JPS59189340A - Photopolymerization initiator composition having high sensitivity - Google Patents
Photopolymerization initiator composition having high sensitivityInfo
- Publication number
- JPS59189340A JPS59189340A JP6379683A JP6379683A JPS59189340A JP S59189340 A JPS59189340 A JP S59189340A JP 6379683 A JP6379683 A JP 6379683A JP 6379683 A JP6379683 A JP 6379683A JP S59189340 A JPS59189340 A JP S59189340A
- Authority
- JP
- Japan
- Prior art keywords
- org
- peroxide
- compounds
- dye
- initiator composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はエチレン性不飽和化合物重合用の光重付開始剤
組成物に関し、さらに詳しくは、紫外光および可視光に
低光量で感光し、またレーザー用に使用可能な高感度光
重合開始剤組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerization initiator composition for the polymerization of ethylenically unsaturated compounds, and more particularly to a photopolymerization initiator composition that is sensitive to ultraviolet and visible light at low doses and is usable for laser applications. This invention relates to a highly sensitive photopolymerization initiator composition.
不飽和結合を分子中に含むモノマー、オリゴマー、及び
ポリマーは光■I合開始剤の存在下で光10合すること
は良く知られている。またこの現象は。It is well known that monomers, oligomers, and polymers containing unsaturated bonds in their molecules undergo photocoagulation in the presence of a photocoagulation initiator. This phenomenon also occurs.
印刷版やプリント基板、IC等を作製する際に用いられ
ろ九重倉型のフォトポリマーやフォトレジストとして広
く利用されている。It is widely used as a Kokonegura-type photopolymer and photoresist, which is used in the production of printing plates, printed circuit boards, ICs, etc.
これらに使用する光M@開始剤としては、従来から種々
の物質が報告され、実際に使用されている。たとえば、
ベンゾイン系化合物としてベンゾイン、ベンゾインメチ
ルエーテル、ベンゾインエチルエーテル等、カルボニル
化合物としてベンジル、ベンゾフェノン、アセトフェノ
ン、ミヘラーズケトン等、アゾ化合物としてアソビスイ
ソブチロニトリル、アゾジベンゾイル等、また硫黄化合
物としてジベンゾチアゾリルスルフィド、テトラエチル
チウラムジスルフィド等、ハロゲン化合物として四臭化
炭素、トリブロムフェニルスルホン等、その他に1.2
−ベンズアントラキノンなどがある。Various substances have been reported and actually used as photo-M@initiators used in these. for example,
Benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, etc. Carbonyl compounds include benzyl, benzophenone, acetophenone, Micher's ketone, etc. Azo compounds include azobisisobutyronitrile, azodibenzoyl, etc. Sulfur compounds include dibenzothiazolyl sulfide , tetraethylthiuram disulfide, etc., halogen compounds such as carbon tetrabromide, tribromphenyl sulfone, etc. 1.2
- Examples include benzanthraquinone.
しかしながら、これらの光重合開始剤は未だ充分満足で
きろものではなく、独々の不飽和化合物と組み合わせた
場合、フォトポリマーとして必ずしも良好な感度を有し
ているとはいえなかった。However, these photopolymerization initiators are still not completely satisfactory, and when combined with individual unsaturated compounds, they cannot necessarily be said to have good sensitivity as a photopolymer.
また、近年、レーザーを用いて画像を形成する方法が検
討され、印刷版作製におけろレーザー直接製版や、1ノ
ーザーファクシミリ、ホログラフィ等がすでに実用化の
段階にあり、さらに今後多くの方面への適用が検討され
、かつ期待されている。In addition, in recent years, methods of forming images using lasers have been studied, and in printing plate production, laser direct plate making, one-north facsimile, holography, etc. are already at the stage of practical application, and many more fields will be developed in the future. Its application is being considered and expected.
この除用いられろレーザー用感光材料としては銀塩感光
材料、電子写真材料、フォトクロミック材料、フォトポ
リマー等が用いられるが、このうちフォトポリマーは銀
塩感光羽村や電子写真材料に比べると非常に感度が低く
、またその感光波長域も紫外から可視光の極短波長領域
である。たとえば銀塩フィルム(コグリスオルソフィル
ム2556タイブ3)の感度はAr+レーザーの波長4
88nmの単色光の必要エネルギー量は0.02 (L
、5rn J /−であるが、フォトポリマー(コダッ
クホリマチツクリソプレートLN −L )では7oo
omJ/cJも必要であり、波長351 / 364
n mの紫外ll1lを用いても] OOm J /
taのエネルキーが必要である。Silver salt photosensitive materials, electrophotographic materials, photochromic materials, photopolymers, etc. are used as photosensitive materials for lasers, but among these, photopolymers have extremely high sensitivity compared to silver salt photosensitive materials and electrophotographic materials. It has a low sensitivity to light, and its sensitive wavelength range is from ultraviolet to visible light. For example, the sensitivity of silver halide film (Cogris Orthofilm 2556 Type 3) is Ar + laser wavelength 4.
The amount of energy required for monochromatic light of 88 nm is 0.02 (L
, 5rn J/-, but for photopolymer (Kodak Horimachi Chrysoplate LN -L) it is 7oo
omJ/cJ is also required, wavelength 351/364
Even if ultraviolet light of nm is used] OOm J /
The energy key of ta is required.
このように従来のフォトポリマーでは感度および感光波
長域ともに満足されろものでなく、特に可視光レーザー
用の感光材料としては不適箔なものであった。As described above, conventional photopolymers are unsatisfactory in both sensitivity and sensitive wavelength range, and are particularly unsuitable as photosensitive materials for visible light lasers.
沫
このような背景から本発明者らが、上記の点に留意し鋭
意研究した結果、有機過酸化物と特定の構造を有する有
機染料化合物とを組み合わせたものが可視光領域におい
ても非常に良好な光重合開始能を有しており、銀塩感光
羽村に近い高KIA度であることを見いだして1本発明
に到達した。Against this background, the inventors of the present invention have conducted extensive research keeping in mind the above points, and have found that a combination of an organic peroxide and an organic dye compound with a specific structure is extremely effective even in the visible light region. The present invention was achieved by discovering that the photopolymerization initiator has a high KIA degree close to that of silver salt photosensitive Hamura.
本発明は、有機過酸化物の1棟または2棟以上と、有機
染料化合物の1種または2種以上とを組み合わせて成る
光重合開始剤組成物を提供するものである。The present invention provides a photopolymerization initiator composition comprising a combination of one or more organic peroxides and one or more organic dye compounds.
本発明に1史用されろ有機過酸化物は、分子中に酸素−
酸素結合を1個以上有する有機化合物のほとんとすべて
が含まれるが、その例としては、メチルエチルケトンパ
ーオキサイド、シクロヘキサノンパーオキサイド、3,
3.5−トリメチルシクロヘキサノンパーオキサイド、
メチルシクロヘキサノンパーオキサイド、アセチルアセ
トンパーオキサイド、1,1−ビス(ターシャリイブチ
ルパーオキシ) −3,3,5−トリメチルシクロヘキ
サン51.1−ビス(ターシャリイブチルパーオキシ)
シクロヘキサン、n−ブチル−4,4−ビス(ターシャ
リイブチルパーオキシ)バレラート、2,2−ビス(タ
ーシャリイブチルパーオキシ)ブタン、ターシャリイブ
チルハイドロパーオキサイド、クメンハイドロパーオキ
サイド、ジイソプロピルベンゼンハイドロパーオキサイ
ド、パラ−メンタンハイドロパーオキサイド、2.5−
ジメチルヘキサン−2,5−シバイドロバ−オキサイド
、1.1.3.3.−テトラメチルブチルハイドロパー
オキサイド、ジサイド、α、α′−ビス(ターシャリイ
ブチルバーオ 5−
キシイソプロピル)ベンゼン、2.5−ジメチル−−2
,5−ジ(ターシャリイブチルパーオキシ)ヘキサン、
2,5−ジメチル−2゜5−ジ(ターシャリイブチルパ
ーオキシ)ヘキシン−3,アセチルパーオキサイド、イ
ソブチリルパーオキサイド、オクタノイルパーオキサイ
ド、デカノイルパーオキサイド、ラウロイルパーオキサ
イド、3,5.5−トリメチルヘキサノイルパーオキサ
イド、過酸化こはく酸、過酸化ベンゾイル、2,4−ジ
クロロベンゾイルパーオキサイド、メタ−トルオイルパ
ーオキサイド、ジイソプロピルパーオキシジカーボネー
ト、ジー2−エチルヘキシルパーオキシジカーボネート
、ジノルマルプロピルバーオキシジカーボネート、ジー
2−エトキシエチルパーオキシジカーボネート、ジメト
キシイソプロピルバーオキシカーボネート、ジ(3−メ
チル−3−メトキシブチル)パーオキシジカーボネート
、ターシャリイブチルパーオキシアセテート、ターシャ
リイブチルパーオキシイソブチレート、ターシャリイブ
チルバニオキシピパレート、ターシャリイブチル 6−
パーオキシネオデカノエート、ターシャリイブチルパー
オキシオクタノエート、ターシャリイブチルバーオキシ
3.5.5− )リメチルヘキサノエート、ターシャリ
イブチルパーオキシラウレート、ターシャリイブチルパ
ーオキジペンゾエート、ジターシャリイソパーオキシイ
ソフタレート、2,5−ジメチル−2,5−ジ(ベンゾ
イルパーオキシ)ヘキサン、ターシャリイブチル過酸化
マレイン酸、ターシャリイブチルパーオキシイソプロビ
ルカーボネート等がある。The organic peroxide used in the present invention has oxygen in its molecule.
Almost all organic compounds having one or more oxygen bonds are included; examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,
3.5-trimethylcyclohexanone peroxide,
Methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy) -3,3,5-trimethylcyclohexane 51.1-bis(tert-butylperoxy)
Cyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroper oxide, para-menthane hydroperoxide, 2.5-
Dimethylhexane-2,5-cybidrobar oxide, 1.1.3.3. -Tetramethylbutyl hydroperoxide, diside, α,α'-bis(tert-butylbaroxyisopropyl)benzene, 2,5-dimethyl-2
, 5-di(tert-butylperoxy)hexane,
2,5-dimethyl-2゜5-di(tert-butylperoxy)hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5.5 -Trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl Peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxyiso Butyrate, tert-butyl vanioxypiparate, tert-butyl 6-peroxyneodecanoate, tert-butyl peroxyoctanoate, tert-butyl peroxy 3.5.5-)limethylhexanoate, Tertiary butyl peroxylaurate, Tertiary butyl peroxydipenzoate, Ditertiary isoperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, Tertiary butyl maleic peroxide acids, tert-butyl peroxyisopropyl carbonate, etc.
本発明で用いられる有機染料化合物とは、黄〜赤〜紫の
色域を呈する以下に例示するような特定構造を有するも
のである。The organic dye compound used in the present invention has a specific structure as exemplified below and exhibits a color range of yellow to red to violet.
Aニジアニン系染料 a) B:メロシアニン系染料 a) 9− c)。A dianine dye a) B: Merocyanine dye a) 9- c).
1
■
CH2C−0X
I
C:キサンテン系染料
=10−
D:チアゾール系染料
a)
本発明の光開始剤組成物は、前記のイNW過1没化物+
PO’)の1種または2棟以上と、上記有機染料化合物
(DYIの1種または2種以上とを有効成分として貧有
するものであり1両者の配合割合は重赦比で (iン(
+1:(DY)が1〜99:99〜1であり、さらに好
ましくは3〜95:97〜5である。この範囲外の組成
では俊才1た効宋が得ら11. i「I、・。 □
本発明の元亜付開始剤4i11成物はほとんどすべての
不Mオロ化付I物を極短時間のうちに紫外光および可視
光によって光重合することができる。これら不飽和化合
物としては重合性のエチレン系不飽和結合を有するモノ
マー、オリゴマー、ポリマーであり、たとえばアクリル
酸、メタクリル酸、イタコン酸、マレイン酸およびその
無水物、フタル酸およびその無水物、フマル酸等の不飽
和酸や(メタ)アクリル酸メチル、(メタ)アクリル酸
エチル、(メタ)アクリル酸ブチル、(メタ)アクリル
酸グリシジル、(メタ)アクリル酸ヒドロキシエチル、
マレイン酸ジメチル、マレイン酸ジエチル。1 ■ CH2C-0X I C: xanthene dye = 10- D: thiazole dye a) The photoinitiator composition of the present invention contains the above-mentioned NW peroxide +
It contains one or more of the above organic dye compounds (DYI) and one or more of the organic dye compounds (DYI) as active ingredients.
+1:(DY) is 1-99:99-1, more preferably 3-95:97-5. If the composition is outside this range, the Song Dynasty, which has a talent of 1, will have 11. i"I,... □
The initiator 4i11 composition of the present invention can photopolymerize almost all non-M chlorinated I compounds in a very short time using ultraviolet light and visible light. These unsaturated compounds include monomers, oligomers, and polymers having polymerizable ethylenically unsaturated bonds, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and its anhydride, phthalic acid and its anhydride, and fumaric acid. Unsaturated acids such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate,
Dimethyl maleate, diethyl maleate.
フマル酸ジメチル、ペンタエリスリトールトリ(メタ)
アクリレート、トリメチロールプロパントリ(メタ)ア
クリレート、エチレングリコールジ(メタ)アクリレー
ト、ブロビレングリコールジ(メタ)アクリレート等の
不飽和酸エステル。Dimethyl fumarate, pentaerythritol tri(meth)
Unsaturated acid esters such as acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, and brobylene glycol di(meth)acrylate.
およびスチレン、アクリルアミド、アクリロニトリル、
N−ビニルピロリドン、酢酸ビニル、さらに柚々の不飽
和酸ポリエステル、不飽和ポリエーテル、不飽和ポリウ
レタンやエポキシ(メタ)アクリレート化合物等がある
。and styrene, acrylamide, acrylonitrile,
Examples include N-vinylpyrrolidone, vinyl acetate, unsaturated acid polyesters, unsaturated polyethers, unsaturated polyurethanes, and epoxy (meth)acrylate compounds.
13−
これらの不飽和化合物の単独かもしくは2種以剤等や適
当な希釈溶媒を加えて光重合組成物とする。13- A photopolymerizable composition is prepared by adding one or more of these unsaturated compounds and a suitable diluting solvent.
光重合開始剤組成物の添加1は不飽和化合物100重量
部に対してO,1〜4ON量部、好ましくは05〜30
重量部である。Addition 1 of the photopolymerization initiator composition is O,1 to 4 parts by weight, preferably 05 to 30 parts by weight, per 100 parts by weight of the unsaturated compound.
Parts by weight.
また適当な希釈溶媒としては1本発明の光重合開始剤組
成物および使用する不飽和化合物を溶解するものならす
べて使用可能であり、たとえば。Further, as suitable diluting solvents, any solvent can be used as long as it dissolves the photopolymerization initiator composition of the present invention and the unsaturated compound used, for example.
水、メタノール、エタノール、プロパツール、ブタノー
ル、アセトン、メチルエチルケトン、メチルイソブチル
ケトン、メチルセロソルブ、エチルセロソルブ、ベンゼ
ン、トルエン、キシレン、酢酸エチル、酢酸ブチル、テ
トラヒドロフラン、ジオキサン、ジクロルメタン、クロ
ロホルム、四塩化炭素、トリクロルエチレン、ジメチル
ホルムアミド、ジメチルスルホキシド等がある。Water, methanol, ethanol, propatool, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, benzene, toluene, xylene, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichlor Examples include ethylene, dimethylformamide, and dimethyl sulfoxide.
このようにして得られた光重合組成物は紫外か14−
ら可視光の巾広い領域の活性光線を照射すること(Cよ
り極短時間のうちに重合反応が達せられろ。The photopolymerizable composition thus obtained is irradiated with actinic light in a wide range from ultraviolet to visible light (a polymerization reaction can be achieved in a very short time).
光源としては超高圧、高圧、中圧、低圧の各水銀灯、ケ
ミカルランプ、カーボンアーク灯、キセノン灯、メタル
ハライド灯、可視および紫外の各種レーザーランプ、螢
光灯、タングステン灯、および太陽光等が使用できる。Light sources used include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, and sunlight. can.
本発明の光重合開始剤組成物は通常の光重合反応に使用
できろ他、光硬化型の塗料、印刷インキ、接着剤や印刷
版作製、さらにプリント基板、IC等作製の際のフォト
レジスト等々多方面に適用することが可能であり、また
その効果も非常に良好である。特に本発明の光重合開始
剤組成物の特長である高感度性と可視光領域までの巾広
い分光感度特性により、 Ar+レーザー等の可視光レ
ーザー用の感光材料に適用すると驚くほど良好な効果が
得られろ。The photopolymerization initiator composition of the present invention can be used not only for ordinary photopolymerization reactions, but also for the production of photocurable paints, printing inks, adhesives and printing plates, as well as photoresists for the production of printed circuit boards, ICs, etc. It can be applied in many fields, and its effects are also very good. In particular, due to the high sensitivity and wide spectral sensitivity characteristics up to the visible light region, which are the features of the photopolymerization initiator composition of the present invention, it has surprisingly good effects when applied to photosensitive materials for visible light lasers such as Ar+ lasers. Get it.
以下実施例および比較例により本発明をさらに詳しく説
明する。なお例中の部は重量部である。The present invention will be explained in more detail below using Examples and Comparative Examples. Note that parts in the examples are parts by weight.
これらの実施例は説明の目的で述べるものであって本発
明になんら制限を加えろものではない。These examples are provided for illustrative purposes and are not intended to limit the invention in any way.
実施例1〜51
不飽和化合物としてペンタエリスリトールトリアクリレ
ート100部、バインダーとしてポリ−N−ビニルピロ
リドン100部を用い、これに本発明の光N会開始剤組
成物を表−1に示す割合で添加し、さらにこれらを1O
flO部のメチルセロに乾燥塗膜厚が1μmとなるよう
にスピンナーを用いて塗布した。Examples 1 to 51 Using 100 parts of pentaerythritol triacrylate as an unsaturated compound and 100 parts of poly-N-vinylpyrrolidone as a binder, the photo-N-initiator composition of the present invention was added in the proportions shown in Table 1. and further add these to 1O
It was coated on methyl cello in the flO section using a spinner so that the dry coating thickness was 1 μm.
感光性試験は、可視光(波長=488nm)。The photosensitivity test was performed using visible light (wavelength = 488 nm).
紫外線(波長−36snm)およびレーザー光(波長=
=488nm)のおのおの単色光を用いた。Ultraviolet light (wavelength - 36snm) and laser light (wavelength =
= 488 nm) was used for each monochromatic light.
可視光の488nmの単色光は5(IOWのキセノン灯
を光源とし、東芝色ガラスフィルターY−47、KL−
49f7’12枚のフィルターを通すことにより得た。The monochromatic light of 488 nm of visible light is
Obtained by passing through 12 49f7' filters.
また365nmの単色光は45nwの高圧水銀灯を光源
とし、東芝色ガラスフィルターTI VI〕35を通す
ことにより得た。レーザー光は25WのAr″−レーザ
ーの波長488nmのシングルラインをビーム径125
朋で使用した。各単色光を用いて前記感光膜に露光し、
塗膜が完全に光硬化するまでの積算光エネルギーにより
感度を測定した。Monochromatic light of 365 nm was obtained by using a 45 NW high-pressure mercury lamp as a light source and passing it through a Toshiba color glass filter TI VI]35. The laser beam is a single line with a 25W Ar'' laser wavelength of 488nm and a beam diameter of 125 nm.
I used it at my friend. exposing the photosensitive film using each monochromatic light;
Sensitivity was measured by the cumulative light energy until the coating film was completely photocured.
結果を表−1に示すが1表中の光重合開始剤組成物の量
はすべてペンタエリスリトールトリアクリレート100
部に対するものである。The results are shown in Table 1, and the amounts of photopolymerization initiator compositions in Table 1 are all pentaerythritol triacrylate 100
This is for the department.
比較例1〜】5
本発明の光重合開始剤組成物の代りに、従来公知の光重
合開始剤、他に有機過酸化物、有機染料化合物のおのお
の単独品を用いた場合について実施例と同様な感光性試
験を行い感度を測定した。Comparative Examples 1 to 5 Same as in Examples, except that instead of the photopolymerization initiator composition of the present invention, a conventionally known photopolymerization initiator, an organic peroxide, and an organic dye compound were used individually. A photosensitivity test was conducted to measure the sensitivity.
結果を表−2に示すが、表中の光重合開始剤の量はすべ
てペンタエリスリトールトリアクリレート100部拠対
するものである。The results are shown in Table 2, and the amounts of photopolymerization initiators in the table are all based on 100 parts of pentaerythritol triacrylate.
17一 −20− 表−1、表−2中の略称は下記のとおりである。17-1 -20- The abbreviations in Table-1 and Table-2 are as follows.
0 有機過酸化物
BPO:ペンゾイルパーオキサイド
PBIF:ジターシャリイプチルジパーオキシイソフタ
レート
POZ:2.5−ジメーfk−2,5−シ(へyソイル
パーオキシ)ヘキサン
PBZ :ターシャリイブチルパーオキシベンゾエート
PXM:α、α′−ビス(ターシャリイブチルパーオキ
シイソプロビル)ベンゼン
DCP:ジクミルバーオキサイド
O有機染料化合物
21−
A −3=
B −1:
B −2:
22−
B −6:
1
C2’F(5
B −8:
C1(2cOOK
C−1:
C−2:
C−3:
D −1:
D −2:
○ 公知の光重合開始剤
BIPE:ベンゾインイソプロピルエーテルBP:ベン
ゾフェノン
MK:ミヘラーズケトン
1.2−BA:1.2−ベンズアントラキノン表−1お
よび表−2から明らかかように、有機過酸化物と有機染
料化合物とを組み合せた実施例のものはすべて比較例の
ものに比べて著しく高感度であることがわかる。0 Organic peroxide BPO: Penzoyl peroxide PBIF: Ditertiary butyl diperoxyisophthalate POZ: 2,5-dimer-fk-2,5-cy(heysoylperoxy)hexane PBZ: Tertiary butyl peroxybenzoate PXM: α,α′-bis(tert-butylperoxyisopropyl)benzene DCP: dicumyl peroxide O organic dye compound 21- A-3= B-1: B-2: 22- B-6: 1 C2 'F (5 B -8: C1 (2cOOK C-1: C-2: C-3: D -1: D -2: ○ Known photoinitiator BIPE: Benzoin isopropyl ether BP: Benzophenone MK: Micher's ketone 1 .2-BA: 1.2-Benzanthraquinone As is clear from Tables 1 and 2, all of the Examples in which an organic peroxide and an organic dye compound were combined were significantly more effective than the Comparative Examples. It can be seen that the sensitivity is high.
特許出願人 日本油脂株式会社 25−Patent applicant: NOF Corporation 25-
Claims (1)
合物の1′81または2種以上とを組み合わせて成る元
1合開始剤組成物。 2 有機染料化合物がシアニン系染料である特許請求の
範囲第1項記載の組成物。 3 有機染料化合物がメロシアニン系染料である特許請
求の範囲第1項記載の組成物。 4 有1幾染料化合物がキサンチン系染料である特許請
求の範囲第1項記載の組成物。 5 有機染料化合物がチアソール系染料である特許請求
の範囲第1項記載の組成物。[Scope of Claims] 1. An initiator composition comprising a combination of one or more organic peroxides and one or more organic dye compounds. 2. The composition according to claim 1, wherein the organic dye compound is a cyanine dye. 3. The composition according to claim 1, wherein the organic dye compound is a merocyanine dye. 4. The composition according to claim 1, wherein the dye compound is a xanthine dye. 5. The composition according to claim 1, wherein the organic dye compound is a thiazole dye.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6379683A JPS59189340A (en) | 1983-04-13 | 1983-04-13 | Photopolymerization initiator composition having high sensitivity |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6379683A JPS59189340A (en) | 1983-04-13 | 1983-04-13 | Photopolymerization initiator composition having high sensitivity |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59189340A true JPS59189340A (en) | 1984-10-26 |
JPH0365541B2 JPH0365541B2 (en) | 1991-10-14 |
Family
ID=13239694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6379683A Granted JPS59189340A (en) | 1983-04-13 | 1983-04-13 | Photopolymerization initiator composition having high sensitivity |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59189340A (en) |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61213838A (en) * | 1985-03-20 | 1986-09-22 | Nippon Oil & Fats Co Ltd | Photosensitive lithographic printing plate |
JPS62263202A (en) * | 1986-05-08 | 1987-11-16 | Unitika Ltd | Photo-polymerizable composition |
JPS63132902A (en) * | 1986-11-22 | 1988-06-04 | Nippon Oil & Fats Co Ltd | Photo-polymerization initiator composition |
JPS63144342A (en) * | 1986-12-09 | 1988-06-16 | Nippon Oil & Fats Co Ltd | Dry film photoresist |
US4766055A (en) * | 1985-08-01 | 1988-08-23 | Nippon Paint Co., Ltd. | Photopolymerizable composition containing a certain xanthene or thioxanthene dyestuff |
JPS6488444A (en) * | 1987-09-29 | 1989-04-03 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
JPH0527422A (en) * | 1991-07-24 | 1993-02-05 | Toyo Ink Mfg Co Ltd | Visible light sensitive resin composition |
JPH05107758A (en) * | 1991-10-14 | 1993-04-30 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
EP0695971A1 (en) | 1994-08-03 | 1996-02-07 | Fuji Photo Film Co., Ltd. | Photosensitive lithographic printing plate |
EP0704764A1 (en) | 1994-09-05 | 1996-04-03 | Mitsubishi Chemical Corporation | Photopolymerizable composition and photosensitive lithographic printing plate |
EP0780731A2 (en) | 1995-12-22 | 1997-06-25 | Mitsubishi Chemical Corporation | Photopolymerizable composition for a color filter, color filter and liquid crystal display device |
EP1626309A2 (en) | 2004-03-25 | 2006-02-15 | Fuji Photo Film Co., Ltd. | Hologram recording material, hologram recording method and holographic optical element |
EP1635219A1 (en) | 2004-08-27 | 2006-03-15 | Fuji Photo Film Co., Ltd. | Photosensitive lithographic printing plate |
EP1757984A1 (en) | 2005-08-22 | 2007-02-28 | Fuji Photo Film Co., Ltd. | Photosensitive lithographic printing plate |
WO2008108406A1 (en) * | 2007-03-05 | 2008-09-12 | Fujifilm Corporation | Compound for photoresist, photoresist solution, and etching method using the photoresist solution |
EP2042532A2 (en) | 2007-09-28 | 2009-04-01 | FUJIFILM Corporation | Polymerizable composition and planographic printing plate precursor using the same, alkalisoluble polyrethane resin, an process for producing diol compound |
JP2009203349A (en) * | 2008-02-28 | 2009-09-10 | Fujifilm Corp | Compound for photoresist, photoresist liquid, and etching method using this |
WO2009119610A1 (en) | 2008-03-25 | 2009-10-01 | 富士フイルム株式会社 | Process for producing lithographic printing plate |
EP2107089A1 (en) | 2005-06-13 | 2009-10-07 | Toshiba TEC Kabushiki Kaisha | Inkjet ink, inkjet recording method, method of evaluating inkjet ink, and method of manufacturing inkjet ink |
EP2109000A1 (en) | 2004-09-10 | 2009-10-14 | FUJIFILM Corporation | Polymer having polymerizable group, polymerizable composition, planographic printing plate precursor, and planographic printing method using the same |
EP2128704A2 (en) | 2008-05-29 | 2009-12-02 | Fujifilm Corporation | Processing Liquid for Lithographic Printing Plate Development and Method of Producing Lithographic Printing Plates |
EP2131239A1 (en) | 2008-05-29 | 2009-12-09 | Fujifilm Corporation | Processing liquid for lithographic printing plate development and method of producing lithographic printing plates |
EP2157478A2 (en) | 2008-08-22 | 2010-02-24 | Fujifilm Corporation | Method of producing lithographic printing plate |
WO2010021364A1 (en) | 2008-08-22 | 2010-02-25 | 富士フイルム株式会社 | Process for producing lithographic printing plate |
EP2159640A1 (en) | 2008-08-29 | 2010-03-03 | Fujifilm Corporation | Method of preparing lithographic printing plate |
WO2013039235A1 (en) | 2011-09-15 | 2013-03-21 | 富士フイルム株式会社 | Method for recycling wastewater produced by plate-making process |
WO2013065853A1 (en) | 2011-11-04 | 2013-05-10 | 富士フイルム株式会社 | Method for recycling plate-making processing waste solution |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS49115312A (en) * | 1973-02-20 | 1974-11-05 | ||
JPS5212825A (en) * | 1975-07-21 | 1977-01-31 | Toyobo Co Ltd | Visible light sensitive composition |
JPS5289915A (en) * | 1976-01-23 | 1977-07-28 | Mitsubishi Paper Mills Ltd | Image forming method |
JPS539519A (en) * | 1976-07-14 | 1978-01-28 | Ricoh Co Ltd | Photosensitive material for forming color image |
JPS54151024A (en) * | 1978-05-18 | 1979-11-27 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
JPS5888739A (en) * | 1981-11-12 | 1983-05-26 | ザ・ミ−ド・コ−ポレ−シヨン | Transfer image formation system |
-
1983
- 1983-04-13 JP JP6379683A patent/JPS59189340A/en active Granted
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS49115312A (en) * | 1973-02-20 | 1974-11-05 | ||
JPS5212825A (en) * | 1975-07-21 | 1977-01-31 | Toyobo Co Ltd | Visible light sensitive composition |
JPS5289915A (en) * | 1976-01-23 | 1977-07-28 | Mitsubishi Paper Mills Ltd | Image forming method |
JPS539519A (en) * | 1976-07-14 | 1978-01-28 | Ricoh Co Ltd | Photosensitive material for forming color image |
JPS54151024A (en) * | 1978-05-18 | 1979-11-27 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
JPS5888739A (en) * | 1981-11-12 | 1983-05-26 | ザ・ミ−ド・コ−ポレ−シヨン | Transfer image formation system |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61213838A (en) * | 1985-03-20 | 1986-09-22 | Nippon Oil & Fats Co Ltd | Photosensitive lithographic printing plate |
US4766055A (en) * | 1985-08-01 | 1988-08-23 | Nippon Paint Co., Ltd. | Photopolymerizable composition containing a certain xanthene or thioxanthene dyestuff |
JPS62263202A (en) * | 1986-05-08 | 1987-11-16 | Unitika Ltd | Photo-polymerizable composition |
JPS63132902A (en) * | 1986-11-22 | 1988-06-04 | Nippon Oil & Fats Co Ltd | Photo-polymerization initiator composition |
JPS63144342A (en) * | 1986-12-09 | 1988-06-16 | Nippon Oil & Fats Co Ltd | Dry film photoresist |
JPS6488444A (en) * | 1987-09-29 | 1989-04-03 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
JPH0527422A (en) * | 1991-07-24 | 1993-02-05 | Toyo Ink Mfg Co Ltd | Visible light sensitive resin composition |
JPH05107758A (en) * | 1991-10-14 | 1993-04-30 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
EP0695971A1 (en) | 1994-08-03 | 1996-02-07 | Fuji Photo Film Co., Ltd. | Photosensitive lithographic printing plate |
EP0704764A1 (en) | 1994-09-05 | 1996-04-03 | Mitsubishi Chemical Corporation | Photopolymerizable composition and photosensitive lithographic printing plate |
EP0780731A2 (en) | 1995-12-22 | 1997-06-25 | Mitsubishi Chemical Corporation | Photopolymerizable composition for a color filter, color filter and liquid crystal display device |
EP1626309A2 (en) | 2004-03-25 | 2006-02-15 | Fuji Photo Film Co., Ltd. | Hologram recording material, hologram recording method and holographic optical element |
EP1635219A1 (en) | 2004-08-27 | 2006-03-15 | Fuji Photo Film Co., Ltd. | Photosensitive lithographic printing plate |
EP3182204A1 (en) | 2004-09-10 | 2017-06-21 | FUJIFILM Corporation | Planographic printing plate precursor using a polymerizable composition |
EP2109000A1 (en) | 2004-09-10 | 2009-10-14 | FUJIFILM Corporation | Polymer having polymerizable group, polymerizable composition, planographic printing plate precursor, and planographic printing method using the same |
EP2107089A1 (en) | 2005-06-13 | 2009-10-07 | Toshiba TEC Kabushiki Kaisha | Inkjet ink, inkjet recording method, method of evaluating inkjet ink, and method of manufacturing inkjet ink |
EP1757984A1 (en) | 2005-08-22 | 2007-02-28 | Fuji Photo Film Co., Ltd. | Photosensitive lithographic printing plate |
WO2008108406A1 (en) * | 2007-03-05 | 2008-09-12 | Fujifilm Corporation | Compound for photoresist, photoresist solution, and etching method using the photoresist solution |
EP2042532A2 (en) | 2007-09-28 | 2009-04-01 | FUJIFILM Corporation | Polymerizable composition and planographic printing plate precursor using the same, alkalisoluble polyrethane resin, an process for producing diol compound |
JP2009203349A (en) * | 2008-02-28 | 2009-09-10 | Fujifilm Corp | Compound for photoresist, photoresist liquid, and etching method using this |
WO2009119610A1 (en) | 2008-03-25 | 2009-10-01 | 富士フイルム株式会社 | Process for producing lithographic printing plate |
EP2128704A2 (en) | 2008-05-29 | 2009-12-02 | Fujifilm Corporation | Processing Liquid for Lithographic Printing Plate Development and Method of Producing Lithographic Printing Plates |
EP2131239A1 (en) | 2008-05-29 | 2009-12-09 | Fujifilm Corporation | Processing liquid for lithographic printing plate development and method of producing lithographic printing plates |
EP2157478A2 (en) | 2008-08-22 | 2010-02-24 | Fujifilm Corporation | Method of producing lithographic printing plate |
WO2010021364A1 (en) | 2008-08-22 | 2010-02-25 | 富士フイルム株式会社 | Process for producing lithographic printing plate |
EP2159640A1 (en) | 2008-08-29 | 2010-03-03 | Fujifilm Corporation | Method of preparing lithographic printing plate |
WO2013039235A1 (en) | 2011-09-15 | 2013-03-21 | 富士フイルム株式会社 | Method for recycling wastewater produced by plate-making process |
WO2013065853A1 (en) | 2011-11-04 | 2013-05-10 | 富士フイルム株式会社 | Method for recycling plate-making processing waste solution |
Also Published As
Publication number | Publication date |
---|---|
JPH0365541B2 (en) | 1991-10-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS59189340A (en) | Photopolymerization initiator composition having high sensitivity | |
US4940648A (en) | Increased sensitivity photoinitiation compositions | |
JP5617941B2 (en) | Photosensitive resin composition, photosensitive element, resist pattern forming method, and printed wiring board manufacturing method | |
JP5051299B2 (en) | Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board | |
JPS591504A (en) | Photopolymerization initiator composition | |
JPS621641B2 (en) | ||
KR101514900B1 (en) | Photosensitive resin composition and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same | |
JP6022749B2 (en) | Photosensitive resin composition, photosensitive element, method for producing resist pattern, method for producing lead frame, and method for producing printed wiring board | |
JPS59140203A (en) | Highly sensitive photoinitiator composition | |
WO2009154194A1 (en) | Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board | |
JPS62174203A (en) | Photopolymerization initiator composition | |
JP2018524285A (en) | Pyrazoline sensitizer, method for producing the same and use thereof | |
JPS6076503A (en) | High-sensitivity photo-reaction initiator composition | |
JPH01201652A (en) | Photocurable composition | |
JPS63168403A (en) | Photopolymerizable composition | |
JPS627703A (en) | Photopolymerization initiator composition | |
JPH02279702A (en) | Photopolymerization initiator composition | |
JPS63132902A (en) | Photo-polymerization initiator composition | |
US4945027A (en) | 1,4 or 9,10 dimethoxyanthracene triggers for 2-tri(chloro or bromo)methyl-4(1H)-quinazolimone polymerization initiators | |
JPS63278906A (en) | Photopolymerization initiator composition | |
JPS63278907A (en) | Photopolymerization initiator composition | |
JPH07103170B2 (en) | Photopolymerization initiator composition | |
JPH0463882B2 (en) | ||
JPS63278905A (en) | Photopolymerization initiator composition | |
JPS6194040A (en) | Nonsilver salt photosensitive film |