JPS60249141A - Diazo copying material - Google Patents
Diazo copying materialInfo
- Publication number
- JPS60249141A JPS60249141A JP10445584A JP10445584A JPS60249141A JP S60249141 A JPS60249141 A JP S60249141A JP 10445584 A JP10445584 A JP 10445584A JP 10445584 A JP10445584 A JP 10445584A JP S60249141 A JPS60249141 A JP S60249141A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- diazo
- density
- forming
- diazo copying
- 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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
【発明の詳細な説明】
厳1」」久鼠四jυL
本発明は、色調がブルーバイオレットのホルマザン金属
キレート色素を呈するジアゾ複写材料に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diazo copying material exhibiting a formazan metal chelate dye of blue-violet color.
従来の技術
ジアゾニウム塩と、該ジアゾニウム塩と電子反応し得る
ヒドラゾンカップラーと、カップリング生成物とキレ−
1−化し得る2価遷移金属化合物とを含むジアゾ複写材
料が開発されている。BACKGROUND OF THE INVENTION A diazonium salt, a hydrazone coupler capable of electronically reacting with the diazonium salt, and a coupling product and a hydrazone coupler.
Diazo copying materials have been developed that contain divalent transition metal compounds that can be converted into monomers.
そして、ジアゾコピーの色調については、人の感覚的に
合う色で従来製品との異和感がないようにと細かい配慮
が払われてきた。Careful attention has been paid to the color tones of diazo copies so that they match the human sensibilities and do not feel out of place with conventional products.
ところが、上記のジアゾ複写材料の分光吸収特性を実験
的にめると、従来のジアゾ複写材料に用いられてきた色
素(λwax 570〜580rv )と全く同じ特性
をもつ化合物の組合せを見つけることが容易でなかった
。すなわち、色調がいずれも長波長(λmay、 60
0nm以上)側にあり、短波長(λmax 600nm
未満)′側で、色調がまだ不満足であり、現像条件によ
っては二色性の恐れがあり、耐光性等の品質にも影響を
及ぼし、調整が困難である。However, when examining the spectral absorption characteristics of the above-mentioned diazo copying materials experimentally, it is easy to find a combination of compounds that have exactly the same properties as the dyes (λwax 570-580rv) used in conventional diazo copying materials. It wasn't. That is, all color tones have long wavelengths (λmay, 60
0nm or more) side, and short wavelength (λmax 600nm
On the lower)' side, the color tone is still unsatisfactory, there is a risk of dichroism depending on the development conditions, and quality such as light resistance is affected, making adjustment difficult.
発明が解決しようとする問題点
ヒドラゾン系カップラーを用いたジアゾ複写材料の色調
を所望の色調にする点にある。The problem to be solved by the present invention is to obtain a desired color tone of a diazo copying material using a hydrazone coupler.
問題点を解決するための手段
本発明は、下記一般式で示されるジアゾ化合物とヒドラ
ゾン系カップラーおよびカップリング生成物とキレート
化しうるニッケル化合物を支持体上に用いたことを特徴
とするジアゾ複写材料である。Means for Solving the Problems The present invention provides a diazo copying material characterized in that a diazo compound represented by the following general formula, a hydrazone coupler, and a nickel compound capable of chelating with the coupling product are used on a support. It is.
(R3、R4はC数1〜3のアルキル基)R2:H,−
CB +−15、C00Rs、C0Rs(Rs−11,
01〜3のア
ルキル基)
X:酸残基又は金属塩と複塩を形成している酸残基であ
る。(R3 and R4 are C1-3 alkyl groups) R2: H, -
CB +-15, C00Rs, C0Rs (Rs-11,
Alkyl group of 01 to 3) X: An acid residue or an acid residue forming a double salt with a metal salt.
なお、Xの酸残基としては、ハロゲンイオンやBF4−
、PF6−などの含フツ素酸の陰イオンであるのが好
ましく、一方、酸残基に対して複塩を形成する金属塩と
しては、例えばZn C12、Cd C12、Sn C
12などがある。上記一般式の化合物としては具体的に
下記のものが挙げられる。ここでXに相当するものはC
1・ 1/ 2Zn C12である。Note that the acid residue of X is a halogen ion or BF4-
, PF6-, etc. are preferable, while metal salts that form double salts with acid residues include, for example, Zn C12, Cd C12, Sn C
There are 12 etc. Specific examples of the compound of the above general formula include the following. Here, the equivalent of X is C
1.1/2 Zn C12.
また、ニッケル化合物としては、下記のものが例示され
る。Moreover, the following are illustrated as a nickel compound.
ペンゼスルホン酸ニッケル、酢酸ニッケル(4水和物)
、ニッケル(II)アセチルアセテート、塩化ニッケル
アンモニウム、硫酸ニッケルアンモニウム、安息香酸ニ
ッケル、臭化ニッケル、炭酸ニッケル(ji基性)、塩
化ニッケル、くえん酸ニッケル、シクロヘキサン酪酸ニ
ッケル、次亜りん酸二水素二ッケル、ぎ酸ニッケル、水
酸化ニッケル、次亜りん酸ニッケル、第一よう化ニッケ
ル、硝酸ニッケル、ニラケロセン、オレイン酸ニッケル
、蓚酸ニッケル、りん酸ニッケル、フタロシアニンニッ
ケル、シアン化ニッケルカリウム、硫酸ニッケルカリウ
ム、セレン酸ニッケル(6水和物)、ステアリン酸ニッ
ケル、スルファミン酸ニッケル、硫酸ニッケル(1水和
物)、硫酸ニッケル(6水和物)、酒石酸ニッケル、チ
オシアン酸ニッケル。Nickel penzesulfonate, nickel acetate (tetrahydrate)
, nickel (II) acetyl acetate, nickel ammonium chloride, nickel ammonium sulfate, nickel benzoate, nickel bromide, nickel carbonate (ji-based), nickel chloride, nickel citrate, nickel cyclohexane butyrate, dihydrogen hypophosphite nickel formate, nickel hydroxide, nickel hypophosphite, nickel primary iodide, nickel nitrate, kerosene, nickel oleate, nickel oxalate, nickel phosphate, nickel phthalocyanine, potassium nickel cyanide, potassium nickel sulfate, Nickel selenate (hexahydrate), nickel stearate, nickel sulfamate, nickel sulfate (monohydrate), nickel sulfate (hexahydrate), nickel tartrate, nickel thiocyanate.
本発明に用いられるヒドラゾンカップラーとしでは下記
のものが挙げられる。Examples of hydrazone couplers used in the present invention include the following.
1 .2.4−ジヒドロキシベンズアルデヒド112−
ヒドロキシベンズアルデヒド
172−ヒドロキシベンズアルデヒド
−2−ベンゾチアゾリルヒドラゾンナトリウム塩180
−スルホベンズアルデヒド
−2−ベンゾチアゾリルヒドラゾンナトリウム増−2−
ビリジルヒドラゾンナi−リウム塩41 アセトアルデ
ヒド−2−キノリルヒドラゾン42 1−プロピルアル
デヒド−2−キノリルヒドラゾン以下実施例により本発
明をさらに詳細に説明する。1. 2.4-dihydroxybenzaldehyde 112-
Hydroxybenzaldehyde 172-Hydroxybenzaldehyde-2-benzothiazolylhydrazone sodium salt 180
-Sulfobenzaldehyde-2-benzothiazolylhydrazone sodium increase-2-
Byridylhydrazonalium salt 41 Acetaldehyde-2-quinolylhydrazone 42 1-Propylaldehyde-2-quinolylhydrazone The present invention will be explained in more detail with reference to the following examples.
実施例1 下記成分を混合して感光層形成液を調製した。Example 1 A photosensitive layer forming liquid was prepared by mixing the following components.
酒石酸 1.5g 2X10−3モル チオ尿素 0.5g ベンゼンスルホン酸ニッケル 5x10−”モル サポニン o、ig 上記組成のものを水で全量を100mβとする。Tartaric acid 1.5g 2X10-3 moles Thiourea 0.5g Nickel benzenesulfonate 5x10-”mol saponin o, ig The above composition was made up to a total volume of 100 mβ with water.
感光紙白色原紙に下記のプレコート層形成液を塗布し、
プレコート層を形成(乾燥重量1.5(+/11 ’
) L/た上に上記の感光層形成液を塗布乾燥して、ジ
アゾ複写紙を作成した。Apply the following pre-coat layer forming liquid to white photosensitive paper base paper,
Form a pre-coat layer (dry weight 1.5 (+/11')
) The above-mentioned photosensitive layer forming liquid was applied onto L/2 and dried to prepare diazo copying paper.
プレコート層形成液
シリカ(粒径1〜5μ)50g
ポリ酢酸ビニルエマルジョン
(固形分40%) 100(]
メチレンブルー 0.01(1
このジアゾ複写紙に画像を有する原図を重ね合せ市販の
ジアゾ半乾式複写機(リコビー5D−205)を使用し
て露光後現像(視像液付着量1.5g/m 2) シて
画像を1qだ。結果を以下に記載した。Precoat layer forming liquid Silica (particle size 1 to 5μ) 50g Polyvinyl acetate emulsion (solid content 40%) 100 () Methylene blue 0.01 (1) The original image with the image was superimposed on this diazo copying paper and commercially available diazo semi-dry copying was performed. After exposure, the image was developed using a machine (Ricobee 5D-205) (visual liquid adhesion amount: 1.5 g/m 2 ) and the image was made into 1 q. The results are described below.
色調二極大吸収波長(ブルーバイオレット)570nl
l1
反射濃度(マクベス濃度計により測定、グリーンフィル
ター使用)
:画像部最大濃度1.20
地肌部濃度 0.11
上記サンプルをカーボンアーク燈を装備したフユードメ
ーター(スガ試験機■製ロングライフフェードメーター
FA−3型)に12時間に亙ってセットし、極大吸収波
長における画像miの経時変化を測定したところ、図の
aの如き結果が得られた。結果が明らかなように画像形
成初期は画像濃度、コントラスト共に大鮮明画像であっ
た。又経時においても視覚濃度的に充分な濃度が維持さ
れた。Color tone dual maximum absorption wavelength (blue violet) 570nl
l1 Reflection density (measured with a Macbeth densitometer, using a green filter): Maximum density in the image area 1.20 Density in the background area 0.11 The above sample was measured using a fade meter equipped with a carbon arc light (Long Life Fade Meter manufactured by Suga Test Instruments ■) FA-3 model) for 12 hours, and the change over time of the image mi at the maximum absorption wavelength was measured, and the results shown in a in the figure were obtained. As the results clearly show, the image was very clear in both image density and contrast at the initial stage of image formation. Also, sufficient visual density was maintained over time.
実施例2
下記成分の感光層形成液を調製し、実施例1と同様の処
置をほどこしてジアゾ複写紙を作成し、実施例1同様に
してコピー画像を得た。Example 2 A photosensitive layer forming liquid having the following components was prepared and treated in the same manner as in Example 1 to prepare diazo copying paper, and a copy image was obtained in the same manner as in Example 1.
酒石酸 1.5g 2X10−3モル C8−’2 0.5g ベンゼンスルホン酸ニッケル 5X10−3モル サポニン 0.1g 上記組成のものを水で全量を100m 12とする。Tartaric acid 1.5g 2X10-3 moles C8-’2 0.5g Nickel benzenesulfonate 5X10-3 mole Saponin 0.1g The total volume of the above composition was made up to 100 m 12 with water.
結果を以下に記載する。The results are described below.
色調:極大吸収波長(ブルーバイオレット)75nm
反射濃度:(実施例1同様)
画像部最大濃度 1.23
地肌部濃度 0.11
変褪色性=(実施例1同様にして測定)結果は図のむの
如き結果が得られ、
画像III、コントラスl〜共に大なる鮮明画像で、又
経時においても視覚
濃度的に充分な濃度が維持された。Color tone: Maximum absorption wavelength (blue violet) 75 nm Reflection density: (same as Example 1) Maximum density in image area 1.23 Density in background area 0.11 Discoloration and fading property = (Measured in the same manner as Example 1) Results are shown in the figure. The following results were obtained: Image III and Contrast I were both very clear images, and sufficient visual density was maintained even over time.
実施例3
実施例1におけるジアゾ化合物の代りにを用いた以外は
同様にしてジアゾ複写紙を得、実施例1と同様の試験を
行なった。結果は下記のとおりである。Example 3 Diazo copying paper was obtained in the same manner as in Example 1, except that diazo compound was used instead of the diazo compound, and the same tests as in Example 1 were conducted. The results are as follows.
色調: 577r++n
反射濃度:画像部最大濃度 1.20
地肌部濃度 0.11
変褪色性:実施例1と同じ
実施例4
実施例2にお(プるジアゾ化合物の代りにを用いた以外
は同様にしてジアゾ複写紙を得、実施例2と同様の試験
を行なった。結果は下記のとおりである。Color tone: 577r++n Reflection density: Maximum density in image area 1.20 Density in background area 0.11 Discoloration and fading property: Same as Example 1 Example 4 Same as Example 2 except that (instead of the diazo compound) A diazo copying paper was obtained, and the same test as in Example 2 was conducted.The results are as follows.
色調: 580rv
反射濃度:画像部最大11度 1.23地肌部濃度 0
.10
変褪色性:実施例2と同じ
比較例1
下記成分を混合して感光層形成液を調製した。Color tone: 580rv Reflection density: Image area maximum 11 degrees 1.23 Background area density 0
.. 10 Discoloration and fading property: Same as Example 2 Comparative Example 1 The following components were mixed to prepare a photosensitive layer forming liquid.
酒石酸 1.5g
カフェイン 1g
2xlO−”モル
08−2 0.5g
Zn C+ 2 5X ’10−”モルサポニン 0.
1g
上記組成のものを水で全量を10011IJ2とする。Tartaric acid 1.5g Caffeine 1g 2xlO-"mol 08-2 0.5g Zn C+ 2 5X '10-"mol Saponin 0.
1g The total amount of the above composition was made 10011IJ2 with water.
以下実施例1と同様にしてジアゾ複写紙を得、実施例1
と同様の試験をした。結果を以下に記載した。Diazo copying paper was obtained in the same manner as in Example 1, and Example 1
I did a similar test. The results are listed below.
色調:極大吸収波長(ブルーバイオレット)75nm
反射濃度:画像部最大濃度 1.20
地肌濃度 0.11
上記サンプルを実施例1同様にフェードメーターにて画
像濃度の経時変化を測定したところ図のCの如き結果で
、実施例1.2の約3倍の劣化を示し視覚濃度的に不充
分でありすなわちコピー画像として支障をきたした。Color tone: Maximum absorption wavelength (blue violet) 75 nm Reflection density: Image area maximum density 1.20 Background density 0.11 The above sample was measured for the change in image density over time using a fade meter in the same manner as in Example 1. The results showed about three times the deterioration of Example 1.2, and the visual density was insufficient, that is, it was a problem as a copied image.
比較例2
実施例1の感光層形成液成分のジアゾニウム塩を下記で
示すジアゾニウム塩に置き換え、実施例1同様の処置を
ほどこしてジアゾ複写紙を作成し、実施例1同様にして
コピー画像を得た。Comparative Example 2 The diazonium salt in the photosensitive layer forming liquid component of Example 1 was replaced with the diazonium salt shown below, and the same treatment as in Example 1 was performed to prepare diazo copying paper, and a copy image was obtained in the same manner as in Example 1. Ta.
結果を以下に記載する。The results are described below.
色調二極大吸収波長(ブルー)
15nm
反射m痩:画像部最大濃度 1.18
地肌濃度 0.11
上記のごとく色調λl1laxが長波長側にがたより所
望の色調(λmax 570〜590nm )は得られ
なかった。Color tone dual maximum absorption wavelength (blue) 15 nm Reflection m thin: Image area maximum density 1.18 Background density 0.11 As mentioned above, the desired color tone (λmax 570 to 590 nm) could not be obtained because the color tone λl1lax shifted toward the long wavelength side. Ta.
変褪色性:結果は図dの如き結果が得られ視覚濃度的に
は、実施例1.2同様に
充分な濃度が雛持された。Discoloration and fading properties: The results shown in Figure d were obtained, and in terms of visual density, sufficient density was maintained as in Example 1.2.
比較例3
下記成分の感光層形成液を調製し、その伯は実施例1と
同様にしてジアゾ複写紙を作成し、実施例1と同様にし
てコピー画像を得た。Comparative Example 3 A photosensitive layer forming liquid having the following components was prepared, and diazo copying paper was prepared in the same manner as in Example 1, and a copy image was obtained in the same manner as in Example 1.
酒石酸 1.5g チオ尿素 0.5g Zn C+ 2 5X10−’モル サポニン 0・1g 結果を以下に記載する。Tartaric acid 1.5g Thiourea 0.5g Zn C+ 2 5X10-'mol Saponin 0.1g The results are described below.
色wI:極大吸収波長(ブルー) eeon+11反射
濃度:画像部最大濃度 1.21
地肌濃度 0.11
上記のごとく色調λmaXが長波長側にかたより所望の
色調(λ1llaX 570〜570nl )は得られ
なかった。Color wI: Maximum absorption wavelength (blue) eeon+11 reflection density: Image area maximum density 1.21 Background density 0.11 As mentioned above, the desired color tone (λ1llaX 570 to 570 nl) could not be obtained because the color tone λmax was biased toward the long wavelength side. Ta.
比較例4
実施例1の感光層形成液成分の金属化合物であるベンゼ
ンスルホン酸ニッケルを塩化亜鉛に置き換え液を調製し
、実施例1同様の処置をほどこしてジアゾ複写紙を作成
し、実施例1同様にしてコピー画像を得た。Comparative Example 4 A solution was prepared in which the metal compound nickel benzenesulfonate in the photosensitive layer forming liquid component of Example 1 was replaced with zinc chloride, and the same treatment as in Example 1 was performed to prepare diazo copying paper. A copy image was obtained in the same manner.
結果は以下のごとくであった。The results were as follows.
色調:極大吸収波長(ブルー) 630nm上記のごと
く色調・(λl1lax)が長波長側にかたより所望の
色調(λmax 570〜590nm )は得られなか
った。Color tone: Maximum absorption wavelength (blue) 630 nm As mentioned above, the color tone (λl1lax) was biased toward the long wavelength side, and the desired color tone (λmax 570 to 590 nm) could not be obtained.
発明の効果
本発明によれば、特定のジアゾ化合物とニッケル化合物
とヒドラゾン系カップラーとを組合せることにより、所
望とする色調(λwax ’5γ0〜590nm )の
画像が容易に得られ、その耐光性も、前記試験結果に示
したように満足の行くものである。Effects of the Invention According to the present invention, by combining a specific diazo compound, a nickel compound, and a hydrazone coupler, an image with a desired color tone (λwax'5γ0 to 590 nm) can be easily obtained, and its light resistance is also improved. , as shown in the above test results, are satisfactory.
図は本発明の実施例並びに比較例における試験結果を示
すグラフである。
特許出願人 株式会社リ コ −
代理人 弁理士 小 松 秀 岳
代理人 弁理士 旭 宏
0 4 8 12The figure is a graph showing test results in Examples and Comparative Examples of the present invention. Patent applicant Rico Co., Ltd. - Agent Patent attorney Hide Komatsu Agent Patent attorney Hiroshi Asahi 0 4 8 12
Claims (1)
プラーおよびカップリング生成物とキレート化しうるニ
ッケル化合物を支持体上に用いたことを特徴とするジア
ゾ複写材料。 (R3、R4はC数1〜3のアルキル基)R2:H,−
C6H5、C00Rs、 −CORs (Rs =H,C1〜3のアルキル基) X:酸残基又は金属塩と複塩を形成している酸残基であ
る。[Scope of Claims] A diazo copying material characterized in that a diazo compound represented by the following general formula, a hydrazone coupler, and a nickel compound capable of chelating with a coupling product are used on a support. (R3 and R4 are C1-3 alkyl groups) R2: H, -
C6H5, C00Rs, -CORs (Rs = H, C1-3 alkyl group) X: An acid residue or an acid residue forming a double salt with a metal salt.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10445584A JPS60249141A (en) | 1984-05-25 | 1984-05-25 | Diazo copying material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10445584A JPS60249141A (en) | 1984-05-25 | 1984-05-25 | Diazo copying material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS60249141A true JPS60249141A (en) | 1985-12-09 |
Family
ID=14381085
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10445584A Pending JPS60249141A (en) | 1984-05-25 | 1984-05-25 | Diazo copying material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60249141A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1037470C (en) * | 1992-10-14 | 1998-02-18 | 朱楚斌 | Agent increasing colourfulness and promoting display for diazo blueprint paper |
US6436479B2 (en) * | 2000-01-17 | 2002-08-20 | President Of Gifu University | Solution for forming nickel metal thin film and method of forming nickel metal thin film using the said solution |
-
1984
- 1984-05-25 JP JP10445584A patent/JPS60249141A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1037470C (en) * | 1992-10-14 | 1998-02-18 | 朱楚斌 | Agent increasing colourfulness and promoting display for diazo blueprint paper |
US6436479B2 (en) * | 2000-01-17 | 2002-08-20 | President Of Gifu University | Solution for forming nickel metal thin film and method of forming nickel metal thin film using the said solution |
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