工业株式会社 | Filter for image display equipment |
| WO2007032325A1 (en) | 2005-09-14 | 2007-03-22 | Toyo Boseki Kabushiki Kaisha | Polyester, process for production of polyester, and polyester molded article |
| JP2007262164A (en) * | 2006-03-27 | 2007-10-11 | Fujifilm Corp | Near-infrared absorbing material |
| WO2007111155A1 (en) * | 2006-03-27 | 2007-10-04 | Fujifilm Corporation | Near-infrared-absorbing material |
| WO2007111157A1 (en) * | 2006-03-29 | 2007-10-04 | Fujifilm Corporation | Near infrared absorbing material |
| WO2007111154A1 (en) * | 2006-03-29 | 2007-10-04 | Fujifilm Corporation | Near-infrared absorbing material |
| US8293150B2 (en) | 2006-03-29 | 2012-10-23 | Fujifilm Corporation | Near-infrared absorbing material |
| JP2009122650A (en) * | 2007-10-23 | 2009-06-04 | Jsr Corp | Radiation-sensitive composition for blue color filter, color filter and liquid crystal display element |
| EP2913375A1 (en) | 2008-10-09 | 2015-09-02 | Fujifilm Corporation | Near-infrared absorptive composition, near-infrared absorptive coated material, near-infrared absorptive liquid dispersion, near-infrared absorptive ink, printed material, and near-infrared absorptive image-forming composition |
| US8603370B2 (en) | 2008-10-09 | 2013-12-10 | Fujifilm Corporation | Near-infrared absorptive composition, near-infrared absorptive coated material, near-infrared absorptive liquid dispersion, near-infrared absorptive ink, printed material, and near-infrared absorptive image-forming composition |
| WO2014050582A1 (en) * | 2012-09-28 | 2014-04-03 | 富士フイルム株式会社 | Metal particle dispersion and heat ray shielding material |
| JP2014071254A (en) * | 2012-09-28 | 2014-04-21 | Fujifilm Corp | Metal particle dispersion and heat ray shielding material |
| CN103838081A (en) * | 2012-11-23 | 2014-06-04 | 奇美实业股份有限公司 | Photosensitive resin composition for color filter and application thereof |
| WO2017047215A1 (en) * | 2015-09-14 | 2017-03-23 | 富士フイルム株式会社 | Near-infrared absorbing composition, film, near-infrared blocking filter and solid-state imaging element |
| JPWO2017047215A1 (en) * | 2015-09-14 | 2018-08-02 | 富士フイルム株式会社 | Near-infrared absorbing composition, film, near-infrared cut filter, and solid-state imaging device |
| KR20190077078A (en) | 2017-01-11 | 2019-07-02 | 후지필름 가부시키가이샤 | Composition, film, optical filter, pattern forming method, solid-state image sensor, image display device and infrared sensor |
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| Publication number | Publication date |
|---|---|
| JP4232062B2 (en) | 2009-03-04 |
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