JPS59211036A - Photopolymerizable image forming composition - Google Patents
Photopolymerizable image forming compositionInfo
- Publication number
- JPS59211036A JPS59211036A JP8562583A JP8562583A JPS59211036A JP S59211036 A JPS59211036 A JP S59211036A JP 8562583 A JP8562583 A JP 8562583A JP 8562583 A JP8562583 A JP 8562583A JP S59211036 A JPS59211036 A JP S59211036A
- Authority
- JP
- Japan
- Prior art keywords
- activator
- dye
- forming composition
- image forming
- group element
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000031700 light absorption Effects 0.000 claims description 6
- 238000003384 imaging method Methods 0.000 claims 1
- 239000012190 activator Substances 0.000 abstract description 16
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 5
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 125000004386 diacrylate group Chemical group 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- 229920005596 polymer binder Polymers 0.000 abstract 1
- 239000002491 polymer binding agent Substances 0.000 abstract 1
- 229910052711 selenium Inorganic materials 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 229910052714 tellurium Inorganic materials 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 18
- -1 P-aminophenyl ketone Chemical class 0.000 description 15
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VUBUXALTYMBEQO-UHFFFAOYSA-N 2,2,3,3,3-pentafluoro-1-phenylpropan-1-one Chemical compound FC(F)(F)C(F)(F)C(=O)C1=CC=CC=C1 VUBUXALTYMBEQO-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000061408 Eugenia caryophyllata Species 0.000 description 1
- 241000255896 Galleria mellonella Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 241000282806 Rhinoceros Species 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- ZWJINEZUASEZBH-UHFFFAOYSA-N fenamic acid Chemical compound OC(=O)C1=CC=CC=C1NC1=CC=CC=C1 ZWJINEZUASEZBH-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は光重合可能な画像形成用組成物に関する0
従来より、高分子材料からなるバインダー、光重合性を
有するモノマーもしくはオリゴマー、光重合開始剤など
からなる組成物を基材面に塗布したものに、陰画等を通
して光を当て、光が当たった部分を重合ないし架橋させ
て溶剤に対し、不溶化させ、光が当たってない部分を溶
出させることにより基材上に画像を形成し5ることが知
られており、この原理は版材やプリント配線板の製造に
応用されている。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerizable image forming composition. The material coated on the substrate is exposed to light through a negative image, etc., and the areas exposed to the light polymerize or crosslink, making them insoluble in solvents, and the areas not exposed to light are eluted, creating an image on the substrate. It is known to form 5, and this principle is applied to the production of plate materials and printed wiring boards.
又、上記組成物に例えばロイコ染料等の光発色剤を加え
ておき、光が当たった部分と当たらなかった部分とを明
確に判別できる様にし、それによって多重露光等を可能
にすることも知られている。It is also known that by adding a photochromic agent such as a leuco dye to the above composition, it is possible to clearly distinguish between areas that are exposed to light and areas that are not, thereby making it possible to perform multiple exposures, etc. It is being
例えば、特公昭48−38403号公報により開示され
たものでは、エチレン系モノマーにイミダゾリルニを体
及びP−アミノフェニルケトンを加わえた組成物に、ロ
イコ染料を混合しているが、光源として一般に用いられ
る高圧水銀灯などの紫外線光源を用いて、組成物中に光
重合ないしは架橋と同時に染料の発色を行なわせる場合
は、染料の存在により、光重合ないしは架橋速度が低下
し、そのため露光時間を長くしなければならなくなる欠
点を生じる。For example, in the method disclosed in Japanese Patent Publication No. 48-38403, a leuco dye is mixed in a composition prepared by adding imidazolyl and P-aminophenyl ketone to an ethylene monomer, but it is generally used as a light source. When coloring a composition using an ultraviolet light source such as a high-pressure mercury lamp, the photopolymerization or crosslinking rate decreases due to the presence of the dye, so the exposure time must be lengthened. This creates the disadvantages of having to do so.
これは、光重合開始剤などに吸収される光エネルギーが
光重合ないしは架橋と、染料の発色の両方に分割して使
用されることに起因するものと推測される。This is presumed to be due to the fact that the light energy absorbed by the photopolymerization initiator and the like is divided and used for both photopolymerization or crosslinking and color development of the dye.
本発明は上記の如き従来の欠点を解消し、染料の発色の
ために感度が低下して露光時間が長くなることのない、
感光性が良好にして、作業性に優れ、多重露光にも適し
た画像形成用組成物を提供することを目的としてなされ
たものである0
即ち、本発明の要旨は高分子材料からなるバインダー、
光重合性を有する七ツマ−もしくはオリゴマー、光重合
開始剤、還元型染料及び前記光重合開始剤とは異なる光
吸収波長域を有する第■b族オニクム塩型光活性化剤を
含有することを特徴とする光重合可能な画像形成用組成
物に存する。The present invention solves the above-mentioned conventional drawbacks, and eliminates the problem of decreased sensitivity and increased exposure time due to dye color development.
The purpose of the present invention is to provide an image forming composition that has good photosensitivity, excellent workability, and is suitable for multiple exposure.
Contains a photopolymerizable hexamer or oligomer, a photopolymerization initiator, a reduced dye, and a Group 1b onicum salt type photoactivator having a light absorption wavelength range different from that of the photopolymerization initiator. The present invention relates to a photopolymerizable image forming composition.
本発明に用いられるバインダーは、高分子材料からなる
もので、従来より画像形成用組成物のバインダーとして
用いられていたものはいずれも使用可能であり、例えば
溶剤現像型では溶剤に良俗であることが重要である。具
体的には、アセチルセルロース、アセチルフチルセルロ
ース、ポリアクリル酸メチル、ポリメタクリル酸、メタ
クリル酸−メタクリル酸メチル共重合体等が挙げられる
。The binder used in the present invention is made of a polymeric material, and any binder conventionally used as a binder for image-forming compositions can be used. is important. Specific examples include acetylcellulose, acetyl phthylcellulose, polymethyl acrylate, polymethacrylic acid, methacrylic acid-methyl methacrylate copolymer, and the like.
本発明に用いられる光重合性を有するモノマーもしくは
オリゴマーとは、光重合開始剤の存在下において、元の
照射により活性化され、重合を開始するものを指し、常
圧で100℃以上の沸点を有し、エチレン系末端基を少
なくとも1個有しているものが好適に用いられる。具体
的には、ペンタエリスリトールアクリレート(クリレー
ト)トリエチレングリコールシアクリ杉
レート(又はメタクリレート)、ポリメチレンタフリレ
ート)等が、あるいはこれらが更にオリゴマー化したも
のが挙げられる。The photopolymerizable monomer or oligomer used in the present invention refers to a monomer or oligomer that is activated by original irradiation and starts polymerization in the presence of a photopolymerization initiator, and has a boiling point of 100°C or more at normal pressure. Those having at least one ethylene terminal group are preferably used. Specifically, examples thereof include pentaerythritol acrylate (acrylate), triethylene glycol cyacrylate (or methacrylate), polymethylene tafrylate), and oligomerized products thereof.
これらの光重合性を有するモノマーもしくは、オリゴマ
ーは、光重合によりバインダーにからみついて不溶化し
たり、感光基を有するバインダー高分子材料と重合ある
いは架橋反応することで強固な画像形成する。These photopolymerizable monomers or oligomers form strong images by being entangled with the binder and becoming insolubilized by photopolymerization, or by polymerizing or crosslinking with the binder polymeric material having a photosensitive group.
本発明に用いられる光重合開始剤は、従来から用いられ
る開始剤が使用できるが、内でもフェニルケトン系の光
重合開始剤が好適である。As the photopolymerization initiator used in the present invention, conventionally used initiators can be used, but phenylketone-based photopolymerization initiators are particularly suitable.
光重合開始剤の具体例としては、ベンゾフェノン、(入
max=330nm)(入mawは光吸収スペクトルの
最高ピークの波長を示す)、P、P’−ビス (ジメチ
ルアミノ)ベンゾフェノン (以下ミヒラーケトンとい
う) (入max−370nm)などのP−アミノフェ
ニルケトン、ベンゾイン、ベンツ゛インメチルエーテル
、ペンツインエチルエーテル、ペンツインエチルエーテ
ル、ベンツインイソプロビルエーテル、ペン5−
ジルアンスラキノン、2−メチル−アンスラキノン、2
−エチル−アンスラキノン、2−tertブチル−アン
スラキノン、2−アミノアンスラキノン等が挙げられ、
多くは320〜370nmの波長の元エネルギーを吸収
して、重合開始剤として作用する。Specific examples of photopolymerization initiators include benzophenone, (input max = 330 nm) (input maw indicates the wavelength of the highest peak of the light absorption spectrum), P,P'-bis (dimethylamino)benzophenone (hereinafter referred to as Michler's ketone) P-aminophenyl ketone, benzoin, benzine methyl ether, pentuine ethyl ether, pentuine ethyl ether, benzine isopropyl ether, pen 5-dylanthraquinone, 2-methyl-anthraquinone (input max - 370 nm), etc. Quinone, 2
-ethyl-anthraquinone, 2-tertbutyl-anthraquinone, 2-aminoanthraquinone, etc.
Many absorb original energy at wavelengths of 320 to 370 nm and act as polymerization initiators.
又、これらの光重合開始剤は2種以上を混合して用いる
こともでき、例えばベンゾフェノンとミヒラーケトンの
混合物は吸収する元の波長がずれており、照射光による
重合開始効率が改良されて、露光時間がよυ短縮される
ので好適である。Furthermore, these photopolymerization initiators can be used as a mixture of two or more types. For example, a mixture of benzophenone and Michler's ketone absorbs at different wavelengths, improving the efficiency of polymerization initiation by irradiation light, and increasing the efficiency of light exposure. This is preferable because it saves a lot of time.
次に、本発明においては、還元型染料及び第vtb族オ
ニクム塩型元活性化剤の組合わせが、元発色剤として用
いられる。該元活性化剤は前記光重合開始剤とは異なる
光吸収波長域を有するものとなされる。Next, in the present invention, a combination of a reduced dye and a Group VTB onicum salt-type original activator is used as the original color former. The original activator has a light absorption wavelength range different from that of the photopolymerization initiator.
即ち、本発明における還元型染料は第vtb族オニウム
塩型元活性化剤により酸化されて着色型となるものであ
り、具体的には、メチルカプリ6−
ルプル−(無色−り、)ルエンブルー (無色−紫)、
フェニルアントラニル酸(無色→赤紫)やラクトン型又
はラクタム型のトリアリールメタン系染料あるいはラク
トン型又はラクタム型のフルオラン系染料、更に具体的
にはクリスタルバイオレットラクトン、マラカイトグリ
ーンラクトン、ローダミンラクタム、次の構造式■。That is, the reduced dye in the present invention is oxidized by the VTB group onium salt type activator to become a colored dye, and specifically, methylcapri-6-ruple-(colorless)-ruene blue ( colorless-purple),
Phenyl anthranilic acid (colorless → reddish purple), lactone type or lactam type triarylmethane dyes, lactone type or lactam type fluoran dyes, more specifically crystal violet lactone, malachite green lactone, rhodamine lactam, the following: Structural formula■.
■で示されるものが挙げられる。Examples include those shown in ■.
本発明において使用される、第■b族オニウム塩型光活
性化剤は、次に示す一般式の化合物を指す。The Group 1b onium salt type photoactivator used in the present invention refers to a compound having the following general formula.
(式中R,,R2,R3はアリール基、■bは硫黄、セ
レン、テルルから選ばれる周期律表第Vl b族元素、
Mは遷移全開、希土類元素、ランクメイド類元素、アク
チノイド類元素及びB、P、As等の半金属から選ばれ
る元素、Xはハロゲンでありnは1〜6の整数を示す。(In the formula, R,, R2, and R3 are aryl groups, and
M is an element selected from a fully transitioned element, a rare earth element, a rank-made element, an actinide element, and a metalloid such as B, P, and As; X is a halogen; and n is an integer of 1 to 6.
)
式中の錯陰イオンとしては、BF、、 PF6.SbF
。) The complex anions in the formula include BF, PF6. SbF
.
Fee/−、SnC/6−、SbC/6ミ旧C15−、
A t F6−3. G a Et4−などがある。Fee/-, SnC/6-, SbC/6mi old C15-,
A t F6-3. Examples include G a Et4-.
これらの第■b族オニワム塩元活性化剤の具体例として
は、次のものが挙げられる。即ち、トリフェニルスルホ
ニクムへキサフルオロアーセネート (入max=29
8 nm)(入maxは光吸収スペクトルの最高ピーク
の波長を示す)、トリス(4−ト)キクフェニル)スル
ホニタムへキサフルオロアーセネート(入max=28
0nm)、ジフェニル−2,5−ジメチルフェニルスル
ホニクムへキサフルオロアーセネート (入max=3
07 nm) 、)リス(4−メチルフェニル)スルホ
ニウムフルオロボーレイト(入max=278nm)、
あるいは
等である。Specific examples of these Group 1b Oniwam salt source activators include the following. That is, triphenylsulfonicum hexafluoroarsenate (input max = 29
8 nm) (input max indicates the wavelength of the highest peak of the optical absorption spectrum), tris(4-to)kyphenyl)sulfonitum hexafluoroarsenate (input max = 28
0nm), diphenyl-2,5-dimethylphenylsulfonicum hexafluoroarsenate (input max=3
07 nm) ,) Lis(4-methylphenyl)sulfonium fluoroborate (input max = 278 nm),
Or, etc.
これらの第■b族オニクム塩は、前記した光重合開始剤
と異なる光吸収波長域を有するものが選択して使用され
るが、両者の光吸収波長域の差は一般に1吸収スペクト
ルの最高のピークを示す波長の差で約20nm以上彦す
れる。但し、上記元活性剤及び光重合開始剤の吸収スペ
クトルのM焉のピークの差が10 nmでもよく、逆に
分布が共に広い場合は例えば50 nm以上必要である
から、両者は、吸収スペクトルのピークの波長及び分布
を考慮して、前元重合開始剤−9=
に主として吸収されて利用される波長の元が、上記元活
性化剤を活性化して酸化剤として働かせ、前記還元型染
料の発色にも利用されて組成物の重合硬化を実質的に阻
害することの彦い波長域の差があるものとなされるので
ある。These Group Ⅲb onicum salts are selected to have a light absorption wavelength range different from that of the photopolymerization initiator described above, but the difference in the light absorption wavelength range between the two is generally determined by the highest absorption spectrum. The difference in wavelength showing the peak is about 20 nm or more. However, the difference between the M peaks of the absorption spectra of the original activator and the photopolymerization initiator may be 10 nm, and conversely, if the distributions of both are wide, the difference is, for example, 50 nm or more. Considering the wavelength and distribution of the peak, the source of the wavelength mainly absorbed and utilized by the former polymerization initiator -9= activates the original activator to act as an oxidizing agent and oxidizes the reduced dye. The difference in the wavelength range is used for color development and substantially inhibits polymerization and curing of the composition.
尚、上記の第■b族オニウム塩の製造については、 J
、Am、Chem、Soc、、91,145 (19
69年)やJ、Org、Chem、、35.A8,23
32 (1970年)によって詳細に説明されている
。Regarding the production of the above Group ■b onium salt, please refer to J.
,Am,Chem,Soc,,91,145 (19
69) and J, Org, Chem, 35. A8,23
32 (1970).
本発明で用いられる第■b族オニウム塩型元活性化剤は
、還元型染料に対する他の元活性化剤とは異なり、気泡
が発生したシ、室温で長期間保存した時KPMしたりす
る恐れがなく、長期の品質安定性に優れている。Unlike other base activators for reduced dyes, the Group B onium salt type base activator used in the present invention may generate bubbles or cause KPM when stored at room temperature for a long period of time. It has excellent long-term quality stability.
本発明組成物を薄い銅箔を張りつけた銅張積層板等に核
層して用いるに際して、その密着性を改善するために密
着促進剤を混合してもよい。When the composition of the present invention is used as a core layer on a copper-clad laminate or the like to which a thin copper foil is attached, an adhesion promoter may be mixed therein in order to improve its adhesion.
又、熱重合禁止剤、可塑剤、難燃化剤等を必要に応じて
加わえることができる。Further, thermal polymerization inhibitors, plasticizers, flame retardants, etc. can be added as necessary.
本発明組成物を得るには、上記した高分子材−1〇−
料から々るバインダー、光重合性モノマーもしくはオリ
ゴマー、光重合開始剤、還元型染料及び前記光重合開始
剤とは異なる光吸収波長域を有する第■b属オニウム塩
型元活性化剤、更に必要があれば密着促進剤等を加わえ
合わせて均一4混合すれば良いのであるが、通常は合成
樹脂等の基材表面に薄膜を形成して用いられるので、メ
チルエテルケトンその他の適宜な溶剤に混合して基材等
に塗布することが可能な粘度を有し、溶剤の揮発により
乾燥させることができる液状組成物とすることが好まし
い。To obtain the composition of the present invention, a binder, a photopolymerizable monomer or oligomer, a photopolymerization initiator, a reduced dye, and a light absorbing material different from the photopolymerization initiator are used. All you have to do is add a Group B onium salt type activator having a wavelength range, and if necessary, an adhesion promoter, etc., and mix them uniformly. Since it is used in the form of a thin film, it is a liquid composition that has a viscosity that allows it to be mixed with methyl ether ketone or other appropriate solvent and applied to a substrate, etc., and that can be dried by evaporation of the solvent. It is preferable.
又、上記組成物の成分の量的関係としては、高分子材料
からなるバインダー100重量部に対し、光重合性を有
するモノマーもしくはオリゴマーが10〜300重菫部
、光重合開始剤が0.1〜20重蓋部、還元性染料が0
.01〜10重量部、第Vlb族オニウム塩元活性化剤
が0001〜2重景部を用いるのがよい。In addition, the quantitative relationship of the components of the above composition is as follows: 10 to 300 parts by weight of a photopolymerizable monomer or oligomer and 0.1 parts by weight of a photopolymerization initiator per 100 parts by weight of a binder made of a polymeric material. ~20-layer lid, 0 reducing dyes
.. It is preferable to use 01 to 10 parts by weight and 0001 to 2 parts by weight of the Vlb group onium salt source activator.
本発明組成物はレリーフ印刷版の作成やフォトレジスト
の用途の用途に用いられることができ、通常は透明なノ
ート状の基材上に本発明組成物を溶剤に溶かした溶液を
塗布し、乾燥させて必要であればその上に保護膜を形成
する。The composition of the present invention can be used for making relief printing plates and photoresist applications. Usually, a solution of the composition of the present invention dissolved in a solvent is applied onto a transparent notebook-like substrate, and then dried. Then, if necessary, a protective film is formed thereon.
そして、これをフォトレジスト像等の画像を形成すべき
部材、例えば薄い銅箔を張りつけた銅張積層板の表面に
対し、必要であれば保護膜を除去して、熱融着等によっ
て積層し、その上からネガフィルム等を通じて活性光を
照射して露光部分を感光させ、その後必要であれば透明
なノート状の基材を剥離し、未旙元部分を溶剤等により
除去して現像を行い、以後表面の未保換部分(溶剤によ
り本発明組成物の除去された部分)をエツチング、また
は金−メッキ処理等を行うやり方で使用される。Then, if necessary, remove the protective film and laminate this onto the surface of a member on which an image such as a photoresist image is to be formed, such as a copper-clad laminate with thin copper foil pasted, by heat fusion or the like. , then irradiate the exposed area with active light through a negative film, etc., then peel off the transparent notebook-like base material if necessary, remove the unstained area with a solvent, etc., and develop. Thereafter, the unrestored portion of the surface (the portion from which the composition of the present invention has been removed by a solvent) is etched or gold-plated.
そして本発明組成物は、その中に含まれる第■b族オニ
クム塩型元活性化剤が還元型染料を光活性化酸化するこ
とにより、露光部分が発色するので、露光過程での露光
部分と非露光部分の判別が容易であり、多重露光する場
合や露光状態を確認する場合に非常に便利である。In addition, in the composition of the present invention, the exposed area develops color by photoactivating and oxidizing the reduced dye by the group (b) onicum salt type original activator contained therein. It is easy to distinguish unexposed areas, and it is very convenient when performing multiple exposures or checking the exposure state.
更に、本発明組成物における還元型染料及び第■b族オ
ニウム塩屋光活性化剤の組合わせの光発色剤は、露光後
短時間で着色像が消えたりすることなく、着色安定性に
優れ作業性が改善されるのである。Furthermore, the photocoloring agent in the composition of the present invention, which is a combination of a reduced dye and a Group 1b onium salt photoactivator, has excellent coloring stability and is easy to work with, without causing the colored image to disappear in a short period of time after exposure. This will improve your sexuality.
又、従来においてロイコ染料系の発色剤が用いられた場
合には、照射光のエネルギーが組成物の重合ないし架橋
と発色の両方に分割されるためと推測されるが、組成物
の重合硬化反応速度が低下し、よシ長時間の露光を要し
ていたのに比べて、本発明組成物においてはこの様な欠
点がなく、短時間の露光で十分であり、露光作業性にも
優れているのである。In addition, when a leuco dye-based coloring agent is conventionally used, it is presumed that the energy of the irradiated light is divided into both polymerization or crosslinking of the composition and color development, but the polymerization and curing reaction of the composition In contrast, the composition of the present invention does not have these drawbacks, requires only a short exposure time, and has excellent exposure workability. There is.
〔実施例1]
ポリメチルメタクリレート(Hw 二z、。xto’)
60 Fトリメチロールプロパントリアクリレート
33yベンゾフエノン
3.5yミヒラーケトン 1
.5yクリスタルバイオレツト2クトン 1.Q
yトリフェニルスルホニウムヘキサフルオロアーセネイ
ト 0.1y13−
以上の化合物をメチルエチルケトンに溶解し、全址を3
00Fとした溶液をポリエチレンテレフタレートフィル
ム支持体に乾燥後の厚みが50μmになるように塗布し
、被膜を乾燥した後、これを115℃の温度で銅が被覆
されたガラス繊維強化エボキノ樹脂板に上記被膜が銅面
と接するように積層した。[Example 1] Polymethyl methacrylate (Hw2z,.xto')
60 F trimethylolpropane triacrylate
33y benzophenone
3.5y Michler Ketone 1
.. 5y Crystal Violet 2 Chton 1. Q
y triphenylsulfonium hexafluoroarsenate 0.1y13- Dissolve the above compound in methyl ethyl ketone and add 3
A solution of 00F was applied to a polyethylene terephthalate film support so that the thickness after drying would be 50 μm, and after drying the film, it was applied to a copper-coated glass fiber-reinforced evoquino resin plate at a temperature of 115°C. The layers were laminated so that the coating was in contact with the copper surface.
次に、上記の感光積層板を400W高圧水銀灯から1m
の所において、テスト用陰画(2V−階段露光ステップ
ガイド=陰画が透明な状態から次第に濃くなされf丁ず
つ21階段に磯くなq h −c イル> @Fll〔
lH’+cX・i、[9!iF−eM、’+= !tL
J及びこれと重ならない様に並べて置かれたプリント配
線回路用陰画を介して、真空枠中で90ミリジユール(
mj)/cdの露光を行った。露光時間は20秒であっ
た0
露光後、ポリエチレンテレフタレートフィルム支持体を
剥離し、露光層を1.1.1−ト’)クロロエタン中に
浸漬して現像しく未露光部分を除去)乾燥した。テスト
用陰画による画像にお14−
いては、9階段画像が銅が被覆されたガラス繊維強化エ
ボキ/樹脂板に残シ、又、プリント配線用画像における
解像力は50μmであった。Next, the above photosensitive laminate was placed 1m from a 400W high pressure mercury lamp.
At the test negative (2V-stair exposure step guide = negative is gradually made darker from a transparent state to 21 steps at a time).
lH'+cX・i, [9! iF-eM,'+=! tL
90 millijoules (
mj)/cd exposure was performed. The exposure time was 20 seconds. After exposure, the polyethylene terephthalate film support was peeled off, the exposed layer was immersed in chloroethane (1.1.1-t'), developed, and the unexposed areas were removed) and dried. In the test negative image, a 9-step image remained on the copper coated glass fiber reinforced epoxy/resin board, and the resolution of the printed wiring image was 50 μm.
又、上記現像前、未露光部分は無色であり、露光部分は
明瞭に紫色に着色され、発色吸光度0.5コントラスト
が鮮明で露光検査を行うのに十分であった。更に、この
露光後−昼夜放置し、翌日現像後エツチングを行い、更
に脱膜してプリント回路を形成したが、脱膜に至る迄露
光部分は明瞭な発色が残っており、現像、エツチング、
脱膜の状態の検査を行うのに便利であった。Furthermore, before the development, the unexposed area was colorless, the exposed area was clearly colored purple, and the color absorbance 0.5 contrast was clear and sufficient for conducting an exposure test. Furthermore, after this exposure, the circuit was left to stand day and night, and the next day it was developed and etched, and the film was removed to form a printed circuit.
This was convenient for inspecting the state of membrane removal.
〔実施例2〕
還元型染料としてクリスタルバイオレットラクトンの代
りにローダミンラクタム、第ylb族オニウム塩型元活
性化剤として、トリフェニルスルホニクムへキサフルオ
ロアーセネイトの代りニ、ジフェニル2.5−シメチル
フェニルスルフオニクムヘキサフルオロアーセネイトを
用いること以外は実施例1と同様にして、テスト用陰画
、プリント配線用陰画の現像、プリント配線の形成を行
った。[Example 2] Rhodamine lactam was used instead of crystal violet lactone as a reduced dye, and di-diphenyl 2,5-sulfonic acid was used instead of triphenylsulfonicum hexafluoroarsenate as a group ylb onium salt type activator. The test negative image, the negative image for printed wiring were developed, and the printed wiring was formed in the same manner as in Example 1 except that methylphenylsulfonicum hexafluoroarsenate was used.
その結果は、露光部分の硬化の程度、解像力、発色の程
度がいずれも実施例1と同様であることが認められた。The results showed that the degree of curing, resolution, and color development of the exposed areas were all the same as in Example 1.
〔比較例1〜4]
下表に示される組成物を用いて、実施例1と同様に露光
、現像、プリント回路の形成を行った。[Comparative Examples 1 to 4] Exposure, development, and formation of a printed circuit were performed in the same manner as in Example 1 using the compositions shown in the table below.
結果は下表に示す通りであった。The results were as shown in the table below.
犀丁斤θ
トキシフェニルイミダゾリルニ量体
注2)実施例1と同様に、テスト用陰画における画像で
光重合で残った階段数を表示
性3)比較例3.4は200μmより大きく解像力が悪
いことを示すRhinoceros clove θ Toxyphenylimidazolyl dimer Note 2) As in Example 1, the number of steps remaining due to photopolymerization can be displayed in the test negative image. 3) Comparative Example 3.4 is larger than 200 μm and has poor resolution. show that
Claims (1)
モノマーもしくはオリゴマー、光重合開始剤、還元型染
料及び前記光重合開始剤とは異なる光吸収波長域を有す
る第1b族オニクム塩型光活性化剤を含有することを特
徴とする光重合可能な画像形成用組成物 2、第■b族オニクム塩がトリアリルスルホニクム塩で
ある特許請求の範囲第1項記載の光重合可能な画像形成
用組成物[Scope of Claims] L A binder made of a polymeric material, a photopolymerizable monomer or oligomer, a photopolymerization initiator, a reduced dye, and a Group 1b onicum having a light absorption wavelength range different from that of the photopolymerization initiator. Photopolymerizable image-forming composition 2 characterized by containing a salt-type photoactivator, the photopolymerizable composition according to claim 1, wherein the Group 1b onicum salt is a triallylsulfonicum salt. Polymerizable imaging composition
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8562583A JPS59211036A (en) | 1983-05-16 | 1983-05-16 | Photopolymerizable image forming composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8562583A JPS59211036A (en) | 1983-05-16 | 1983-05-16 | Photopolymerizable image forming composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS59211036A true JPS59211036A (en) | 1984-11-29 |
Family
ID=13864015
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8562583A Pending JPS59211036A (en) | 1983-05-16 | 1983-05-16 | Photopolymerizable image forming composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59211036A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63261352A (en) * | 1987-04-20 | 1988-10-28 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPH01298348A (en) * | 1988-05-27 | 1989-12-01 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
EP1251400A3 (en) * | 2001-04-20 | 2005-02-23 | E.I. Du Pont De Nemours And Company | A photopolymerizable element for use as a flexographic printing plate and a process for preparing the plate from the element |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS542720A (en) * | 1977-06-08 | 1979-01-10 | Konishiroku Photo Ind Co Ltd | Forming method of photopolymerized image |
JPS54147829A (en) * | 1978-05-09 | 1979-11-19 | Dynachem Corp | Carbonyl halogenide as activator of phototropism composition |
JPS5513780A (en) * | 1978-05-09 | 1980-01-30 | Dynachem Corp | Fluoran coupler containing phototropic photosensitive composition |
-
1983
- 1983-05-16 JP JP8562583A patent/JPS59211036A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS542720A (en) * | 1977-06-08 | 1979-01-10 | Konishiroku Photo Ind Co Ltd | Forming method of photopolymerized image |
JPS54147829A (en) * | 1978-05-09 | 1979-11-19 | Dynachem Corp | Carbonyl halogenide as activator of phototropism composition |
JPS5513780A (en) * | 1978-05-09 | 1980-01-30 | Dynachem Corp | Fluoran coupler containing phototropic photosensitive composition |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63261352A (en) * | 1987-04-20 | 1988-10-28 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPH01298348A (en) * | 1988-05-27 | 1989-12-01 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
EP1251400A3 (en) * | 2001-04-20 | 2005-02-23 | E.I. Du Pont De Nemours And Company | A photopolymerizable element for use as a flexographic printing plate and a process for preparing the plate from the element |
US7754412B2 (en) | 2001-04-20 | 2010-07-13 | E. I. Du Pont De Nemours And Company | Process for preparing a flexographic printing plate from a photopolymerizable element |
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