JPS60263144A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. improved in stability and made of a leuco dye and a photooxidant by incorporating a specified cyclic hydrazide dimer. CONSTITUTION:The photosensitive compsn. comprised of the leuco dye and a photooxidant contains at least one cyclic hydrazide dimer represented by formula I in which R1, R4 are each H, optionally substd. alkyl, optionally substd. aryl, or optionally substd. aminocarbonyl; R2 is H, optionally substd. alkyl, or optionally substd. aryl; and R3 is H, optionally substd. alkyl, alkoxy, or formula II. Said cyclic hydrazide dimer acts as a stabilizer, and it is used, preferably, in an amt. of 1-200wt% of the leuco dye, thus permitting the obtained leuco dye to be stable without discoloration even after being stored for a long period under high temp. and high humidity or even after being left under a safe light for a long period.

Description

Detailed Description of the Invention: "Industrial Application Field" The present invention relates to photosensitive compositions, in particular stable compositions that, when irradiated with actinic rays, exhibit a visible contrast in relation to unirradiated areas. The present invention relates to a photosensitive composition.

"Traditional technical field" Many photographic applications, e.g. photoresists.

In printing plates and the like, it is highly preferable that the exposed areas be visible after exposure and before exposure.

Particularly effective in this regard are the stone processes in which various leuco dyes are oxidized to their corresponding dyes using organic polyhalogen compounds or the original oxidizing agent gold.

(For example, Phot, Sci, Bng, , j,
? I-/03 (/ri4/) and U.S. Patent No. 3.
0 gukos.

See No. 111. ) In order to prevent discoloration due to exposure to air or oxygen, the composition consisting of such a leuco dye and a photooxidizing agent contains
Contains antioxidants. For example, U.S. Patent No. 3.
04'Co, No. 316 has a hydroxyl group on the benzene ring,
Organic reducing agents in which at least another hydroxyl or amine group is located elsewhere on the benzene ring, such as hydroquinone, catechol, resorcinol, hydroxyhydroquinone, pyroglycitur, and 0-aminophenol and p-aminophenol. A method of preventing discoloration of leuco dyes that occurs upon exposure to air or oxygen in the presence of light or heat or both is disclosed by adding amine phenols). Also, U.S. Patent No. 4
4,061. , <tj> fully discloses that by adding certain compounds to a print-out composition containing a leuco dye and a photooxidizing agent, a stable composition with little discoloration during storage can be obtained.

``Problems to be Solved by the Invention'' However, even with these compositions, when stored for a longer period of time, or when stored at high temperatures and high humidity, they discolor, or as described below, become baked. There are problems such as lowering the sensitivity of the photocurable component used in the dispensing composition to actinic radiation.

In addition, the photosensitive composition of the present invention is usually handled under light (safelight) that blocks active radiation in the absorption wavelength range of the photooxidizing agent (safelight), but even under such safelight, it cannot be left for a long time. However, there is a problem in that it becomes discolored and cannot be washed, and further improvements have been desired.

It is therefore an object of the present invention to provide a photosensitive composition comprising a leuco dye and a photooxidizing agent with improved stability.

Specifically, leuco dyes and leuco dyes that have substantially the same performance as before storage, even after being stored for a long time under high temperature and high humidity conditions, or even after being left under the above-mentioned safelight for a long time. An object of the present invention is to provide a photosensitive composition comprising a photooxidizing agent.

Another object is to provide a photosensitive composition comprising a leuco dye and a photooxidizing agent that does not reduce the sensitivity of the photocurable component used in combination to actinic radiation.

"Means for Solving the Problems" In order to achieve the above-mentioned object, the present inventors have conducted five different studies, and as a result, the following general formula (I ) By containing the cyclic hydrazide dimer, the product will not change color even after being stored under high temperature and high humidity conditions for a long time, or even after being left under a safelight for a long time. It has been found that a photosensitive composition can be obtained which is stable, has suppressed dark reactions during storage, and does not reduce the sensitivity of the photocurable component used in combination. Although the mechanism is not clear, the cyclic hydrazide dimer appears to act as a stabilizer.

General formula (I) R1 and R4 represent a hydrogen atom, an alkyl group, an alkyl group substituted with 1, an aryl group, a substituted aryl group, an aminocarbonyl group, or a substituted aminocarbonyl group.

R2t1. Hydrogen atom, alkyl group % substituted alkyl group, aryl group, or substituted aryl group, R3 is hydrogen atom, alkyl group, IIv-substituted alkyl group.

R.

In the photosensitive composition of the present invention, the stabilizer cyclic hydrazide dimer, which is the most characteristic component, specifically includes the following, but is not limited to these.

(1) )IH HH (4) 1(H 0(11-IH Q7JHH cl! α) These and stabilizers are 7 to 10
Preferably used at 0% by weight.

A range of ˜ioo weight percent is most preferred.

On the other hand, typical leuco dyes that can be used in the present invention include the following. Aminotriarylmethanes such as bis(p-dibutylaminophenyl)-rp-(λ-anoethyl)methylaminophenyl)methane, bis(p-dimethylaminophenyl)-coquinolylmethane, tris(p-dibutylaminophenyl)methane, etc. kind,
J, 1-bis(diethylamino)-dephenylxanthine, 3-amino-6-dimethylamino-λ-methyl? Aminoxanthine IL3.6-bis(diethylamino)-9-(o
-ethoxycarbo'nylphenyl)thioxanthine, 3
, 6-bis(dimethylamino)thioxanthin and other aminothioxanthines, 3.6-bis(diethylamino)
-ta, 10-dihydroterphenylacridine, j,
Amino-? such as A-bis(benzylamino)-ta, IO-dihydromethylacridine, , 10-dihydroacridines, aminophenoxazines such as 3,7-bis(diethylamino)phenoxazine, aminophenothiazines such as 3.7-bis(ethylamine)phenothiazine, 3.7-bis(diethylamino 1-j- hexyl
Aminodihydrophenazines such as r,io-dihydrophenazine, aminophenylmethanes such as bis(p-dimethylaminophenyl)anilinomethane, Hiro-amino-μ
leucohindamines such as '-dimethylaminodiphenylamine, aminohydrocinnamic acids such as V-amino-α,β-di/anohydrocinnamic acid methyl ester, /-(λ
-naphthyl)-λ-phenylhydrazine and other hydrazines, /,ii<-bis(etheramino)-2,3-dihydroanthraquinone and other aminocos, 3-dihydroanthraquinones, N,N-diethyl-p-phenethylaniline, etc. phenethylaniline m, 10-aceteru3.
Acyl derivatives of leuco dyes containing basic Nl (groups) such as 7-bis(dimethylamino)phenothiazine; single color-forming compounds that do not have oxidizing hydrogen such as tris(hiro-diethylamino-0-lyl)ethquine carbonylmethane; Leuco-like compounds, leucoindigoid dyes that are oxidizable to the nose, U.S. Pat. Nos. 3,0172,611 and 3,
01t, 2.

Organic amines that can be oxidized to the 'i5 color form as described in No. 577. Typical compounds of this type include primary compounds. Ge.

μ′-ethylenediamine, diphenylamine, N.

N-dimethylaniline, g, 4L'-methylenediamine triphenylamine, N-vinylcarbazole.

Preferred photooxidants are inert until exposed to actinic radiation, such as visible light, ultraviolet light, infrared light, X-rays, and the like. Various photooxidants have different peak sensitivities across the spectrum depending on the structure of the compound. As such, the particular photooxidant selected will depend on the nature of the actinic radiation. When exposed to such radiation, the photooxidizing agent produces an oxidizing agent that oxidizes the color former to its color forming form.

Typical photo-oxidizing agents include U.S. Pat.
Carbon tetrabromide and N-promosuccinimide described in No. 11 and Nos. 3 and 50 of the same, and Gua No. 6.

) Halogenated hydrocarbons such as IJ-j lomomethyl phenyl sulfone, azide polymers described on page 3 of the Abstracts of the 1YTR Spring Research Presentation of the Photographic Society of Japan, and U.S. Patent No. 3. azide compounds such as mono-acytobenzoxazole, benzoyl azide, and co-azidobenzimidazole described in Co-rλ, No. 623; and 3-ethyl-/-methoxy-copyridotheacyanine described in U.S. Pat. No. 3,6ij, sHr. Examples include, but are not limited to, compounds such as nonolylolate, l-methoxycometerubiridium p-)luenesulfonate, and the like.

The photosensitive element is prepared by conventional methods such as a leuco dye, a photooxidizing agent and a binder and/or a photocuring component, ie, a dispersion or solution of a color forming agent and a photooxidizing agent is prepared as a binder and/or a photocurable component.

can be prepared by blending the photosensitive composition with a photocurable component and coating, impregnating, or forming a self-supporting layer from the photosensitive composition.

Binders to be added to this composition include synthetic polymer compounds such as acrylic resin, styrene resin, P-lyamide, polyester, polyurethane, and polyvinyl alcohol, modified products of synthetic polymer compounds such as polyvinyl formal and polyvinyl butyral, cellulose, gelatin, etc. Natural polymer compounds and modified products thereof can be mentioned.
The photocurable component that may be added to the composition, including but not limited to, acts as a binder, i.e., binds the mixture of leuco dye and photooxidant to the support. In addition to being a substance, it also plays a role in forming the polymer image gI after 1w.

Representative photocurable components suitable for use in the compositions of the present invention may include the following.

See, for example, U.S. Patent No. 110. Polyvinyl cinnamate described in /20%j, U.S. Patent No. 3.030, polyester incorporating a photosensitive group into the main chain as described in COOX, azide described in the Abstracts of the Spring Research Presentation of the Photographic Society of Japan/Pi, page 66 Polymer (Doubling as Photooxidant), U.S. Patent No. J
, &7Q, 74'j, and U.S. Patent No. j, Pλ.

<Photo-crosslinkable polymer described in try issue, etc. In addition, Tokuko Showa 3
Photopolymerizable composition comprising the ethylenically unsaturated compound described in S-RE No. 5, an initiator and a binder, JP-Ko-Sho 4t
j-/9/, a photopolymerizable composition comprising an unsaturated polyester, a crosslinking agent, and a photooxidizing agent described in No. 2j, JP-Ko-Sho pl-
Ethylenically unsaturated compound described in No. 327/μ, initiator,
A photopolymerizable composition comprising a polymer having a free acid group in a side chain and a protective layer can be mentioned.

The photocurable component is approximately /,1 for the leuco dye type 7 ψ part.
Preferably, one part of 00θ weight is used.

A range of 10-60 θ additional parts is most preferred.

For leuco dyes, stabilizers, photooxidants, binders and/or photocurable components, inert solvents are commonly used to dissolve these compounds.

They can be mixed together in this solvent to form a liquid medium photosensitive composition that can be conveniently and easily applied to a support. Solvents that can be used to form the compositions of the invention include the following. Amides such as formamide, N,N-dimethylformamide, N,N-dimethylacetamide, methanol, ethanol,
Alcohols such as 1-prop/-ol, +2-propyl, butanol, acetone, mether enal ketone.

Ketones such as cyclohexanone, esters such as ethyl acetate and ethylbenzoate, ethers such as tetrahydrofuran and dioxa 7, chlorinated hydrocarbons such as menalene chloride, ethylene chloride and dichloroethane, aromatic hydrocarbons such as benzene and toluene. and dimethyl sulfoxide % 0-dichlorobenzene, dicyanocyclobutane & other common solvents like nometer-cooxohexamethelenimine and mixtures of these solvents.

In producing the composition of the present invention, it is preferable to mix the leuco dye and the photooxidizing agent in a total ratio of 1:1 to 1:100. A particularly preferred ratio is 2:/ to 1;λO. When a binder is used, it can be used in a range of 7 parts by weight of the binder fO, jr to 100 Seishei-type O in a combined amount of Leuco Shikisha and photooxidizing agent.

When the composition is applied and dried.

Preferably, its thickness is between 0.06 and 0.000 microns. A particularly preferable range is 0. / to 100 microns.

In applying the composition to a support, the composition may be impregnated or spread by spraying, spraying, coating with a roller or dip coater, flowing onto the surface of the support, picking up after dipping, or other means. The elements thus produced are dried under vacuum at room temperature or at elevated temperatures.

The material used as the support can be selected from among various materials that do not cause a direct chemical reaction with the coating composition. As such a support material, 11! Fiber-based materials, such as paper, polyethylene coated paper, parchment, cloth, etc., sheet casings or foils of metals such as aluminium, copper, zinc, glass and metals such as chrome, @1 chain, gold, platinum, etc. Coated glasses, synthetic resins and polymeric materials, such as polyalkyl acrylates - for example polymethyl methacrylate; polyesters - for example.

Polyethylene terephthalate; polyvinyl acetal;
Polyamides - for example nylon and cellulose esters - Examples 1-1' Cellulose nitrate, cellulose acetate, cellulose acetate propionate, etc. may be mentioned.

The support can also have a filter layer or an antihalation mt consisting of a colored polymer layer, in order to absorb the exposing radiation after passing through the photosensitive layer and to prevent undesirable reflections from the support. .

a layer of polymer binder containing a yellow pigment (the polymers mentioned above can be used as the polymer pin);
K is particularly effective as an antihalation layer when ultraviolet radiation is used as the exposure radiation.

The element is then imagewise exposed by actinic radiation;
An image (II'it) is formed on the support. Exposure is performed by the contact blind method, projection by a lens, single reflection, and double reflection.
This can be done from the original with # or by other known methods.

If it contains a photocurable component, after exposure to radiation, the radiation-sensitive layer may be flushed, soaked, or swabbed with a solution that selectively dissolves unexposed areas of the radiation-sensitive layer. This can be purified by processing.

The photosensitive compositions of the present invention can be used for a wide range of purposes such as phosphor plates, photoresists, relief mold making, optical reproduction, etc.

"Examples" The present invention will be explained in more detail based on Examples below, but the present invention is not limited to these Examples.

Example 1 A photosensitive composition consisting of the following was prepared.

Furthermore, specific examples (5) and (9) of the cyclic hydrazide dimer which is the stabilizer of the present invention, α- or J
The following 0 known antioxidants (a) to () 1 each 0.
A photosensitive material was prepared using the following method.

(A) Co, 6-di-t-butyl-p-cresol (B) Thiourea (C) Triphenyl phosphate) Resol 7-(E) m-Aminephenol (H) L-Ascorbic acid (T)-p- The photosensitive material obtained above with t-butyl-catechol was coated on a polyethylene terephthalate support to a dry film thickness of 30 μm and dried. This film has a relative humidity of 7! H. It was aged at a temperature of AS6C, and changes over time at 72 hours and ltr hours were followed. The results are shown in Table 1.The concentrations shown in Table 1 were determined by measuring the absorption value at the printout peak of the leuco dye.

"Effects of the Invention" From the results in Table 7, it can be seen that the composition of the present invention has significantly superior stability over time compared to known compositions.

That is, as a stabilizer, the cyclic hydrazide dimer of the present invention has an excellent stabilizing effect compared to conventional stabilizers. Furthermore, the coating solution to which no stabilizer was added began to change color when left to stand, but the coating solution to which the stabilizer of the present invention was added did not change color.

Example 2 A photosensitive composition consisting of the following was prepared.

Furthermore, specific examples (8) and (11)% C of the cyclic hydrazide dimer of the present invention were added to 30 ttl of the above composition as a stabilizer.
I! l) or the following known compounds (c) to (51)
A photosensitive material was prepared by adding λ and oW#9.

(G) Salicylaldehydoxime (U.S. Patent No. A, OTT, <TRY) (W) Dimethylglyoxime (U.S. Patent No. G, O6T, 4As) (x) N, N'
-bis(salicylidene)-/,2-ethylenediamine (U.S. Pat. No. 06&,Uj) The above-obtained photosensitive material was spin-coated onto an electrolytically treated aluminum support at a rotational speed of 20 Orpm and dried. did. This plate was aged under conditions of a relative humidity of 7J and a temperature of 0C, and the reflection density was determined at 11 degrees in Table 1 for 7.2 hours.

"Effects of the Invention" From the results in Table 2, 1. The composition using the cyclic hydrazide dimer of the present invention has significantly superior stability over time compared to those using conventional stabilizers. I understand that.

Ota. The coating solution to which no stabilizer was added began to discolor when left standing, but the coating solution to which the stabilizer of the present invention was added did not discolor.

Example 3 A photosensitive composition was prepared in the same manner as in Example 1, and the compound (9) of the present invention or the known no-hydroquinone and p-aminephenol were added as stabilizers at 0.0/f and coated. A liquid was prepared. This coating solution was applied onto a polyethylene terephthalate support.

A coating layer having a dry film thickness of jOμ was formed. The density of this film 1 at 72 hours was measured in the same manner as in Example 1.

Furthermore, the photosensitive surface of this film was laminated on a copper-clad laminate, and after exposure from the support side, it was developed by spraying a chlorocene solution, and the sensitivity was measured as in Example 1. is the value of absorption.

Moreover, the relative sensitivity is a relative value when the case without additives is set to 10O.

"Effects of the Invention" As described above, the cyclic hydrazide dimer used as a stabilizer in the present invention has a stabilizing effect over time and does not have an adverse effect on the photopolymerizable composition. Recognize.

Example 4 Photosensitive composition 1 was prepared in the same manner as in Example 1, and compound (8) of the present invention or known resorcinol was added as a stabilizer at 0.0/? Dry film thickness on polyethylene terephthalate support after addition! A coating film of Oμ was formed. The film is then used as a yellow fluorescent light (Mitsubishi Neolumisu/
e-FLR4'OY-F II/M) was left under μOO lux conditions to examine its stability over time. The results are shown in the table below.

The measured concentration values in Table μ are absorption values as in Example 1.

"Effects of the Invention" From the results in Table μ, the cyclic hydrazide dimer used as a stabilizer in the present invention also prevents baking out with Safelite F and discoloration of the agent, and is much superior to known stabilizers. I know that there is.

Patent issued by Fuji Photo Film Co., Ltd.-2 (

Claims (1)

[Scope of Claims] A photosensitive composition comprising a leuco dye and a photooxidizing agent, further comprising at least one cyclic hydrazide dimer represented by the general formula 2N). A photosensitive composition. General formula (I) Here, R1 and R4 represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aminocarbonyl group, or a substituted aminocarbonyl group, and R2 represents a hydrogen atom, an alkyl group, and a substituted alkyl group. group, aryl group, or substituted aryl group, and bR3 is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, or 1