JPS58190947A - Composition for formation of radiant sensitive image - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides radiation #sensitivity (τα
d, 1atioz-sensitive). This type of printing (print-out)
The composition has a wide range of uses. For example, it can be included in a lithographic printing plate composition to make the exposure given to the printing plate visible.

With this voice, the present invention can be applied to any photoresist (photoresist) when it is desired to make the light visible to the naked eye.
itt) compositions.

The present invention can also be used, for example, during the creation of scrapes during extra volume processing. By incorporating this composition into an int or lacquer applied to a metal surface and irradiating it through a template, a printout image can be formed of the area of the gold maple to be cut or otherwise worked.

Lithographic printing plate compositions often include printout compositions that include leuco dyes and photosensitizers (also referred to in the literature as accelerators or sensitizers). When the composition is exposed to activating radiation, the photooxidizing agent converts the leuco dye into a form with a color different from that of the leuco dye. Applying the printing composition to the printing plate is advantageous in that the degree of exposure imparted to the composition can be visually determined. If it is determined that the exposure is too low or that some of the composition is not exposed, the printing plate can be re-irradiated. To be effective for this purpose, the oven-exposed composition must yield sufficient dye density that upon exposure, it can be quickly removed without significantly compromising the speed of the printing plate. As is well known, the addition of photooxidizing agents and/or printed dyes is selected so as not to significantly interfere with the activation of the photopolymer.

Prior art φ extraction compositions featured photooxidants primarily of the carboxylic acid conductor type. Examples of photooxidizing agents of this type used in a variety of applications including lithographic printing plates are shown in US Pat. No. 3.359.109. A wide variety of useful leuco dyes are shown in the above specification. Useful photooxidants described therein include N, N, O
-) contains lyacylhuman 90xylamine. A large number of photooxidants of this type are described, for example in U.S. Pat.
It has been found that when used with the tris(7)-aminoaryl)methaneleuco dyes mentioned in the list of dyes in ., No. 109, only a pale print-out pattern is produced. Therefore, this type of photo-oxidizing agent is difficult to achieve at low concentrations, which limits its use.

It is an object of the present invention to overcome the shortcomings of prior art compositions by providing radiation-sensitive imaging compositions that give good contrast.

This objective is achieved by using certain compounds derived from sulfonic acids as photooxidizing agents in the composition.

According to the invention, a leuco dye having one or more removable hydrogen atoms, the removal of which forms a compound exhibiting a different coloration than that of the leuco type, and a leuco dye of the following formula (wherein R is 5 to 10 a substituted or unsubstituted carbocyclic or heterocyclic ring system containing 5 ring atoms;
Z represents a group of nonmetallic atoms necessary to complete one or more substituted or unsubstituted rings containing 5 to 17 ring atoms) and one composition is activated. A photosensitive 1Ifii imaging composition is provided that includes a photooxidizing agent that is capable of converting a leuco dye into a differently colored compound when exposed to radiation.

R1 is a substituted or unsubstituted carbocyclic ring system, such as a substituted or unsubstituted aryl group;
For example, phenyl group, p-chlorophenyl group or naphthyl group may be used.

R1 is a substituted or unsubstituted heterocyclic ring system, such as 2- or 6-thiophene, 2- or 6-
It may also be furan, 2-16- or 4-pyridine, imidazole, triazole or pyrazole.

Substituents that may be present on carbocycles or heterocycles include orthosubstituents such as chlorine and bromine atoms, or alkoxy groups such as methoxy groups.

Regarding the preferred group of photooxidants, Z is 5 to 17
Indicates a group of nonmetallic atoms necessary to complete a substituted or unsubstituted ring containing ring atoms, where the atoms adjacent to the nitrogen shoji are substituted with an oxo group and further replaced with a ketone group.・It is a carbon atom that forms. A preferred group of photooxidants of this type can be represented by the following formula.

1 In the above formula, Z represents a group of nonmetallic atoms necessary to complete one or more substituted or unsubstituted rings containing 5 to 17 ring atoms, and R1 is as defined above. It is something that

Z preferably represents the atoms necessary to form one or more rings containing from 4 to 16 ring carbon atoms, for example forming succinimide, glutarimide, phthalimide, naphthalimide, pyribin or quinolone. Preferably 2 is 1-4, optionally substituted by an oxo group at a position adjacent to the nitrogen atom to further form a ketone group.
6 to 1 forming a monocyclic moiety or a polycyclic moiety containing 6 to 1 rings
5 carbon atoms are shown. Most preferably Z represents such atoms completing one or two rings.

Specific representative examples of photooxidizing agents for use in the present invention include the following.

N-(4-chloroynesulfonyloxy)-1,8
-Naphthalimide, N-(4-Chlorzoninsulfonyloxy)phthalimide, 'fJ-Inzeninphonyloxyphthalimibi, N-
Banynesulfonyloxy-1,8-naphthalimibi, N-yneinsulfonyloxy-2(IH)-pyribine and N-yneinsulfonyloxy-2(IH)-quinolone.

The above photo-oxidizing agents are synthesized by conventional methods, and the following are typical among them.

Production method 1゜Synthesis of N-yneinsulfonyloxyphthalimide 9 A solution of triethylamine (3,1,9,0,0306 mol) in dichloromethane (50 m/) was mixed with N-hydroxyphthalimide (5.0 g, 0.016 mol). ) and vaninsulfonyl chloride (5.4 g, 0.016 mol) in dichloromethane (50 tA') (stirred) were added slowly at K water bath temperature. Bring the stirred reaction mixture to ambient temperature for approx.
It lasted for 4 hours. The product was partitioned between dichloromethane and distilled water and the dichloromethane extract was dried over magnesium sulfate. The solvent was removed under reduced pressure and the residue was crystallized with ethyl acetate-hanthanum (2:IV/V) to yield 8.0μ (87%) of colorless crystals. Melting point 186°; mass squictor M+305 (calculated value M+1O3).

Calculated value% 55.4 3.0 4.6 Actual value% 5
5.4 2.6 5.1 Production method 2 Synthesis of N + ”-ynsulfonyloxy-1,8-naphthalimide 9 N-hydroxy-1,8-naphthalimide (6,OS,
0.028 mol), benzenesulfonyl chloride (5,.

I, 0.028 mol) and triethylamine (6,.

I, 0.060 mol) of tetrahyP lofuran (4o.

d) The mixture was kept at ambient temperature for 18 hours with continuous stirring.

This mixture was poured into distilled water, and the precipitated crude product was washed with distilled water and then recrystallized from tetrahydrofuran to obtain pale yellow crystals. - point 211-216℃.

Calculated value% 61.2 3.1 4.0 Actual value%
61.0 3.5 4.5 Production method 6 Synthesis of N-(410 rubenzenesulfonyloxy)phthalimide 9 Dichloromethane y (10
0 m/) to N-hydroxyphthalimide 16.69 (
0.1 Qmol). 21.1 g (0.10 mol) of 4-chloroyninsulfonyl chloride was added to the dough. This suspension was added to 10.1 g of triethylamine (0,
10 mol) was added dropwise.

The reaction mixture was kept at ambient temperature with stirring for 72 hours. Further dichloromethane and 100 d of water were then added to the suspension. The dichloromethane extract was dried with magnesium sulfate. The solvent was removed under reduced pressure, and the residue was recrystallized from 500 d of ethyl acetate to obtain 102 g of a white solid. Melting point: 178-180°C.

CHN S Ci Calculated value % 49.8 2.4 4.1 9.5 10
．． 5 Actual value% 50.0 2.1 4.4 8.9
1Q, 6 Production method 4 N-(410 rubaneinsulfonyloxy)-1,8-
Synthesis of ``naphthalimide'' N-human 90x-1,8-naphthalimide (10,0,9,0,04
7 mol) and triethylamine (4.7 g, 0.04
4-chloroinsulfonyl chloride (10.0 g, 0.047 mol) was added to a suspension of 6 mol) with stirring,
:.

The mixture was kept at ambient temperature for 18 hours with stirring.

The mixture was poured into distilled water, and the precipitated solids were washed with distilled water and then spun. This 1,8-naphthalimide was converted into p-
Crystallized once from dioxane to give 8.0 g of colorless crystals (
44%). Melting point: 265-240°C; mass: M+587 (calculated value: M+687).

Calculated % 55.8 2.5 6.6 9.0 Observed % 55.6 2.2 3.9 8.7 Leuco dyes that transform into different colored forms when one or more hydrogen atoms are removed The difference is also useful. When the compositions of the invention are used with a photopolymer, dyes that do not exhibit significant absorption at the wavelength used to activate the photopolymer are preferred. Most preferred are leuco dyes in which the removable hydrogen atoms have no steric hindrance. For example, useful leuco dyes are described in the aforementioned US patent [,5
59,109 or U.S. Pat. No. 4.159.39 ()
Selected from the types shown in the specification. This includes, for example: Aminotriarylmethane, for example 4.4'.

4"-Methyly-Puntolis (N,N-dipropylaniline) and 4.4',4"-Methyly-Puntolis (N.

N-dimethylaniline); aminoquinanthenes such as '556-bis(dimethylamino)-9-(p-dimethylaminophenyl)xanthine and 3,6-bis(
:) ethylamino)-9-(P-dimethylaminophenyl)xanthine; aminothioxanthines; aminophenoxazines; aminophenothiazines; aminodihydrophenazines; and 6,6-bis(dimethylamino)-9 -(P-dimethylaminophenyl)phenazine and 3,7-bis(dimethylamino)-5,10-dihydro-5-phenylphenazine; aminodiphenylmethanes, such as 1,1-bis(p-dimethylaminophenyl)methane; Leucoidamines; aminohydrocinnamic acids, such as 4-(p-chloroanilino)-α,
β-dicyanohyrlocinnamic acid, methyl ester and 4
-anilino-α,β-S) cyanohydrocinnamic acid, methyl ester; human 9-radines, such as 1-(2-naphthyl)-2-phenyl, 1-radine and 1-(p-dimethylaminophenyl/I) /)-2-(2-pyridyl)hivirazine; leuco diide dyes; amino-2,6-sihydroanthraquinones; and phenethylanilines, such as N-(2-cyanoethyl)-p-phenethylaniline and N,N -diethyl-P-phenylethylaniline.

The compositions of the invention can be used with photopolymers and optionally photosensitizers. Negative or positive working photopolymers can be used.

The compositions of the present invention are lithographic printing plate compositions comprising a photosensitive polymer (eg, most preferably the negative-working photocrosslinkable polymers described in the aforementioned U.S. Pat. No. 1!4,159,590). It is particularly useful for Examples of particularly useful photopolymers include negative-working polyesters, polycarbonates, and polysulfonates containing repeating units containing the photosensitive moiety -G=OH-C- as an integral part of the polymer backbone. . A lithographic printing plate can be prepared by coating a composition containing a leuco dye, a photooxidizing agent, and a photosensitive polymer from a suitable solvent onto a suitable support in a conventional manner. Particularly when using a negative-working photosensitive polymer, a photosensitizer may be included if desired.

Useful examples of photosensitizers for photopolymers, other additives for compositions, supports and solvents include those described in the aforementioned U.S. Pat. No. 4,162,390. It will be done.

A negative-working lithographic printing plate composition is coated on a support,
After drying, the polymer in the exposed zones is crosslinked,
It is used by exposing the stiffness to activating radiation that removes hydrogen atoms from the leuco dye and printing out in this zone. Development of the photosensitive polymer is carried out by removing the unexposed areas with a suitable developer. The developer used is a common developer selected depending on the photosensitive polymer used in the lithographic printing plate composition. The above polyester,
Particularly useful developers for polycarbonates and polysulfonates are those consisting of the following components:

4-Butyrolactone 100 Q, Qa
/Nonionic ethylene oxybe ester condensate (E, I, obtained from DuPont-Dennemores under the trade name "Zonyl A")> 10.0d Methyl abietate 10.Od Hydrogenated rosin (from Verculous Powder Company) Obtained under the trade name “Stabelite”) 1
0.9 Glycerin 100.0
1/Wednesday
100,0I111 phosphoric acid
25.0d triethanolamine
12.511j The following examples further illustrate the invention.

Examples 1-6 The following lithographic printing plate compositions were prepared to demonstrate the excellent printout densities obtained using the compositions of the present invention.

Polyester of 1,4-di-β-hydroxyethoxy)cyclohexine and p-phenylene diacrylic acid (1948% by weight in 1,2-dichloroethane) containing the following repeating units: 24.4
49 Polystyrene (Binder) (A!nsil is available from Near Industrial Chemicals under the trade name Picolastic A-50') 1.65. ! 72-
[Bis-(2-furoyl)methylene-1-methylnat[1,2-d]thiazoline (B
FT) (Photosensitizer for polymers) 0.14. li
+2.6-sheet tart, butyl-P-cresol (stabilizer) o, 19 g dihydroanhydropyridinohexose reductone (antioxidant) 0.02 g4
．． 4′,4″-Methyly-Puntris (N.

N-)-10viraniline) (leuco dye')
0.25f; / Monastral
B dye (7.80% in 1,2-dichloroethane)
) (E, 1. Obtained from DuPont-Dennemores Company')
24.41 g Modaflow (1% in 1,2-dichloroethane) (surfactant') 0.87f
i Photooxidizing agent in Table 1 0.46-0.62
91.2-dichloroethane (solvent) 198.0
6g sound 1 sun
Return to °C/°＼ All photooxidants were used in equimolar amounts.

The total dry adhesion was 1110.87 by the drum coating machine.
DM on a support consisting of an anodized aluminum substrate with a 0.461 #g/”m carboxymethylluulose/zinc acetate undercoat. A uniform coating of excellent quality with no dye agglomeration was obtained. 5 coating solution exhibited good dye stability upon standing. To determine printout, each coated sample was exposed for 60 seconds on a 000 Watt NgAr vibrating xeno exposure frame. Untreated - Reflection density of 1st material
) Measured using a Macbeth RD-514 densitometer through a filter. , ΔD or density was calculated as the difference between the density of the exposed printing plate and the density of the unexposed background. No.D is a measure of out-of-furnace contrast.

To examine the Sensitomet IJ-reaction, each coating was similarly exposed for 60 seconds through a Kogutsu-14 wedge in a Terarc exposure unit (density increase of 0.15). The washout process was carried out by wiping the printing plate with a cotton swab impregnated with a developer solution (for which the preferred composition is shown above).

After the current monk, the sample that formed the painting book was transferred to Maquis RD-514.
Traced through a raften 58 green filter by a densitometer 1
The OR (relative) rate was used to analyze the lithographic sensitometric rate response based on the determined reflection density (for each T-14 culm exposure). A change in 150 R units corresponds to a change in 0.15 LoyE. Each coated sample was incubated at 50° C. and 50% relative humidity for two weeks and then freshly fogged. The samples were again subjected to bakeout and sensitometric tests. The results of these tests for fresh and incubated samples are shown in Table INK.

Table ■ Incubation Incubation Example Number New After - New - After Control A
O,010,01116127 Control B O,020
,0211612210,120,08107115 Control G O,050,0510811020,11
0,08103116 Control D O,040,0211011350,12
0,09102112 These results show that the arylsulfonyloxy compounds consistently give higher extrusion concentration differences than the corresponding aryloxy reference compounds, which are common photooxidants. The OR rate of the composition of the invention was also within an acceptable range.

Examples 4 to 7 The operations of Examples 1 to 5 were repeated using the photooxidizing agent of Example 1 and equimolar amounts of the compounds of Table 1 as leuco dyes. Prior to relative velocity measurements, mechanical development was performed using a different but similar developer solution.

The supports were subjected to slightly different priming treatments. Neither the basecoat change nor the developer change appeared to affect the printout density. In each example, the control was Control D (4),
Repeated as D(5), D(6) and D(7).

The results measured only for new samples are shown in Table ■. A comparative example was included to demonstrate a leuco dye that was found to be unusable (possibly due to steric hindrance of the removable hydrogen atom).

Table ■ Example number Leuco dye 4 1.1-bis-(P-dimethylaminophenyl)methane Pr 1pr=inpropyl Comparative example 1.1-bis-(2-methyl-4-diethylaminophenyl)butane Table W Control D ( 41,01119 4,05116 Control D (51,00112 5,05107 Control D (61,012116 6.01” 110 Comparative Example ,,00 1151
, the speed of each pair differs for each of the six pairs, primarily because differences in the dye density of the printout compositions have different effects on the speed of the printing plate.

2. Mainly because the colored type of leuco dye (ticket type) has insufficient contrast with the red dye of the printing plate composition, no difference was observed in this comparison. When no dye is used, superior results can be expected by using the photooxidizing agent of Example B compared to the control.

3. The lower relative speed for this pair compared to the 6 pairs above is due to the green printing dye produced, which is a type of compound that would otherwise activate the sensitizer in the photopolymer. When it acts to absorb the rays of light, it bends. These OR rates are still adequate and therefore the Example 70 leuco dye is acceptable.

Example 8 In order to investigate the behavior of a specific quinolone photooxidant, the following composition was prepared.

Table ■ Polyester of Example 1 (16.2% by weight solution) 50
0. V2.6-di-t-butyl-P-cresol (stabilizer) 1.5.
9 Example 10 BFT photosensitizer
6.5g leucopropyl violet (leuco pigment)
1.5g Photooxidizer from table ■
-dihydroanhydropiperidinohexose reductone (stabilizer for photooxidizing agents)
0.15.9 Monastral Blue BF dye (1,2-dichloroethane 9F, 5% by weight) (E, 1
．． (obtained from DuPont-Dennemore) 55.2
9 Fluorine compound surfactant (obtained from 3M under the trade name "FC-450") 0.29
1.2-dichloroethane (solvent) 8
859 Table ■ Example number Photooxidizer Amount control E
/・8.7＼ 2.14. ? 11
1 °\, /°\N/”%O 8, /・8.7・8. 2.45.!i+1
11 \, /°\N"'0 080 -CH 65 These two compositions were coated on a support similar to that of Example 1 at approximately 14.66 WIg/dWL2. The bakeout density was measured. The film was applied to the exposure unit of Example 1 for about 6 hours.
After exposure for 0 seconds, the ΔD density was measured in the same manner as in Example 1. The results measured for the new sample are shown in Table ■.

Table ■ Example number ΔD Control K O,01 80,05 These results show that ΔD is better when N-oxy is replaced by a sulfonyl group than by a carbonyl group.

Example 9 The procedure of Example 8 was repeated, except that the photooxidizing agent was a pyridone of Table 1, the amount of the ingredients was reduced, and no dye was included. Molar equivalents were used for photooxidants.

The results shown in Table 1 show that ΔD is better when the N-oxy substituent is a sulfonyl group than when it is a carbonyl group.

Compositions of the present invention containing photooxidants derived from sulfonic acids exhibit higher densities than those obtained with compositions containing similar conventional photooxidants derived from carboxylic acids. Gives the concentration.

Another advantage of using the compositions of the present invention with photopolymers is that they significantly impair the speed of the photopolymer compared to when using compositions containing photooxidants derived from carboxylic acids. The point is that an improved print-out density can be obtained without any problems.

Patent Applicant: Eastman Kodak Company [
390,488 0 Inventor Philip Paul Seniz Jr. - 73 Bontiack Drive, Chester, New York 46170, United States 0 Inventor Michael Jeffrey Lindstrom 15 Teiringham Road, Chester, New York 146170, United States

Claims (1)

[Scope of Claims] A leuco dye having one or more removable hydrogen atoms, which upon removal forms a compound exhibiting a color different from that of the leuco type, and a leuco dye having the following formula (% formula % (wherein R is a substituted or unsubstituted carbocyclic or heterocyclic ring system containing 5 to 10 ring atoms; 2 is one substituted or unsubstituted ring containing 5 to 17 ring atoms; (indicating the non-metallic atomic groups necessary to complete the process), which can transform leuco-type dyes into compounds of different colors when the composition is exposed to activating radiation. A radiation-sensitive imaging composition comprising a beaking agent.