JPS58207042A - Image forming composition and image forming method - Google Patents

Abstract

PURPOSE:To obtain an image high in optical density only by light or heat, by using a compsn. contg. as main components, a tetrazolium salt (component A), a reducing agent capable of reducing this component A by light or heat, and a compd. capable of forming a chelate with a reduction product, especially a transition metal or an activated complex. CONSTITUTION:The compsn. contains, as essential components, the component A represented by formula I , II in which R1, R2 are each optionally substd. aryl or hetero ring; R3 is H, alkyl, optionally substd. aryl, or functional group, such as OH, COOH, or NH2; X is an anion; Y is -(CH2)n-, n being 1-12, phenylene, or diphenylene; a component B of a reducing agent capable of reducing the component A by irradiation of >=300nm long wavelength active radiation, or by application of heat; and the activated transition metal, such as Co<++> or Zn<++> salt, or the activated complex, such as chloroferric complex, capable of forming a chelate together with formazane of the reduction product of the component A. A base, such as paper, is coated with a soln. of said compsn. and dried to obtain a recording material, and a sharp colored image is obtd. on this material by irradiation of UV rays or argon laser beams.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive or heat-sensitive image forming composition and an image forming method using this composition.

Photographic films using silver halide and diazo copying materials using alkaline media are known as typical recording materials containing image-forming compositions, but these require developing solutions and fixing solutions. However, the major drawback is that it is very cumbersome to operate.

The first object of the present invention is to provide a simple image-forming composition that can form images with high optical density simply by using light or hot liquid.

A second object of the present invention is to provide an image-forming composition that has high light or heat sensitivity and is inexpensive.

A third object of the present invention is to provide a simple method for forming images using light and/or heat.

The image forming composition of the present invention comprises a) a tetrazolium salt;
b) A photoreducing agent capable of reducing the component a) when exposed to active radiation (light) with a wavelength longer than 300 nm, or a thermal reducing agent capable of reducing the component a) when heat is applied; c) It is characterized by containing as a main component an active transition metal and/or an active metal capable of forming a chelate together with the reduction product of component a).

Furthermore, the image forming method of the present invention uses such an image forming composition and has been known for a long time.

(1) a) Tetrazolium salt, b) 300
When exposed to active radiation with a wavelength longer than nm, the above a
) a photoreducing agent capable of reducing component a), or a thermal reducing agent capable of reducing component a) upon application of heat; and C) a transition metal in an active state capable of forming a chelate with the reduction product of component a). and/or a recording member VC300mm in which an active surrounding material is coated or impregnated on a support; an image forming method characterized by performing imagewise exposure with active radiation having a longer wavelength or imprinting an ll1iI image thermal pattern; .

(2) a) Tetrazolium salt and b) 30
When exposed to active radiation with a wavelength longer than 0 nm, the above a
) A recording member having a support coated or impregnated with a photoreducing agent capable of reducing component (a) is subjected to imi image exposure with actinic radiation having a wavelength longer than 300 nm, and then this and the reduction product of component a) are An image forming method comprising heating a recording member in which a support is coated or impregnated with a transition metal and/or an active complex capable of forming a chelate in a dense layer.

(3) A recording member having a support coated or impregnated with a) a tetrazolium salt and b) a thermal reducing agent that can reduce the component a) when heat is applied, and a chelate together with the reduction product of the component a). II!, characterized in that a recording member is coated or impregnated with a transition metal and/or an active complex in an active state capable of forming an active state on a support, and an image thermal pattern is applied to the recording member. Li image forming method.

In the image-forming composition of the present invention, the tetrazolium salt or its derivative and the light or M reducing agent form a redox couple, so that the composition itself has image-forming ability. The present inventor previously developed a lithographic printing original plate using an image forming composition comprising this redox couple in Japanese Patent Application No. 56-194417.
No. 56-194418, No. 56-151206, and No. 56-129090.

The present invention further adds a transition metal and/or a complex in an active state to the proposed 11111 image-forming composition, and utilizes the ability of formazan, which is a reduction product of a tetrazolium salt, to convert into a Φ rate. By simultaneously carrying out a specific amplification reaction and imparting internal strengthening ability, it is possible to form an image with high optical density, and the light or heat sensitivity of the composition is improved.

The tetrazolium salt used in the present invention is widely used as an indicator in biochemistry for confirming reduction fermentation and reduction activity. Examples of compounds having the following general formula include:

General formula (1) R, -N-N' (where R,, R, is an aryl group, substituted aryl group or heterocyclic group, R, is hydrogen; alkyl group; aryl group; substituted aryl group; OH group; C0OH group; functional group such as NH, group, X is an anion) General formula (n) (R,, R,, R,, X is the same as general formula (1)) General formula (l[I) R1, X are the same as general formula H, Y is -(cHt)
n (where n represents t~12) or zeco)-group or 10% group. ] General formula CN) [However, turtle, R, and X represent the same as in general formula (1).

] All of these tetrazolium salts are water-soluble or hydrophilic, insoluble in organic solvents, and have a colorless or yellow color, but in an excited state by light or heat, they are reduced by a proton abstraction reaction from a proton donor and form a formazan structure. As a result, it develops a red color and is water-insoluble.
Moreover, it becomes insoluble in organic solvents. This reduction reaction is expressed by the general formula (1
In the case of tetrazolium salts or derivatives thereof, the following reaction mechanism is considered to proceed.

(1) 8.5, / (l') The formazan thus produced is a Lewis base and has an imino group proton that can be substituted with a metal, so it is a Lewis acid such as Cu or Ni.

Reacts with active transition metals such as Co or active complexes to form chelates. For example, in the case of formazan of the general formula (I'), the following chelate (in the formula, M is a metal) is formed.

However, the rate of chelation reaction varies depending on the type of substituent. For example, in general formula (I'), R, R, and R are each an aryl group (R, is generally directly related to the reaction, except in the case of dithizone). However, formazan in which the ○-position of these aryl eyebrows is substituted with a functional group of S such as a hydroxyl group, a carboxyl group, an arunic acid group (-AO, H,), or R1 is a heterocyclic group. Holmazan is fast. In particular, formazan in which the heteroatom of the heterocyclic group is nitrogen is the earliest. This is because all of the donor atoms involved in the reaction in formazan are nitrogen, which further promotes the reaction with metal ions. In addition, the color tone of these formazans varies depending on the 'm class of transition metals or the type of metal in the complex. For example, in the general formula (I'), R1, bird is an allyl group, and the o-position is a hydroxyl group, a carboxyl group, Formazan, which has an Arun group, reacts with copper, nickel, copal metal, silver, etc., and exhibits colors such as blue, purple, green, and black. The bathochromic color tone is deeper for those with functional groups than for those without functional groups.
It gets deeper. The vividness of the color tone becomes brighter in the order of aryl group, substituted aryl group, and heterocyclic group. The above tendency is the same for formazan obtained from tetrazolium salts of other general formulas.

The chelated product of formazan, which is a reduction product of a tetrazolium salt, formed in step 5 above is water-insoluble and non-bathable in organic solvents, like formazan itself, and forms strong images due to its internal strengthening ability. do.

Next, specific examples of the tetrazolium salts represented by the above general formulas (1) to (■) will be shown. In the present invention, from the viewpoint of image formation speed, those capable of producing formazan with a fast chelation reaction rate are preferred.

1) Example of general formula (1): (R1+Rz is an aryl group, a substituted aryl group or a heterocyclic group, R is hydrogen; an alkyl group; an aryl group; a substituted aryl group; an OH group; a C0OH group; an N4 group, etc.) functional group, X is an anion) 2) Example of general formula (U) (RHa R*# R1# X is the same as general formula (1))
(Left below) ) Example of general formula (lft) (lit) (R1, R,, X are the same as general formula (1), Y is (CHI
) n - (where n is 1 to 12) e f / ) (blank space below) 4) Example of general formula <N) <N) [However, Rs e R@ # X is the same as general formula (1),
The above tetrazolium salts can be easily synthesized by a known combination method. RIJ's tetrazolium salt of general formula (1,) is synthesized according to the following reaction formula. General formula (
The Al3c method for synthesizing the tetrazolium salt of IJ is almost the same.

The tetrazolium salt of the general formula (IJ) is synthesized by the following reaction method.

Furthermore, the tetrazolium salt of the general formula (IV) is synthesized by the method shown in the reaction formula below.

R1-Y-N, "+2R, -CH=N-NH-R, -→
Synthesis examples of tetrazolium salts of general formulas (1) to (IV) such as those described above are described in detail in the following literature.

S, S, Karmark@r, A, G, E, Psari.
e, A, M, Se21gmaa: J, Org, Ch@
m, , 25,575 (lsJ60JP, Fr1se
: Ber, 24, 4178 (1875) Ei Suenaga: Yakushu, υ, 803, 850 (1959) 8, A.
Lomonosov, 1. N, (T*tsova, Yu
,A,Ry15akova:J,Anal,Ch*m,
USSR, 21, 206 (19663 Akira Kawase: Ja
pan Anal, 16.1364 (1967) E, F
1++ch*r: Ann, 190, 118 (1878
) Kuhn, R, Murzlng, H: Ch@m, B@
r,, 86.858 (1953) Chemlcal
RsvL@w@, 55,335-483 Mayu, some of these are Eastmann OrganicCb@m1c
It is commercially available from Aldriah Ch@m1oi1 and Tokyo Kasei.

The yt reducing agent and the thermal reducing agent will be briefly explained. The original reducing agent or the thermal reducing agent is a substance that generates protons in the form of -gII when light or heat is applied, and both of them are A RL base agent is generated, and the coexisting tetrazolium salt is reduced to generate formazan. All known base reducing agents that generate a reducing agent by one-component decomposition or photon rearrangement can be used. For example, (Gnot cyroin (HJ aromatic carbazide <1) aromatic diaryzonulphonate (2I (-pennui tanul) (l) i-
Hydrogen sources such as quinones (quinones combined with an active hydrogen atom source such as polyethylene glycol) such as 1,4-naphthoquinone, 2-methyl-1,4-
Naphthoquinone. 2,3-dimethyl-1,4-naphthoquinone, 2,3-dichloro, 1,4-naphthoquinone, 2-thiomethyl-1,4-naphthoquinone, 2-(1-formyl-2-propyl)-1,4- Naphthoquinone.

2-(2-benzoyl-ethylfu 1,4-naphthoquinone, 9.10-phenanthrenequinone, 2-t-butyl-
9,10-anthraquinone, 2-methyl-1,4-anthraquinone.

2-Methyl-9,1〇-anthraquinone fat.

Further, typical examples of hydrogen donors that can be combined with these external hydrogen source quinones are as follows.

l) Polyethylene glycol 2) 2-enyl-1,2-ethanediol 3) Nitrotricetonitrile 4) Triethylnitrilotriacetate 5) Polyvinyl butyral 6) Polyvinyl acetal 7) 1,4-Benzenedimetatool 8) Methylcellulose 9) Cellulose acetate Butyrate 1 Li 2,2-bis(hydroxymethyl,)propion 藏11J l,3-bis(hydroxymethyl LMX12
) 4-nitrobenzyl alcohol 13) 4-methoxypencyl alcohol 14) 2,4-dimethoxybenzyl alcohol 15) 3,4-dichlorophenyl glycol 167N-(Hydroxymethyl J benzyl alcohol
7) N-(hydroxymethyl)phthalimide 18) 5-
(Hydroxymethylnow 2sil hei hydrate 19) Ni Tori Ro Toro Toro coin 2QJ
2, 2', 2'-)
Re-e-chi-ru, =, To-ri-ro-to
21) 2,2',2'-ditrilotricetophenone 22) Polyvinyl acetate 23 Polyvinyl alcohol 24) Ethyl cellulose 25) Caliximethi9 cellulose 26 Polyvinyl formal CM) Uchianezuigen quinone ( Quinone containing active hydrogen atoms inside 1) 5,8-dihydro-1,4-naphthoquinone 2) 5
．． 8-dihydro-2a 5 #8-trimenal-1,
4-naphthoquinone 3J1,4-dihydro-1,4-dimethyl-9゜10-
gamma-nthraquinone a) 2-dimethyl-minol 1,4-naphthoquinone 5-2-methoxy-1,4-naphthoquinone e) 2-henzoyloxy-1,4-naphthoquinone 7) 2-methoxy-3-chloro-1, 4-naphthoquinone 8 2,3-dimethoxy-1,4-naphthoquinone 9) 2,3-jethoxy-1,4-naphthoquinone 0) 2-ethoxy-], 4-naphthoquinone 11) 2-
7 enethoxy 1,4-naphthoquinone 12 2-(2-methoxyethoxy-1,4-naphthoquinone 13) 2-(2-ethoxyethoxy-2 1,4-naphthoquinone 14) 2-(2-phenokidinoethoxy-1° 4-naphthoquinone 15) 2-ethoxy-5-methoxy-1,4-eggplant
Toquinone 16) 2-ethoxy-6-methoxy-1,4-naphthoquinone 17) 2-ethoxy-7-methoxy-1,4-naphthoquinone 18) 2-n-propoxy-1,4-naphthoquinone 19
2-(3-hydroxyzoloboxyJ-1,4-naphthoquinone 20) 2-impropoxy], 4-naphthoquinone 2
1) 7-medoxy 2-inzolophoxy 1,4-naphthoquinone 22) 2-n-butoxy-1,4-naphthoquinone 23J
2-11@(+-butoxy-1,4-naphthoquinone 24) 2-n-pentoxy-1,4-naphthoquinone 2
5'J2-n-hexoxy-1,4-naphthoquinone 26
2-n,-hebutoxy-1,4-naphthoquinone 27
) 2-acetoxymethyl-3-methyl-1,4-naphthoquinone 28 2-methoxynonal-3-methyl-1,4-naphthoquinone 29) 2-(β-chocetoxyshetyl-1,4-naphthoquinone 30J 2 -'N, N-bis(cyazmethyl) pinomethyl-3-methyl-1,4-naphthoquinone 3])
2-Methyl-3-molpolytumethyl-1,4-naphthoquinone 32 2-hydroxymethyl-1,4-naphthoquinone 33) 2-hydroxymethyl-3-methyl-1,4-naphthoquinone 34 2-(l-hydroxyethyl )-1,4-su7
Toquinone 35 2-(2-hydroxyethyl, 4'-naphthoquinone 36J2-(1,1-dimethyl-2-hydroxyethyl 1,4-naphthoquinone 37) 27 Promo 3-impropoxy-1,4-naphthoquinone 38 2-ethoxy-3-methyl-1,4-naphthoquinone 39) 2-chloro-3-piperidino-1,4-naphthoquinone 4-2-morpholino-1,4-naphthoquinone 41) 2
．． 3-Noviperisino 1.4-Naphtginone 42) 2-
Benzylamine d-chloro-1,4-naphthoquinone 43 2-methyloxycarbonylmethoxy-1゜4
-Naphthoquinone44)2-(N-ethyl-N-benzyl1))-3-
Chloro-1,4-naphthoquinone 45) 2-morpholino-3-riC1o-1v'-naphthoquinone 4li 2-piperidino-3-chloro-1,4-naphthoquinone 47no 2-gel chloride is no 3-chloro -1,4-naphthoquinone 48) 2-diethyl minnow 1,4-naphthoquinone 49
) 2-piperidino-1,4-naphthoquinone 50) 2-(
2-hexyloxyno-1,4-naphthoquinone 51) 2-neo-pentyloxy-1,4-naphthoquinone 52) 2-(2-n-pentyloxy)-1,4-naphthoquinone 53) 2-(3-methyl -n-butoxy)-1,4-
naphthoquinone 54J2-(6-hydroxy-re-hexoxy)-1,
4-Naphthoquinone 55 2-L (6-hydroxy-n-hexyl-1,4-naphthoquinone 56) 2-ethoxy-3-chloro-1,4-naphthoquinone 57) 2-ethoxy-3-chloro-1,4- Naphthoquinone 58) 2-, di(phenylnomethoxy1,4-naphthoquinone 59) 2-(2-hydroxyethoxy)-3-chloro-
1,4-naphthoquinone 60) 2-Methyl-3-(l-hydroxymethyl)ethyl-1,4-naphthoquinone 61 2-acetidino 3-chloro 1,4-naphthoquinone 62) 2-(2-hydroxyethyl)・)-3-bromo-1,4-naphthoquinone 6372.3-dimorpholino 1,4-naphthoquinone 64) 2-ethylamino 3-piperidino-1,4-'
naphthoquinone 65) 2-ethoxymethyl-1,4-naphthoquinone 66
2-phenoxyme, 1,4-naphthonanone Note that the internal hydrogen source quinone is also the same as the external hydrogen source quinone, water'
In combination with a cumulative donor, V! Ru.

In this case, the conversion to a reducing agent is further promoted.

Other first order ゛・quinonization+! R items can also be used as a detoxifying agent.

1.2-naphthoquinone 91: For example, 1.2-naphthoquinone, 8-methyl-1,2-naphthoquinone, 8-ethyl, -1°2-naphthoquinone, 8
-4-propyl-1゜2-naphthoquinone, 8-isotu'
Ex, 1,2-naphthoquinone, 8-hydro 2-naphthoquinone, 3-methyl, 1,2-naphthoquinone, 3-ethyl-1,2-naphthoquinone, 3-impropoxy- 1,2-naphthoquinone, 3-inzolobyl-1,2-naphthoquinone, 3.-hydroxy-1,2-
Naphthoquinone, 3,8-dihydroxy-1,2-naphthoquinone, 3-hydroxy-8-methyl-112-naphthoquinone, 3-hydroxy-8-inzolobyl-1,2-
naphthoquinone, 3-hydroxy-8-isopropoxy-
1,2-naphthoquinone, 3-methyl-8-hydroxy-
1,2,,-naphthoquinone, etc.

Xanthone M For example, xanthones. 4-Methylxayton.

1,4-dimethylxanthone, 4,5-dimethyl-xanthone, 4-impropyl-xanthone, 4-hydroxyxanthone, 4,5-dihydroxyxanthone. 4.
5-diingropyrsaquinthone, 4-pencylxanthone, 4,5-dibenzylxanthone.

9. l〇-anthraquinone and its υ〇-lyrylic fatty conductors: ylllll eva-anthraquinone-methyl-lyanthraquinone, l-ethyllyanthraquinone, 1-anthraquinone, 1-benzylanthraquinone. 1,5-Dimethylanthraquinone, 1,5-diethylanthraquinone, 1,5-diisopropylanthraquinone, 1.5-dibenzylanthraquinone. 1-Hydroxy, cyanthraquinone, 1,4-dihydroxyan)laquinone, 1-diminorintraquinone, 1,4-cyanthraquinone, 1
．． 5-dihydroxy intraquinone, etc.

0-Rubenzophenones in alcohol 21'll L Hahenzophenone, 2-methylpenzophenone + 2-ethylbenzophenone, 2-izolobilpenzophenone, 2-benzylbenzophenone, 2,
4,6.2',4',6'-hexamethylpenzophenone, 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, etc.

1.6-pyrenequinone, ], 8-pyrenequinone,
9. Polyquinones such as 10-phenanthrenequinone can be used.

All of the above reducing agents perform a redox reaction together with a tetrazolium salt when exposed to active radiation of 300 nm or more, but there are some differences in the manner and mechanism of the reaction. Many photoreducing agents react rapidly with tetrazolium salts due to active radiation. The polar ones containing quinone photoreductants exhibit this reaction characteristic. Other photoreducing agents are also #1! , VC oxidation-reduction and binding reaction are carried out when the source and base are combined.

It takes a long time to reduce the tetrazolium salt. In many cases, it is preferable to heat the redox solution made from a reducing agent and a tetrazolium salt to bring the reaction to just the right time. The optimum heating temperature varies by Ω depending on the photoreductor present, the tetrazolium salt, and the true velocity, and specifically, the range of 80 to 15 (1°C is preferable).

Among the above photoreducing agents, one of the quinones used in the present invention is quinone, and among them (M), water source quinone is preferred.

As a thermal reducing agent, t, Q) 1 group or Nfl in the molecule
, has two or more groups r, and they are mutually O- or p-
Those in the highest position are most effective. In other words, a method that satisfies the conditions of ordinary silver halide photography is also valid in the case of 4: Invention.

For example, polyphenols having two or more Soe/-A-'Msk, mononaphthols, bisnaphthols, polyhydroxybenzenes having two or more hydroxyl groups, polyhydroxynaphthalenes having two or more hydroxyl groups,
Ryo Scorubin 1 Cap 3-Pyrazolidone M.

Pyrazolin-5-ones, pyrazolone copper, noenylene dilene chloride, hydroxylamine chloride, 1-hydroquinone 7-ether fA, hydrooxane chloride, hydrazide field, cycloba dooxime 4J, N-hydroxy urine'JA lin, etc. Can be mentioned.

Depletion VL f transition metal in the occupancy state or as an active complex r y in the reduction product of a tetrazolium salt or its derivative h'o
Any substance that can form a chelate with small lumasan can be used. This I'i! + The active complex in the S transfer state is a Lewis acid as mentioned above,
It reacts with formazan, a Lewis base, to form a chelate. Here, the transition metal in an active state refers to a selected metal with a divalent or trivalent valence, or a transition metal that is active in an atomic state.9. In addition, an active complex refers to a combination of formazan and a ligand. Specifically, 2 recommendations or 3
Zn is a salt of a valent transition metal.

co+4. Cu++, N, 7 F@++, Fe+
++ ion chloride and acetate are listed as 0゜7tl
ZII51 is N1 as an active S transfer can in the JA child state.
A powder of θ is mentioned. On the other hand, examples of complexes that can exchange ligands with formazan include Ba5olo: Unscrupulous Reaction Preparation (Tokyo Kagaku Doujin Shuppan, Taube: Ch*m, R
@v, , 50, 69 (1952) and Adamson
: J, A, Ch@m, , 73, 4789 (1951J
For example, Chloro kk (IJ clam body, Hexakis (thiocyanite Jli & (1) Ryomonni r)
2) Rephonoptan-1.2.4-trical cod salt complex salt, hexametaphosphoric acid-zinc complex salt, tripolyline enemy-zinc salt, dimethylglyoxime -Zinc complex salt, l,2-cyclohexanedione diane-kisime-zinc side salt, setone-nickel Mj! , 2-phosphonobutane-1,2,4
-i ricarzenic acid-nickel complex salt, tripolyphosphoric acid-nickel lead salt, hexamethalin [edge-nickel*m, 2-
Examples include furyldioxime-nickel complex salts.

In addition to the above-mentioned components, the composition of the present invention may contain binders and other auxiliary agents. As the 0° binder, a wide variety of natural or synthetic d-mers can be used.

Among others, linear fluoroforming polymers such as gelatin, 7L reulose, etc.

Silieba ethyl cellulose, butyl cellulose.

Cellulose cetate, cellulose, cellulose cetate,
Cellulose butyrate, cellulose acetate, etc.: pinyl polymers, e.g. polyvinyl acetate &
Polyvinylidene chloride, polyvinyl acetal Examples include polyvinyl butyral, poly(vinyl chloride doruvinyl acetate), polystyrene, polybutadiene,
Polyvinylpyrrolidone, electrocombination or cocombination of acrylic acid or methacrylic acid or their esters; polyesters such as poly(ethylene glycol to isophthalic acid to terephthalic acid), poly(p-cyclohexanedicarboxylic version to inphthalic acid to cyclohexylene bismethanol) No, poly(p-cyclohexanecyclocarpic acid ~2,2
, 4,4-tetranorcyclobutane-1,3-diol) is preferably used.

Condensation products such as epichlorohydrin and bisphenol are also useful binders. Examples of other auxiliary agents include synthetic or natural waxes, such as stearic acid, taro wax, carnauba wax, microcrystalline wax, and low-molecular polyethylene.

In the composition of the present invention consisting of the above-mentioned components, the tetrazolium salt, the entire transition of the active state, or the useful charge of the T-occupied complex is 0 per 1 light-speed source or 1 mole of thermal reducing agent, respectively.
．． 1-10 mol, 0.5-10 mol@degree is suitable.

-When using a primary pinter, it is appropriate to use 10 to 90% of the composition of the king salmon.

Since the composition of the present invention is photosensitive or heat-sensitive, it is generally used as a single-type recording material by coating it on a support such as paper, snack film, or gutter board. Convenient formula. In this case, the 111111M formation method uses a light-velocity base agent, and the coating surface is 300 am
Longer wavelength activity 4! Is it okay to use i11 irradiation and form it into a medium rate image, or is it even more color reaction? Promote and share 11! II. It is preferable to heat the bamboo bales to about 80 to 150°C. Is this heating particularly important for the reduction length ratio, the speed of light precursor that has a slow rate, or formazan that has a slow chelation reaction rate? Tetrathurium field generated? It is effective when used. In addition, the stability of the image is due to heating 1.
This is thought to be due to the removal of external images.

-For those using Manbumoku 47c agent, the applied surface KAh
・VP-n (including heat from infrared sources, laser sources, etc.) τ
What is necessary is just to apply it and form a chelate image feature.

The inventive composition is divided into a redox couple of a tetrazolium salt and a primary or thermal reducing agent, and a transition metal in an active state or an active substance. The transition metal or sardine body is coated on a normal support such as paper, glass film or skeleton board to form a recording base material A, A combination of these can also be used as a combined type Q) self-recording embroidery. l of this @ meeting
Il]l1JllI formation method is to densely layer the forming cloth surface of the ball distribution member A and the material of the recording age port B, and for the recording member A Vt4 using the 1 light velocity prime agent, 11ill wedding silk is formed from the recording material A side of this recording 6b. Originally, for the heat distributing member A using a thermal reducing agent, it is sufficient to apply a heat pattern from the side of the V-layer recording member A in the same manner, and to apply the same heat pattern to the V-chelate 111Ij stage r shape.

However, in the case of the image-forming FfJl method using exposure, it is preferable to heat the above-mentioned N@ as in the case of the single-B1 recording member in order to promote the color reaction.

It should be noted that the quality of the recorded matter obtained by using either the single-type or single-balanced type recording phase is as follows: Lbν, -
Well, the skin part is soluble in the original mama 7.

A lithographic printing original plate having an oil-refining area on a hydrophilic substrate can be prepared by bathing the background area with water.

Examples of the present invention are shown below.

Examples 1 to 36 Tetrazolium salt of compound 'kdJ 4 shown in Table 1 below 2.5 x 11 J molar fraction, 2.6-dinitoxy 1
, 4-he7so*/71. Of (5, OXl 0-”mol) and 2.OP C6,43Xl
0 mol) was dissolved in 20 liters of ethanol in dark sugar to make a uniform bath. Next, 1.4 p (10" moles) of zinc chloride was dissolved in 50 m of water, and this was impregnated onto 80% high-quality paper using glass*1, and then dried with warm air. Further, the sled was impregnated with the ethanol flour solution 1 in a dark place using a glass roll, and then dried with warm air to prepare a recording member.

Next eThe light intensity of the wing surface Vt material surface of the Kiku member here is 3
When ultraviolet light from a 20W black ray was passed through a temporary heated roller at 120°C to give 300μW/c- at 65nm, the 1wI light area showed a clear color as shown in Table 1. Color development at time-health is also listed in Table-1. The skin part (unexposed part) of the obtained Kiki 9bA product was colorless or pale yellow, and it was confirmed that there was almost no change even if it was kept under normal indoor light for several weeks. .

Table 1 Table -1 (Part 2) Note) *: Filter according to the color tone of the valley sample Macbeth's 1F needle is 6t11.

Example 37 Compound AId-47 gold was used as the tetrazolium salt, and 1.0y of 2,6-jethoxy-1,4-benzoquinone
OEl, 4-dinaphthol 1, IF (4,0Xjt
A recording member was prepared in the same manner as in Examples 11 to 36, except that 1-"mol) was used.

Next, in this recording material, the cloth seller Fryokusia IJIc Village, F
1a T To thermal head (temperature around the head: 25
The printed part is printed at 0℃) and the printed part is from Toguchi Netsu VC.
A purple color developed and a clear image was obtained.

Examples 88-44 Using transition metals or active complexes in the r-occupied state shown in Table 2 below in place of zinc chloride, and a method for preparing these sapon solutions? −
As shown in the same table, nine recording members were prepared in the same manner as in Example 34.

Next, a painter's shape 55 is placed on this recording member in the same manner as in Example 37.
I went to L1. The results are shown in Table-2.

In addition, the same table also includes the background part (non-exposed m).Example 45 2-isogloboxy 1,4-naphthoquinone 2,9 F
(12,5X l O-' mol] and styrene-butadiene co-polymerized 1.OP t ) was dissolved in 10 mg of toluene, and this was spread on a 75 μm thick polyester film with 4 i
Apply it using the doctor blade 1 of Example 34, dry it with warm air, and then apply the tetrazolium used in Example 34 on top of it.
1.9 II (2,s
A fC solution containing mgVC dissolved therein was applied using a 2-bill doctor blade and dried with warm air.This was used as the d-pipe member AI.

On the other hand, chloride! Il! Lead 2.8P (2X10 mol) l
Z water 50xtllC bath solution, this is 1! -55 kg/cancer was impregnated with a glass rod, and dried with hot air.

This is t! I will write my own record as PBL.

Next, 1 lkl was applied to the non-coated surface of the ball distribution member AI of the 1'c composite mold fM member obtained in this manner in the same manner as in Examples 1 to 36.
- Noisy light! After that, place the coated surface in the drawer of the recording member Bl, heat it to 100°C, and roll it with two rollers 1&i.
When passed through J, a transfer IAL'0.9 was recorded on the recording member Al.
6 dark blue images were formed.

Large h1 example 46 Used in actual IM example 37. Compound I d-47 was applied using a 2 mil doctor blade to a 12 µIn thick polyester film along an ethanol bath containing tetrazolium enriched, 1,4-dinaphthol, and sterol. This is then dried with warm air. This is used as recording member A2, and this is combined with the recording member Blr created in Example 45 to form a composite type recording member. B1 on the A2 coating side
A dense layer of blood was placed on the surface of the blood cloth, and printing was performed on the recording member A2 in the same manner as for IJ37.Next, a dark boar-colored artist with a manufacturing size of 1.02 was placed on the printed part of the recording member A2. Formed into a circle.

47.・ 9.1O-phenanthrene beef non 2.1 '9 (10
-”Morne, polyethylene glycol (min-7-in
6oo) 0.8y and f compound A, tetrazolium salt of Id-48 5.7 F (1,5X I C1” mole)
Dissolve ethanol/impropylfurcol = 1/1 (mixed bath medium with a mixing ratio of 2 Btml VC, dissolve this and copal chloride) 2.38 PC, 10 mol) in 20 mg VC of water, and then mix with the solution to make a homogeneous solution. This was made into a solution, treated to make it hydrophilic, coated on a Tsujiko aluminum plate using a 2 mil doctor blade in a dark place, and dried with hot air for 7 tons.

The curved surface of the obtained recording member was irradiated with an argon laser with a wavelength of 488 nm at a heating density of 5 am J/cd, and then heated to 120°C and heated to a low temperature of 241°.
- Heat it between 7 and 7, leave it for a few minutes, and then heat 1.
A clear w6 crystal with a degree of 0.91 was formed. ,
Cobalt chloride absorbs moisture from the air and contains the original water of crystallization.
C Go back. Therefore, the background part becomes colorless. ] Next, this record @ is immersed in water Vc and dy treatment part (skin part)
By removing the base material, a lithographic printing plate was obtained in which the non-containing base part was hydrophilic and the base part was lipophilic. The image formed in this way is strong due to the internal reinforcement of the chelate.

Procedural Amendment 1, Indication of Case Relationship to Patent Application No. 89725 of 1982
Patent applicant Ricoh Co., Ltd. 1-3-6 Nakamagome, Ota-ku, Tokyo (674) - Representative Takeshi Oue 4, Agent 5 Contents of amendment l) Specification 1 Page 10 #! Line 3 r Nlt After J, “Z
n) Join J.

2) In the second line from just below No. 66, "stearamide" is corrected to "stearylamine acetate."

3) At the end of page 69, “densitometer ga” is replaced with “densitometer de” +
Have sex.

4) In the 71st member table-2, "stearamide" in Example 4420 is corrected to "stearylamine acetate". amended to ``Amin''.

6) 1 yen 73rd line 6th line F "stearate aon" is corrected to "stearylamine acetate".

that's all

Claims (1)

[Claims] 1. a) Tetrazolium salt, b) 300 nm
A photoreducing agent capable of reducing the component a) when exposed to longer wavelength active radiation, or a thermal reducing agent capable of reducing the component a) when heat is applied, and 0) a component of the component a). An image-forming composition comprising as a main component an active transition metal and/or an active complex capable of forming a chelate with a reduction product. 2.&) Tetrazolium salt, 1)) A photoreducing agent that can reduce the component a) when exposed to active radiation with a wavelength longer than 300 nm, or a photoreducer that can reduce the component a) when heat is applied. and c) a transition metal and/or an active complex in an active state that can truly form a chelate with the reduction product of component a). The iTI image forming method is characterized by performing imagewise exposure using actinic radiation having a longer wavelength or by applying an image-wise thermal pattern. 31) Tetrazolium salt and b) A photoreducing agent capable of reducing the component a) when exposed to actinic radiation having a wavelength longer than 300 nm is applied to a recording member coated or impregnated on a support with active radiation having a wavelength longer than 300 nm. A record in which a support is coated or impregnated with an active state of transition gold, a silicone and/or an active complex capable of forming a chelate together with the reduction product of the IL) component after imagewise exposure with actinic radiation. An image forming method characterized by heating a member by heating it. 4. Hatake) A recording member having a support coated or impregnated with a tetrazolium salt and b) a thermal reducing agent that can reduce the component a) when heat is applied, and a chelate together with the reduction product of the component a). 1. An image forming method, which comprises bringing into close contact with a recording member in which a support is coated or impregnated with a transition metal and/or an active complex in an active state that can be formed, and applying an image thermal pattern.