JPH05297208A - Diffraction grating having wide diffraction wavelength range and manufacture thereof - Google Patents
Diffraction grating having wide diffraction wavelength range and manufacture thereofInfo
- Publication number
- JPH05297208A JPH05297208A JP10467392A JP10467392A JPH05297208A JP H05297208 A JPH05297208 A JP H05297208A JP 10467392 A JP10467392 A JP 10467392A JP 10467392 A JP10467392 A JP 10467392A JP H05297208 A JPH05297208 A JP H05297208A
- Authority
- JP
- Japan
- Prior art keywords
- diffraction grating
- diffraction
- developing solution
- wavelength range
- different
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 230000002522 swelling effect Effects 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 230000008961 swelling Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- AMBJXYFIMKHOQE-UHFFFAOYSA-N 2-(2,4,6-tribromophenoxy)ethyl prop-2-enoate Chemical compound BrC1=CC(Br)=C(OCCOC(=O)C=C)C(Br)=C1 AMBJXYFIMKHOQE-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SANIRTQDABNCHF-UHFFFAOYSA-N 7-(diethylamino)-3-[7-(diethylamino)-2-oxochromene-3-carbonyl]chromen-2-one Chemical compound C1=C(N(CC)CC)C=C2OC(=O)C(C(=O)C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=CC2=C1 SANIRTQDABNCHF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H1/024—Hologram nature or properties
- G03H1/0248—Volume holograms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/04—Processes or apparatus for producing holograms
- G03H1/18—Particular processing of hologram record carriers, e.g. for obtaining blazed holograms
- G03H2001/186—Swelling or shrinking the holographic record or compensation thereof, e.g. for controlling the reconstructed wavelength
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/12—Photopolymer
Landscapes
- Diffracting Gratings Or Hologram Optical Elements (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、回折格子及びその作製
方法に関し、特に、熱線反射膜のように広い波長範囲の
光を回折をする回折格子及びその作製方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diffraction grating and its manufacturing method, and more particularly to a diffraction grating which diffracts light in a wide wavelength range such as a heat ray reflective film and its manufacturing method.
【０００２】[0002]
【従来の技術】従来、回折格子の１つとして、フォトポ
リマー、重クロム酸ゼラチン、銀塩等の膜に光を干渉さ
せてボリュームホログラムの形で記録したものがよく知
られている。しかし、これらは何れも回折波長の範囲が
狭く、広い波長範囲のものは得られていない。2. Description of the Related Art Heretofore, as one of diffraction gratings, one in which a film of photopolymer, dichromated gelatin, silver salt or the like is made to interfere with light and recorded in the form of a volume hologram is well known. However, all of them have a narrow diffraction wavelength range, and a wide wavelength range has not been obtained.
【０００３】[0003]
【発明が解決しようとする課題】ところで、このような
回折格子を熱線反射膜等に用いようとする場合、回折波
長が数１００ｎｍ以上の範囲にわたる必要がある。By the way, when such a diffraction grating is used for a heat ray reflective film or the like, it is necessary that the diffraction wavelength is in the range of several hundreds nm or more.
【０００４】本発明はこのような状況に鑑みてなされた
ものであり、その目的は、フォトポリマーを用いたボリ
ュームホログラムタイプの回折格子において、回折波長
範囲を広げることである。The present invention has been made in view of such circumstances, and an object thereof is to widen the diffraction wavelength range in a volume hologram type diffraction grating using a photopolymer.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
に、まず、本発明の原理を説明すると、感光層中のフォ
トポリマーのバインダーポリマーとして、現像液に対す
る膨潤性が異なるものを同時に混合して用いると、フォ
トポリマーの現像液による膜膨潤性が部位により異なる
ようになるので、光の干渉記録後、フォトポリマー中の
モノマーと異なるモノマーを溶解した現像液を用い、感
光層中の未反応のモノマーと現像液中のモノマーとを膨
潤過程で置換させると、置換されるモノマーの割合が部
位により異なり、そのため屈折率も部位により異なるこ
とになるので、部位により干渉縞間の光学距離が異な
り、回折波長範囲が広くなる。これが本発明の原理であ
る。In order to achieve the above object, first, the principle of the present invention will be explained. As a binder polymer of a photopolymer in a photosensitive layer, binder polymers having different swelling properties in a developing solution are simultaneously mixed. When used as a photopolymer, the film swelling property of the photopolymer in the developing solution will differ depending on the site.Therefore, after interference recording of light, a developing solution in which a monomer different from the monomer in the photopolymer is dissolved is used. Replacing the monomer in Example 1 with the monomer in the developing solution in the swelling process, the ratio of the replaced monomer varies depending on the site, and therefore the refractive index also varies depending on the site.Therefore, the optical distance between the interference fringes varies depending on the site. , The diffraction wavelength range becomes wider. This is the principle of the present invention.
【０００６】この場合、バインダーポリマーを数種類用
いることにより、回折波長域が広くなり、例えば熱線反
射膜等の応用に有用なものとなる。In this case, by using several kinds of binder polymers, the diffraction wavelength range is widened, which is useful for applications such as heat ray reflective films.
【０００７】以下、より具体的に述べると、バインダー
ポリマーとしては、ポリメタクリル酸エステル又はその
部分加水分解物、ポリ酢酸ビニル又はその加水分解物、
ポリスチレン、ポリビニルブチラール、ポリクロロプレ
ン、ポリ塩化ビニル、塩素化ポリエチレン、塩素化ポリ
プロピレン、ポリ−Ｎ−ビニルカルバゾール又はその誘
導体、ポリ−Ｎ−ビニルピロリドン又はその誘導体、ス
チレンと無水マレイン酸の共重合体又はその半エステ
ル、アクリル酸、アクリル酸エステル、メタクリル酸、
メタクリル酸エステル、アクリルアミド、アクリルニト
リル等の共重合可能なモノマー群から選択されるモノマ
ーを重合成分とする共重合体等が用いられる。More specifically, as the binder polymer, polymethacrylic acid ester or its partial hydrolyzate, polyvinyl acetate or its hydrolyzate,
Polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinylcarbazole or a derivative thereof, poly-N-vinylpyrrolidone or a derivative thereof, a copolymer of styrene and maleic anhydride or Its half-ester, acrylic acid, acrylic acid ester, methacrylic acid,
A copolymer having a monomer selected from the group of copolymerizable monomers such as methacrylic acid ester, acrylamide, and acrylonitrile as a polymerization component is used.
【０００８】また、モノマーとしては、１分子中に少な
くともエチレン性不飽和二重結合を１個有する光重合、
光架橋可能なモノマー、オリゴマー、プレポリマー及び
それらの混合物であり、モノマー及びその共重合体の例
としては、不飽和カルボン酸及びその塩、不飽和カルボ
ン酸と脂肪族多価アルコール化合物とのエステル、不飽
和カルボン酸と脂肪族多価アミン化合物のアミド等があ
げられる。Further, as the monomer, photopolymerization having at least one ethylenically unsaturated double bond in one molecule,
Photocrosslinkable monomers, oligomers, prepolymers and mixtures thereof, examples of monomers and copolymers thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds. Examples thereof include amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds.
【０００９】上記したバインダーポリマーの中、現像液
膨潤性の異なるものを選択し、数種類組み合わせるとよ
い。その際、現像液膨潤性は溶解性と密接な関連がある
ので、溶解性を計算することにより、選択の効率化が図
れる。Of the above binder polymers, those having different developing solution swelling properties may be selected and combined with several kinds. At that time, since the swelling property of the developing solution is closely related to the solubility, the efficiency of selection can be improved by calculating the solubility.
【００１０】溶解性を表す溶解パラメータδは、Ｆｅｄ
ｏｒｓが開発した方法により、次の式から求められる。 δ＝（ΣΔｅi ／ΣΔｖi ）1/2 ここで、Δｅi 、ΣΔｖi はそれぞれ原子又は原子団の
蒸発エネルギー、モル体積である。例えば、ポリメタク
リル酸ｎ−ブチルについて計算すると、δ＝９．５４に
なる。The solubility parameter δ representing the solubility is Fed
It is calculated from the following formula by the method developed by ors. δ = (ΣΔe i / ΣΔv i ) 1/2 Here, Δe i and ΣΔv i are the evaporation energy and the molar volume of an atom or an atomic group, respectively. For example, when calculated for poly (n-butyl methacrylate), δ = 9.54.
【００１１】具体的には、例えば、ポリ−Ｎ−ビニルカ
ルバゾール（δ＝１２．４）、スチレン−マレイン酸イ
ソブチル共重合体（δ＝１１．８）、ポリメチルメタク
リレート（δ＝１０．０）を混合し、アセトンとエチル
セロソルブの混合溶媒等で現像するとよい。Specifically, for example, poly-N-vinylcarbazole (δ = 12.4), styrene-isobutyl maleate copolymer (δ = 11.8), polymethylmethacrylate (δ = 10.0). It is advisable to mix them and develop with a mixed solvent of acetone and ethyl cellosolve or the like.
【００１２】また、同じ又は類似の構造のバインダーポ
リマーで重量平均分子量が異なるものを数種混合しても
同様の効果がある。The same effect can be obtained by mixing several kinds of binder polymers having the same or similar structure but having different weight average molecular weights.
【００１３】例えば、スチレン−マレイン酸モノイソブ
チル共重合体の重量平均分子量が数千、数万、数十万の
ものを組み合わせるとよい。For example, a styrene-monoisobutyl maleate copolymer having a weight average molecular weight of several thousand, tens of thousands, or hundreds of thousands may be combined.
【００１４】また、置換する反応性モノマーとしては、
相互に屈折率差の大きなものの組み合わせ選択する。Further, as the reactive monomer to be substituted,
A combination of those having a large difference in refractive index is selected.
【００１５】上記以外の成分である光重合開始剤、増感
色素については、通常のものを使用すればよい。As the photopolymerization initiator and the sensitizing dye which are the components other than those described above, conventional ones may be used.
【００１６】これら成分を含む感光層に、レーザ干渉露
光、現像により、回折波長範囲が広い回折格子が得られ
る。A diffraction grating having a wide diffraction wavelength range can be obtained by laser interference exposure and development on the photosensitive layer containing these components.
【００１７】すなわち、本発明の回折波長範囲が広い回
折格子は、フォトポリマーに記録した屈折率分布型の干
渉縞からなる回折格子において、バインダーポリマーが
現像液に対する膨潤性が異なるものの複数の混合物から
なることを特徴とするものである。That is, the diffraction grating having a wide diffraction wavelength range of the present invention is a diffraction grating composed of interference fringes of a refractive index distribution type recorded in a photopolymer, and the binder polymer has different swelling properties with respect to a developing solution. It is characterized by becoming.
【００１８】また、本発明の回折波長範囲が広い回折格
子の作製方法は、フォトポリマーに記録された屈折率分
布型の干渉縞からなる回折格子の作製方法において、現
像液に対する膨潤性が異なるポリマーを複数混合したも
のをバインダーポリマーとして用い、これに反応性モノ
マー、光重合開始剤を分散させてなる記録媒体に干渉縞
を記録後、前記記録媒体中の反応性モノマーと異なる反
応性モノマーを溶解した現像液を用いて現像することを
特徴とする作製方法である。The method for producing a diffraction grating having a wide diffraction wavelength range according to the present invention is the same as the method for producing a diffraction grating composed of a refractive index distribution type interference fringe recorded on a photopolymer. A mixture of two or more is used as a binder polymer, and after recording interference fringes on a recording medium in which a reactive monomer and a photopolymerization initiator are dispersed, a reactive monomer different from the reactive monomer in the recording medium is dissolved. The developing method is characterized in that development is performed using the developer.
【００１９】この場合、複数のポリマーとして、相互に
溶解度の異なるものを用いればよく、また、相互に構造
が類似で分子量が異なるものを用いてもよく、相互に構
造が異なり現像液に対する膨潤率が異なるものを用いて
もよい。In this case, as the plurality of polymers, those having mutually different solubilities may be used, and those having similar structures and different molecular weights may be used, and the swelling ratio in the developing solution may be different from each other. Different may be used.
【００２０】[0020]
【作用】本発明においては、フォトポリマーのバインダ
ーポリマーが現像液に対する膨潤性が異なるものの複数
の混合物からなるので、記録媒体中の反応性モノマーと
異なる反応性モノマーを溶解した現像液を用いて現像す
ると、記録媒体中の未反応の反応性モノマーと現像液中
の反応性モノマーとが膨潤過程で置換され、置換された
モノマーの割合が部位により異なることになるので、屈
折率も部位により異なることになる。したがって、部位
により干渉縞間の光学距離が異なり、回折波長範囲が広
くなる。In the present invention, since the binder polymer of the photopolymer is composed of a plurality of mixtures having different swelling properties with respect to the developing solution, development is carried out using a developing solution in which a reactive monomer different from the reactive monomer in the recording medium is dissolved. Then, the unreacted reactive monomer in the recording medium and the reactive monomer in the developer are replaced in the swelling process, and the ratio of the replaced monomer varies depending on the site, so that the refractive index also varies depending on the site. become. Therefore, the optical distance between the interference fringes differs depending on the part, and the diffraction wavelength range becomes wider.
【００２１】[0021]
【実施例】以下、本発明回折波長範囲が広い回折格子及
びその作製方法の実施例に付いて説明する。 実施例１ バインダーポリマーとして、ポリ−Ｎ−ビニルカルバゾ
ール、スチレン−マレイン酸イソブチル共重合体、スチ
レン−アクリル酸共重合体を合計５０部、反応性モノマ
ーとして、トリブロモフェノキシエチルアクリレート４
５部、光重合開始剤として、ベンゾフェノンを３部、増
感色素として、３，３’−カルボニルビス−（７−ジエ
チルアミノクマリン）を２部、をジオキサン中に溶解
し、１０ｗｔ％の感光液とした。EXAMPLES Examples of a diffraction grating having a wide diffraction wavelength range and a method of manufacturing the same according to the present invention will be described below. Example 1 A total of 50 parts of poly-N-vinylcarbazole, styrene-isobutyl maleate copolymer, and styrene-acrylic acid copolymer were used as the binder polymer, and tribromophenoxyethyl acrylate 4 was used as the reactive monomer.
5 parts, 3 parts of benzophenone as a photopolymerization initiator and 2 parts of 3,3′-carbonylbis- (7-diethylaminocoumarin) as a sensitizing dye were dissolved in dioxane to prepare a 10 wt% photosensitive solution. did.
【００２２】この感光液をガラス板上にアプリケーター
を用いて塗布し、乾燥して、２０μｍ厚の膜にした。This photosensitive solution was applied onto a glass plate with an applicator and dried to form a film having a thickness of 20 μm.
【００２３】この上に、ポリビニルアルコール（ＰＶＡ
２０５、クラレ（株）製）の１０ｗｔ％をコーティング
して、酸素バリア層とした。On top of this, polyvinyl alcohol (PVA
205, 10 wt% of Kuraray Co., Ltd. was coated to form an oxygen barrier layer.
【００２４】次に、この記録媒体に二光束干渉法でアル
ゴンイオンレーザーの４８８ｎｍ光を露光した。Next, this recording medium was exposed to 488 nm light of an argon ion laser by a two-beam interference method.
【００２５】次いで、酸素バリア層を粘着テープで剥離
した。Then, the oxygen barrier layer was peeled off with an adhesive tape.
【００２６】次に、現像液として、ヒドロキシエチルア
クリレートをアセトン：エチルセロソルブの１：１溶液
中に５０ｗｔ％溶解したものを用い、この現像液中に３
０秒間浸漬し、未露光のトリブロモフェノキシエチルア
クリレートを抽出し、ヒドロキシエチルアクリレートを
膨潤したバインダーポリマーに注入した。Next, as a developing solution, a solution prepared by dissolving 50% by weight of hydroxyethyl acrylate in a 1: 1 solution of acetone: ethylcellosolve was used.
It was immersed for 0 seconds, unexposed tribromophenoxyethyl acrylate was extracted, and hydroxyethyl acrylate was injected into the swollen binder polymer.
【００２７】その後、超高圧水銀ランプで１Ｊ／ｃｍ2
の紫外線を照射し、注入したヒドロキシエチルアクリレ
ートを硬化させた。After that, with an ultra-high pressure mercury lamp, 1 J / cm 2
Was irradiated with ultraviolet rays to cure the injected hydroxyethyl acrylate.
【００２８】このようにして得られた回折格子は、４７
０ｎｍから６５０ｎｍ付近の光を回折するものとなっ
た。The diffraction grating thus obtained has 47
The light in the vicinity of 0 nm to 650 nm was diffracted.
【００２９】なお、回折波長範囲を数１００ｎｍまで広
げるには、回折波長領域が異なるように形成された上記
のような回折格子を複数枚積層して用いればよい。In order to extend the diffraction wavelength range to several hundreds of nm, a plurality of diffraction gratings having different diffraction wavelength regions may be stacked and used.
【００３０】実施例２ バインダーポリマーとして、スチレン−マレイン酸共重
合体類の重量平均分子量Ｍｗの異なるものを以下の６種
類を混合した。Example 2 As binder polymers, the following 6 kinds of styrene-maleic acid copolymers having different weight average molecular weights Mw were mixed.
【００３１】Ｍｗ＝１７００（ＳＭＡ１７３５２）、 Ｍｗ＝１９００（ＳＭＡ２６２５）、 Ｍｗ＝２３００（ＳＭＡ３８４０）、 Ｍｗ＝２５００（ＳＭＡ１４４０）、 Ｍｗ＝１０５，０００（ＳＣＲ１ＰＳＥＴ５５０）、 Ｍｗ＝１８０，０００（ＳＣＲ１ＰＳＥＴ５４０） 反応性モノマー、光重合開始剤、増感色素として、実施
例１と同じものを用い、実施例１と同様に、塗布し、乾
燥し、同様に酸素バリア層を設け、同様に露光した。Mw = 1700 (SMA17352), Mw = 1900 (SMA2625), Mw = 2300 (SMA3840), Mw = 2500 (SMA1440), Mw = 105,000 (SCR1PSET550), Mw = 180,000 (SCR1PSET540) Reactivity The same monomers, photopolymerization initiators, and sensitizing dyes as in Example 1 were used, and coating and drying were carried out in the same manner as in Example 1, an oxygen barrier layer was similarly provided, and exposure was carried out in the same manner.
【００３２】酸素バリア層を剥離後、現像液として、ビ
スコート１７Ｆ（大阪有機化学（株）製、フッ素含有ア
クリレート）をイソプロピルアルコール：エチルセロソ
ルブの１：１溶液中に３０ｗｔ％溶解したものを用い、
この現像液中に３０秒間浸漬して現像した。After peeling off the oxygen barrier layer, a developer in which biscoat 17F (a fluorine-containing acrylate manufactured by Osaka Organic Chemical Co., Ltd.) was dissolved in a 1: 1 solution of isopropyl alcohol: ethyl cellosolve in an amount of 30 wt% was used.
It was developed by immersing it in this developer for 30 seconds.
【００３３】その後、超高圧水銀ランプで１Ｊ／ｃｍ2
の紫外線を照射し、注入したビスコート１７Ｆを硬化さ
せた。After that, 1 J / cm 2 with an ultra-high pressure mercury lamp
Was irradiated with ultraviolet rays to cure the injected viscoat 17F.
【００３４】このようにして得られた回折格子は、５５
０ｎｍから６８０ｎｍ付近の光を回折するものとなっ
た。The diffraction grating thus obtained is 55
The light in the vicinity of 0 nm to 680 nm was diffracted.
【００３５】なお、回折波長範囲を数１００ｎｍまで広
げるには、回折波長領域が異なるように形成された上記
のような回折格子を複数枚積層して用いればよい。In order to extend the diffraction wavelength range to several hundreds of nm, a plurality of diffraction gratings having different diffraction wavelength regions may be stacked and used.
【００３６】比較例 上記実施例２において、バインダーポリマーとして、Ｍ
ｗ＝２５００のＳＭＡ１４４０のみにしたところ、回折
波長域の幅は、約２０ｎｍと狭いものとなった。Comparative Example In the above-mentioned Example 2, as the binder polymer, M
When only SMA1440 with w = 2500 was used, the width of the diffraction wavelength region was as narrow as about 20 nm.
【００３７】[0037]
【発明の効果】以上の説明から明らかなように、本発明
の回折波長範囲が広い回折格子及びその作製方法による
と、フォトポリマーのバインダーポリマーが現像液に対
する膨潤性が異なるものの複数の混合物からなるので、
記録媒体中の反応性モノマーと異なる反応性モノマーを
溶解した現像液を用いて現像すると、記録媒体中の未反
応の反応性モノマーと現像液中の反応性モノマーとが膨
潤過程で置換され、置換されたモノマーの割合が部位に
より異なることになるので、屈折率も部位により異なる
ことになる。したがって、部位により干渉縞間の光学距
離が異なり、回折波長範囲が広くなる。As is apparent from the above description, according to the diffraction grating having a wide diffraction wavelength range and the method for producing the same according to the present invention, the binder polymer of the photopolymer is composed of a plurality of mixtures having different swelling properties in a developing solution. So
When developed using a developing solution in which a reactive monomer different from the reactive monomer in the recording medium is dissolved, the unreacted reactive monomer in the recording medium and the reactive monomer in the developing solution are replaced during the swelling process, and Since the ratio of the removed monomer varies depending on the site, the refractive index also varies depending on the site. Therefore, the optical distance between the interference fringes differs depending on the part, and the diffraction wavelength range becomes wider.
【００３８】回折波長範囲を８００〜２０００ｎｍにす
ると、可視光を通過し熱線を反射する良好な熱線反射膜
が得られる。この熱線反射膜を自動車や建物の窓に用い
ることにより、車内及び室内の温度上昇を低減すること
ができる。When the diffraction wavelength range is set to 800 to 2000 nm, a good heat ray reflective film that transmits visible light and reflects heat rays can be obtained. By using this heat ray reflective film for a window of an automobile or a building, it is possible to reduce the temperature rise inside the vehicle and in the room.
【００３９】[0039]
Claims (5)
の干渉縞からなる回折格子において、バインダーポリマ
ーが現像液に対する膨潤性が異なるものの複数の混合物
からなることを特徴とする回折波長範囲が広い回折格
子。1. A diffraction grating having a refractive index distribution type interference fringe recorded on a photopolymer, characterized in that a binder polymer is composed of a plurality of mixtures having different swelling properties with respect to a developing solution and having a wide diffraction wavelength range. lattice.
型の干渉縞からなる回折格子の作製方法において、現像
液に対する膨潤性が異なるポリマーを複数混合したもの
をバインダーポリマーとして用い、これに反応性モノマ
ー、光重合開始剤を分散させてなる記録媒体に干渉縞を
記録後、前記記録媒体中の反応性モノマーと異なる反応
性モノマーを溶解した現像液を用いて現像することを特
徴とする回折波長範囲が広い回折格子の作製方法。2. A method for producing a diffraction grating composed of a refractive index distribution type interference fringe recorded on a photopolymer, wherein a mixture of a plurality of polymers having different swelling properties with respect to a developing solution is used as a binder polymer, and reactivity to this is obtained. After recording interference fringes on a recording medium in which a monomer and a photopolymerization initiator are dispersed, development is performed using a developing solution in which a reactive monomer different from the reactive monomer in the recording medium is developed. A method of manufacturing a diffraction grating with a wide range.
度の異なるものを用いることを特徴とする請求項２記載
の回折波長範囲が広い回折格子の作製方法。3. The method for producing a diffraction grating having a wide diffraction wavelength range according to claim 2, wherein polymers having different solubilities are used as the plurality of polymers.
が類似で分子量が異なるものを用いることを特徴とする
請求項２記載の回折波長範囲が広い回折格子の作製方
法。4. The method for producing a diffraction grating having a wide diffraction wavelength range according to claim 2, wherein polymers having similar structures and different molecular weights are used as the plurality of polymers.
が異なり現像液に対する膨潤率が異なるものを用いるこ
とを特徴とする請求項２記載の回折波長範囲が広い回折
格子の作製方法。5. The method for producing a diffraction grating having a wide diffraction wavelength range according to claim 2, wherein polymers having different structures and different swelling rates with respect to a developing solution are used as the plurality of polymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10467392A JPH05297208A (en) | 1992-04-23 | 1992-04-23 | Diffraction grating having wide diffraction wavelength range and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10467392A JPH05297208A (en) | 1992-04-23 | 1992-04-23 | Diffraction grating having wide diffraction wavelength range and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05297208A true JPH05297208A (en) | 1993-11-12 |
Family
ID=14386995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10467392A Pending JPH05297208A (en) | 1992-04-23 | 1992-04-23 | Diffraction grating having wide diffraction wavelength range and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05297208A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080131626A1 (en) * | 2005-02-09 | 2008-06-05 | Bastiaansen Cees C | Process for Preparing a Polymeric Relief Structure |
-
1992
- 1992-04-23 JP JP10467392A patent/JPH05297208A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080131626A1 (en) * | 2005-02-09 | 2008-06-05 | Bastiaansen Cees C | Process for Preparing a Polymeric Relief Structure |
| US8927178B2 (en) * | 2005-02-09 | 2015-01-06 | Stichting Dutch Polymer Institute | Process for preparing a polymeric relief structure |
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