JPH0335337B2 - - Google Patents
Info
- Publication number
- JPH0335337B2 JPH0335337B2 JP57045993A JP4599382A JPH0335337B2 JP H0335337 B2 JPH0335337 B2 JP H0335337B2 JP 57045993 A JP57045993 A JP 57045993A JP 4599382 A JP4599382 A JP 4599382A JP H0335337 B2 JPH0335337 B2 JP H0335337B2
- Authority
- JP
- Japan
- Prior art keywords
- dichromate
- water
- resin composition
- cyclic
- crown
- 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.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 21
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000011342 resin composition Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000004292 cyclic ethers Chemical class 0.000 claims description 10
- -1 aromatic crown ether Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229920005565 cyclic polymer Polymers 0.000 claims description 2
- 108010020346 Polyglutamic Acid Proteins 0.000 claims 1
- 229920002643 polyglutamic acid Polymers 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 6
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229930195712 glutamate Natural products 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AXWCVSOBRFLCJG-UHFFFAOYSA-N 2,5,12,15,22,25-hexaoxatetracyclo[24.4.0.06,11.016,21]triaconta-1(30),6,8,10,16,18,20,26,28-nonaene Chemical compound O1CCOC2=CC=CC=C2OCCOC2=CC=CC=C2OCCOC2=CC=CC=C21 AXWCVSOBRFLCJG-UHFFFAOYSA-N 0.000 description 1
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- SVJYFWHFQPBIOY-UHFFFAOYSA-N 7,8,16,17-tetrahydro-6h,15h-dibenzo[b,i][1,4,8,11]tetraoxacyclotetradecine Chemical compound O1CCCOC2=CC=CC=C2OCCCOC2=CC=CC=C21 SVJYFWHFQPBIOY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 125000000320 amidine group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- XAQCJVGGJJFLPP-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium Chemical compound N.N.O[Cr](=O)(=O)O[Cr](O)(=O)=O XAQCJVGGJJFLPP-UHFFFAOYSA-L 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002633 crown compound Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- YYGBVRCTHASBKD-UHFFFAOYSA-M methylene green Chemical compound [Cl-].C1=CC(N(C)C)=C([N+]([O-])=O)C2=[S+]C3=CC(N(C)C)=CC=C3N=C21 YYGBVRCTHASBKD-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 229920003170 water-soluble synthetic polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は耐水性感光性樹脂組成物に関し、さら
に詳しくは、水不溶性で、かつ、有機溶媒可溶の
高分子化合物中に、重クロム酸塩を均質に混和さ
せて成る耐水性を有する感光性樹脂組成物に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-resistant photosensitive resin composition, and more specifically, the present invention relates to a water-resistant photosensitive resin composition, and more specifically, a water-resistant photosensitive resin composition in which dichromate is homogeneously mixed into a water-insoluble and organic solvent-soluble polymer compound. The present invention relates to a photosensitive resin composition having water resistance.
感光性樹脂は、光照射によつて誘起される反応
により短時間に樹脂の分子構造が化学変化を起
し、例えば溶媒に対して不溶性となるといつた物
性的変化を生ずる樹脂であり、その性質を利用し
て印刷製造材料、フオトエツチング、フオトミリ
ングなどのフオトレジストとして、あるいは塗料
や印刷インキの感光性ビヒクルとして多くの分
野、例えば印刷、家電・電子、インキ、塗料、ワ
ニスなどの分野に幅広く用いられている。 Photosensitive resin is a resin whose molecular structure undergoes a chemical change in a short period of time due to a reaction induced by light irradiation, resulting in a physical change such as becoming insoluble in a solvent. It is widely used in many fields such as printing, home appliances/electronics, ink, paint, varnish, etc. as a printing manufacturing material, photoresist for photoetching, photomilling, etc., or as a photosensitive vehicle for paints and printing inks. It is used.
ところで、重クロム酸塩は歴史的に最も古い光
架橋剤としてよく知られているが、その重金属汚
染性によつて使用範囲が著しく限定されており、
そのためのこの光架橋剤に代るものとして、近年
有機系感光材料についての研究・開発がさかんに
行われている。 By the way, dichromate is historically well known as the oldest photocrosslinking agent, but its range of use is severely limited due to its heavy metal contamination properties.
As an alternative to this photocrosslinking agent, research and development on organic photosensitive materials has been actively conducted in recent years.
しかしながら、重クロム酸塩は前記のような不
利な点を有しているにもかかわらず、低価格であ
ること、比較的光感度が高く、解像度も高いこ
と、任意の高分子化合物と組合わせうることなど
の理由によつて、依然として金属微細加工やグラ
ビア印刷、あるいはカラーテレビブラウン管のけ
い光面作成などに用いられている。また、近年重
クロム酸塩−ゼラチンがホログラム感材として適
していることが知られるようになつて、この重ク
ロム酸塩がさらに見直されてきている。 However, despite the above-mentioned disadvantages, dichromate has low cost, relatively high photosensitivity, high resolution, and can be combined with any polymeric compound. Due to its ability to absorb light, it is still used in metal microfabrication, gravure printing, and the creation of fluorescent surfaces for color TV cathode ray tubes. Furthermore, in recent years, it has become known that dichromate-gelatin is suitable as a hologram sensitive material, and this dichromate has been further reconsidered.
しかしながら、重クロム酸塩は水溶性あるため
に、マトリツクスとしての高分子化合物は水溶性
であることが必要であつて、例えばゼラチン、カ
ゼインなどの天然高分子化合物、ポリビニルアル
コールなどの水溶性合成高分子化合物が実際に用
いられている。したがつて、重クロム酸塩を混和
したこれらの高分子化合物から得られる画像は強
い親水性を有していて、空気中の水分の影響によ
り画像が変化する欠点がある。特にホログラムと
して用いる場合、この水分の影響が重大な問題と
なり、画質を安定にするために、画像面を密封す
るなど繁雑な措置が不可欠とされている。したが
つて、このような繁雑さを除くために、重クロム
酸塩のもつ優れた光架橋性能を損うことなく、耐
水性を有する高分子化合物を光不溶化する方法の
開発が要望されている。 However, since dichromate is water-soluble, the polymer compound used as the matrix needs to be water-soluble.For example, natural polymers such as gelatin and casein, and water-soluble synthetic polymers such as polyvinyl alcohol, Molecular compounds are actually used. Therefore, images obtained from these polymer compounds mixed with dichromate have strong hydrophilic properties, and have the disadvantage that the images change due to the influence of moisture in the air. Particularly when used as a hologram, the influence of this moisture becomes a serious problem, and complicated measures such as sealing the image surface are essential to stabilize the image quality. Therefore, in order to eliminate such complications, there is a need for the development of a method for photo-insolubilizing water-resistant polymer compounds without impairing the excellent photo-crosslinking properties of dichromate. .
本発明者は、このような事情に鑑み、重クロム
酸塩を混和した耐水性感光性樹脂組成物を開発す
べく鋭意研究を重ねた結果、重クロム酸塩と環状
エーテルとから形成される錯化合物は有機溶媒に
可溶となり、この錯化合物を、有機溶媒中で活性
水素を有する水不溶性の高分子化合物と均一に混
合すれば、その目的を達しうることを見出しこの
知見に基づいて本発明を完成するに至つた。 In view of these circumstances, the present inventor conducted extensive research to develop a water-resistant photosensitive resin composition containing dichromate, and as a result, discovered a complex formed from dichromate and cyclic ether. The compound becomes soluble in an organic solvent, and it was discovered that this objective could be achieved by uniformly mixing this complex compound with a water-insoluble polymer compound having active hydrogen in an organic solvent.Based on this knowledge, the present invention was developed. I was able to complete it.
すなわち、本発明は、活性水素を有する高分子
化合物中に、重クロム酸塩と環状エーテルとから
成る錯化合物を含有させることを特徴とする耐水
性感光性樹脂組成物を提供するものである。 That is, the present invention provides a water-resistant photosensitive resin composition characterized in that a complex compound consisting of a dichromate and a cyclic ether is contained in a polymer compound having active hydrogen.
本発明において用いる重クロム酸塩としては、
例えばアンモニウム、リチウム、カリウム、ナト
リウムなどの塩が挙げられる。 As the dichromate used in the present invention,
Examples include ammonium, lithium, potassium, and sodium salts.
また、本発明で用いる環状エーテルは、重クロ
ム酸塩と錯化合物を形成し、重クロム酸塩を有機
溶媒に対して可溶化させるものであつて、通常無
機塩を可溶化させる環状エーテルが用いられる
〔平岡著「クラウン化合物」講談社サイエンテイ
フイツク（1978）参照〕。この環状エーテルのな
かで、特に芳香族クラウンエーテル、脂環族クラ
ウンエーテル、アルキレンオキシド環状ポリマ
ー、ヘテロ環族クラウンエーテル、環状ポリエー
テルエステルなどが好ましく、このようなものと
しては、例えばシクロヘキサノ−12−クラウン−
４、ジベンゾ−14−クラウン−４、ジベンゾ−18
−クラウン−６、ジシクロヘキサノ−18−クラウ
ン−６、トリベンゾ−18−クラウン−６などのク
ラウンエーテル類、２，４−ジケト−16−クラウ
ン−５、２，４−ジケト−19−クラウン−６、
２，６−ジオキソ−18−クラウン−６などの環状
ポリエ−テルエステル類が挙げられる。また、こ
れらの環状エーテルには、イオウ原子や窒素原子
が一部組込まれていてもよい。 Furthermore, the cyclic ether used in the present invention forms a complex compound with the dichromate and solubilizes the dichromate in an organic solvent, and a cyclic ether that solubilizes an inorganic salt is usually used. [See "Crown Compounds" by Hiraoka, Kodansha Scientific Publishing (1978)]. Among these cyclic ethers, aromatic crown ethers, alicyclic crown ethers, alkylene oxide cyclic polymers, heterocyclic crown ethers, cyclic polyether esters, etc. are particularly preferred, and examples of such ethers include cyclohexano-12 -Crown-
4, dibenzo-14-crown-4, dibenzo-18
- Crown ethers such as crown-6, dicyclohexano-18-crown-6, tribenzo-18-crown-6, 2,4-diketo-16-crown-5, 2,4-diketo-19-crown- 6,
Examples include cyclic polyether esters such as 2,6-dioxo-18-crown-6. Furthermore, these cyclic ethers may partially incorporate sulfur atoms or nitrogen atoms.
環状エーテルと重クロム酸塩とから成る錯化合
物が感光性を示すことは本発明者によつてはじめ
て見いだされたことである。 It was discovered for the first time by the present inventor that a complex compound consisting of a cyclic ether and a dichromate exhibits photosensitivity.
本発明において用いる有機溶媒としては、例え
ばベンゼン、トルエン、キシレンなどの芳香族炭
化水素、クロムホルム、塩化メチレン、トリクレ
ンなどのハロゲン化炭化水素、あるいはアセト
ン、メチルエチルケトン、エタノール、メター
ル、ジメチルホルムアミドなどが挙げられる。こ
れらの溶媒は単独で用いてもよいし、２種以上混
合して用いてもよい。 Examples of the organic solvent used in the present invention include aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chromium form, methylene chloride, and trichlene, and acetone, methyl ethyl ketone, ethanol, methanol, and dimethyl formamide. It will be done. These solvents may be used alone or in combination of two or more.
本発明において用いる高分子化合物は、光エネ
ルギーを吸収した重クロム酸塩との間に新たに化
学結合が生ずるために必要な活性水素を有するも
のであつて、例えば水酸基、アミノ基、アミド
基、イミド基、ウレタン基、カルボキシル基、又
はそれらの残基、尿素残基、アミジン残基などを
有するものであり、これらのなかで好ましくは、
水酸基、アミノ基、アミド基、カルボキシル基、
又はそれらの残基を含有するものである。このよ
うな高分子化合物の具体例を示すと、水酸基を有
するものとしては、ブチラール樹脂、ビニルアル
コールとエチレンの共重合体、ポリ酢酸ビニルの
低けん化物、ヒドロキシメタクリレートの共重合
物、アセチル化セルロースなどが、またアミド基
を有するものとしては、各種ナイロン、メチロー
ル化ナイロン、ポリベンジルグルタメート、アク
リルアミドの共重合物などが挙げられる。 The polymer compound used in the present invention has an active hydrogen necessary for forming a new chemical bond with the dichromate that has absorbed light energy, and has, for example, a hydroxyl group, an amino group, an amide group, It has an imide group, a urethane group, a carboxyl group, or a residue thereof, a urea residue, an amidine residue, etc., and among these, preferably,
hydroxyl group, amino group, amide group, carboxyl group,
or contains those residues. Specific examples of such polymeric compounds include those having hydroxyl groups such as butyral resin, copolymers of vinyl alcohol and ethylene, low saponification products of polyvinyl acetate, copolymers of hydroxymethacrylate, and acetylated cellulose. Examples of those having an amide group include various nylons, methylolated nylons, polybenzyl glutamate, and acrylamide copolymers.
本発明の感光性樹脂組成物を得るには、これら
の高分子化合物を前記の有機溶媒に溶解させ、こ
の溶液にあらかじめ環状エーテルによつて可溶化
された重クロム酸塩の有機溶媒溶液を混合すれば
よい。この際、重クロム酸塩の量は高分子化合物
に対して0.1〜1.0重量％の範囲にあることが望ま
しく、特に0.3〜２重量％の範囲が好適である。
その量が0.1％未満では不溶化に要する露光時間
が著しく長くなり、また10重量％を越えても不溶
化に要する露光時間をそれ以上短縮することがで
きず、事実上無意味である。また、この高分子化
合物と重クロム酸塩の混合溶液に、必要に応じて
メチレンブルーやメチレングリーなどの増感剤を
添加してもよい。 In order to obtain the photosensitive resin composition of the present invention, these polymer compounds are dissolved in the above-mentioned organic solvent, and an organic solvent solution of a dichromate salt previously solubilized with a cyclic ether is mixed with this solution. do it. At this time, the amount of dichromate is preferably in the range of 0.1 to 1.0% by weight, particularly preferably in the range of 0.3 to 2% by weight, based on the polymer compound.
If the amount is less than 0.1%, the exposure time required for insolubilization becomes significantly longer, and even if it exceeds 10% by weight, the exposure time required for insolubilization cannot be further shortened, which is practically meaningless. Furthermore, a sensitizer such as methylene blue or methylene green may be added to the mixed solution of the polymer compound and dichromate, if necessary.
このようにして得られた感光性樹脂組成物は、
従来の重クロム酸塩系感光材料が水を溶媒として
いるのに対し、有機用媒を用いているので製膜時
間を著しく短縮しうる利点があり、また不溶化の
ための感光速度は、例えばブチラール樹脂を用い
た場合には、通常のポリビニルアルコールを用い
た場合と同程度かむしろ数倍の高感度を示す。こ
のように、ブチラール樹脂はポリビニルアルコー
ルに比べて水酸基含有量が約60％減少しているに
もかかわらず、高い感光速度を示すことは意外な
ことである。 The photosensitive resin composition thus obtained is
While conventional dichromate-based photosensitive materials use water as a solvent, using an organic medium has the advantage of significantly shortening film-forming time. When resin is used, the sensitivity is comparable to or even several times higher than when ordinary polyvinyl alcohol is used. Thus, it is surprising that butyral resin exhibits a high photosensitivity rate even though the hydroxyl group content is reduced by about 60% compared to polyvinyl alcohol.
本発明の感光性樹脂組成物を露光によつて不溶
化したものは、出発原料の高分子化合物の物性を
受け継いでいるので耐水性であり、この耐水性の
度合は高分子化合物の選択により任意に調節しう
る。 The photosensitive resin composition of the present invention made insolubilized by exposure to light inherits the physical properties of the starting material polymer compound and is therefore water resistant, and the degree of water resistance can be determined arbitrarily by selecting the polymer compound. Can be adjusted.
本発明の感光性樹脂組成物は、その特長を生か
すことにより、特にホログラフイー感材の簡便な
製法を提供するばかりでなく、耐熱性樹脂を高分
子マトリツクスに採用することによつて、感光能
を有する耐熱性樹脂とすることができるので、特
殊な電子回路作成用として極めて有用である。 By taking advantage of its features, the photosensitive resin composition of the present invention not only provides a particularly simple method for producing holographic sensitive materials, but also provides photosensitivity by employing a heat-resistant resin in the polymer matrix. Since it can be made into a heat-resistant resin having the following characteristics, it is extremely useful for creating special electronic circuits.
次に実施例によつて本発明をさらに詳細に説明
する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
ジシクロヘキサノ−18−クラウン−６ 90mgを
塩化メチレン２cm3に溶解し、これに重クロム酸ア
ンモニウム30mgを加え、よくかきまぜて黄色の溶
液とした。一方、ブチラール樹脂1.0ｇをジオキ
サン13ｇに溶解し、この溶液１ｇに前記の重クロ
ム酸アンモニウム塩の溶液を50mg及び100mg加え
た。このようにして得られた溶液をアルミ板にス
ピンナで塗布し、キセノン灯を用いてステツプタ
ブレツト越しに45秒間露光したところ、前者は４
段、後者は５段まで不溶化した。Example 1 90 mg of dicyclohexano-18-crown-6 was dissolved in 2 cm 3 of methylene chloride, 30 mg of ammonium dichromate was added thereto, and the mixture was stirred well to obtain a yellow solution. On the other hand, 1.0 g of butyral resin was dissolved in 13 g of dioxane, and 50 mg and 100 mg of the above-mentioned ammonium dichromate salt solution were added to 1 g of this solution. The solution obtained in this way was applied to an aluminum plate with a spinner and exposed for 45 seconds through a step tablet using a xenon lamp.
The latter was insolubilized up to 5 stages.
実施例 ２
アルコール可溶ナイロン〔東レ（株）製〕の５
％溶液１ｇに、実施例１で調製した重クロム酸ア
ンモニウムの溶液200mgを添加した。このように
して得た溶液を実施例１と同様にして１分間露光
したところ、３段まで不溶化した。また、ジシク
ロヘキサノ−18−クラウン−６の代りにジベンゾ
−18−クラウン−６を用いてもほぼ同様の結果を
得た。Example 2 Alcohol-soluble nylon [manufactured by Toray Industries, Inc.] 5
% solution was added 200 mg of the ammonium dichromate solution prepared in Example 1. When the solution thus obtained was exposed for 1 minute in the same manner as in Example 1, up to 3 layers were insolubilized. Furthermore, almost the same results were obtained when dibenzo-18-crown-6 was used instead of dicyclohexano-18-crown-6.
実施例 ３
実施例１で調製した重クロム酸アンモニウムの
溶液200mgをポリベンジルグルタメートの５％塩
化メチレン溶液１ｇを混和し、これをアルミ板に
塗布した。この膜をネガ像越しにキセノン灯で１
分間照射し、塩化メチレンで現像したところ鮮明
な画像を得た。Example 3 200 mg of the ammonium dichromate solution prepared in Example 1 was mixed with 1 g of a 5% methylene chloride solution of polybenzyl glutamate, and this was applied to an aluminum plate. This film was examined using a xenon lamp through a negative image.
After irradiation for a minute and development with methylene chloride, a clear image was obtained.
Claims (1)
溶媒に可溶の高分子化合物中に、重クロム酸塩と
環状エーテルとから成る錯化合物を含有させるこ
とを特徴とする耐水性感光性樹脂組成物。 ２ 活性水素を有する水に不溶性で、かつ、有機
溶媒可溶の高分子化合物が、ブチラール樹脂、ア
ルコール可溶ナイロン、ポリグルタミン酸エステ
ルである特許請求の範囲第１項記載の樹脂組成
物。 ３ 環状エーテルが芳香族クラウンエーテル、脂
環族クラウンエーテル、アルキレンオキシド環状
ポリマー、ヘテロ環族クラウンエーテル、環状ポ
リエーテルエステルである特許請求の範囲第１項
記載の樹脂組成物。[Claims] 1. A complex compound consisting of a dichromate and a cyclic ether is contained in a water-insoluble and organic solvent-soluble polymer compound having active hydrogen. Water-resistant photosensitive resin composition. 2. The resin composition according to claim 1, wherein the water-insoluble and organic solvent-soluble polymer compound containing active hydrogen is a butyral resin, alcohol-soluble nylon, or polyglutamic acid ester. 3. The resin composition according to claim 1, wherein the cyclic ether is an aromatic crown ether, an alicyclic crown ether, an alkylene oxide cyclic polymer, a heterocyclic crown ether, or a cyclic polyether ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4599382A JPS58162662A (en) | 1982-03-23 | 1982-03-23 | Water-resistant photo-sensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4599382A JPS58162662A (en) | 1982-03-23 | 1982-03-23 | Water-resistant photo-sensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58162662A JPS58162662A (en) | 1983-09-27 |
| JPH0335337B2 true JPH0335337B2 (en) | 1991-05-27 |
Family
ID=12734644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4599382A Granted JPS58162662A (en) | 1982-03-23 | 1982-03-23 | Water-resistant photo-sensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58162662A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6251589B2 (en) * | 2014-02-05 | 2017-12-20 | 旭化成株式会社 | Polyamide resin composition and molded product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4866151A (en) * | 1971-12-13 | 1973-09-11 | ||
| JPS5251202A (en) * | 1975-10-20 | 1977-04-25 | Hitachi Ltd | Photoosensitive resin composition |
-
1982
- 1982-03-23 JP JP4599382A patent/JPS58162662A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4866151A (en) * | 1971-12-13 | 1973-09-11 | ||
| JPS5251202A (en) * | 1975-10-20 | 1977-04-25 | Hitachi Ltd | Photoosensitive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58162662A (en) | 1983-09-27 |
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