JPH04333850A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To provide the photopolymerizable compsn. which has a high sensitiv ity, is sensitive to a viable light laser of low output and is usable for printing plates for plate making by incorporating an ethylenic unsatd. compd. and binder resin into the compsn. and further, incorporating a specific pyrolopyrrole compd., quinacridone compd. or azo compd. therein. CONSTITUTION:This compsn. contains the ethylenic unsatd. compd. and the binder resin and further, the pyrolopyrrole compd. expressed by formula I. In the formula I, A and B are the same or different alkyl group, alalkyl group, cycloalkyl group, or arom. group of a carbon ring or heterocyclic group. R1 and R2 respectively denote a hydrogen atom or substituent which is not imparted with water solubility; E denotes a sulfur atom or oxygen atom.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a photopolymerizable composition,
More specifically, the present invention relates to a photopolymerizable composition containing a novel photopolymerization initiator.

0002

BACKGROUND OF THE INVENTION Conventionally, in the production of lithographic printing plates, a halftone dot negative or the like is brought into close contact with a photosensitive layer, and then strong ultraviolet light is applied to the photosensitive layer.
For example, a method has been used in which light is irradiated using a high-pressure mercury lamp or a metal halide lamp, and then development is performed with an appropriate developer.

However, in recent years, a method has been proposed that simplifies the plate-making process by directly irradiating the photosensitive layer in a linear pattern using a laser beam. For example, U.S. Patent No. 3
, 664,737 describes a method for producing a lithographic printing plate by directly irradiating a recording material with a UV-sensitive layer, especially a diazo-sensitive layer, on an aluminum support with laser light.

However, since this method uses a layer conventionally known as an ultraviolet light-sensitive layer, applying this method to laser light is dependent on the luminous efficiency of the laser and the sensitivity wavelength range of the photosensitive material. The discrepancies between the two countries were extremely disadvantageous from an economic standpoint. In other words, in lasers that can be used for plate making, such as argon ion lasers, most of the total emission energy is in the visible light range of 450 nm or more, and the emission efficiency of ultraviolet rays is less than 5% of the total emission energy, so the output is low. It was necessary to use a large laser of about 30W.

"Photopolymer Technology" (Nikkan Kogyo Shimbun, 1986) discloses a photopolymerizable composition containing a dye that absorbs in the visible light range; Although it has sensitivity in the laser range, it is not sufficient, so it is still necessary to use a high-output laser, which poses problems in terms of cost and increasing the size of the device.

[0006] Accordingly, an object of the present invention is to provide a photopolymerizable composition that has high sensitivity and is sensitive to low-power visible light laser and can be used for plate making printing plates.

[0007]

Composition of the Invention As a result of intensive research, the present inventors have found that the above object of the present invention is to provide a pyrrolopyrrole compound containing at least an ethylenically unsaturated compound and a binder resin, and further represented by the following general formula [1], Quinacridone compounds represented by the general formula [4] and the following general formula [5] or [
We have found that this can be achieved by providing a photopolymerizable composition characterized by containing at least one azo compound represented by [6].

[0008]

embedded image (wherein A and B represent the same or different alkyl group, aralkyl group, cycloalkyl group, or carbocyclic or heterocyclic aromatic group, and R1 and R2 are each a hydrogen atom or a water-soluble (E represents a sulfur atom or an oxygen atom.)

[0009]

embedded image (wherein R1 represents a hydrogen atom or an alkyl group, R
2 represents an alkyl group or a perhalogenated alkyl group. )

0010

(In the formula, R1 represents an alkyl group, and R2 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a carboxyl group, a hydroxy group, an acyloxy group, an alkylmercapto group, or an alkyl group) (Represents a carbonyl group.)

The present invention will be explained in more detail below.

The photopolymerizable composition used in the present invention consists essentially of a photopolymerization initiator, an ethylenically unsaturated compound, and a binder resin.

The ethylenically unsaturated compound consists of an addition-polymerizable unsaturated compound, preferably a vinyl monomer having at least two terminal vinyl groups.

[0014] As this vinyl monomer,
No. 5093, No. 35-14719, No. 44-2872
Those described in each publication No. 7 are used. For example, acrylic or methacrylic esters of polyols,
That is, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc., or methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, etc. bis(meth)acrylamides, or unsaturated monomers containing urethane groups, such as di-(2'-methacryloxyethyl)-2,4-tolylene diurethane, di-(2-acryloxyethyl)tri Diol mono(meth) such as methylene diurethane etc.
Examples include reaction products of acrylate and diisocyanate.

These ethylenically unsaturated compounds are preferably contained in the photopolymerizable composition in an amount of 20 to 80% by weight based on the solid content thereof.

In the present invention, as a photopolymerization initiator, a pyrrolopyrrole compound represented by the above general formula [1], a quinacridone compound represented by the above general formula [4], or a quinacridone compound represented by the above general formula [5] or [6] is used. The azo compound represented (
The above are collectively referred to as "the photopolymerization initiator of the present invention").

In the general formula [1], the alkyl group represented by each of A and B can be linear or branched, saturated or unsaturated, and preferably 1
having from 1 to 18 carbon atoms, most preferably from 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-butyl, Amyl group, n-pentyl group, n-hexyl group, 1,1,3,3-tetramethylbutyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, undecyl group, dodecyl group or stearyl group It is.

The aralkyl group represented by each of A and B is preferably a straight chain or branched chain having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 carbon atom. It contains a monocyclic to tricyclic, most preferably monocyclic or bicyclic aryl group having from 1 to 4 alkyl groups or alkenyl groups. Examples of such aralkyl groups include benzyl and phenylethyl groups.

The homocyclic aromatic group represented by each of A and B is preferably a monocyclic to tetracyclic group, most preferably a monocyclic or bicyclic group, such as phenyl. group, diphenyl group or naphthyl group.

The heterocyclic aromatic group represented by each of A and B is preferably a monocyclic to tricyclic group. The group may be a pure heterocyclic group or a heterocyclic group and 1
It can contain one or more fused benzene rings, such as pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, coumarinyl, benzofuranyl, Benzimidazolyl group, benzoxazolyl group, dibenzofuranyl group, benzothiophenyl group, dibenzothiophenyl group, indolyl group, carbazolyl group, pyrazolyl group, imidazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, indazolyl group, benzothiazolyl group group, pyridazinyl group, cinnolyl group, quinazolyl group, quinoxalyl group, phthalazinyl group, phthalazinedionyl group, phthalimidyl group, chromonyl group, naphtolactamyl group, benzopyridonyl group, maleimidyl group, naphthalidinyl group, benzimidazolonyl group,
Benzoxazolonyl group, benzothiazolonyl group, benzothiazolinyl group, quinazolonyl group, pyrimidyl group, quinoxalonyl group, phthalazonyl group, dioxapyrimidinyl group, pyridonyl group, isoquinolonyl group, isoquinolinyl group, isothiazolyl group, benzisoxa These are a zolyl group, a benzisothiazolyl group, an indazolonyl group, an acridinyl group, an acridonyl group, a quinazolinedionyl group, a quinoxalinedionyl group, a benzoxatinedionyl group, or a naphthalimidyl group.

Both the homoaromatic and heteroaromatic groups described above can contain water-insolubilizing substituents. As the water-insolubilizing substituent, for example, those listed below are used.

1) Halogen atoms such as chlorine, bromine or fluorine atoms.

2) Branched or unbranched alkyl groups containing preferably 1 to 18, even 1 to 12, especially 1 to 8 and most preferably 1 to 4 carbon atoms. These alkyl groups may contain water-insolubilizing groups such as the following: fluorine atom, hydroxyl group, cyano group, -OCOR3, -OR4,
-COOR3, -CONR4R5 or -R3-OCO
NHR3 (where R3 is an alkyl group, an aryl group such as a naphthyl group, or a benzyl group or a halogen atom,
Represents a benzyl group substituted with an alkyl group or an -O-alkyl group, or a heterocyclic group; R4 and R5
is a hydrogen atom, an alkyl group or an alkyl group substituted with a cyano group or a hydroxyl group, or a cycloalkyl group having 5 to 6 carbon atoms, an aryl group or a heteroaryl group, in particular a phenyl group or a halogen atom, an alkyl group or -O- It represents a phenyl group substituted with an alkyl group, or R4 and R5 together with the nitrogen atom form a 5- or 6-membered heterocycle, such as a morpholine, piperidine or phthalimide ring. )
. Possible substituents of the alkyl radicals are furthermore mono- or dialkylated amino radicals, aryl radicals such as naphthyl radicals or phenyl radicals preferably substituted with phenyl radicals or halogen atoms, alkyl radicals or -O-alkyl radicals, or likewise Non-basic heteroaromatic groups such as 2
-thienyl group or 6-benzimidazolonyl group.

Further, when the substituents specified in the above 2) contain an alkyl group, the alkyl group may be branched or unbranched, and preferably 1 to 18, It further contains 1 to 12, especially 1 to 8 and most preferably 1 to 4 carbon atoms.

Examples of unsubstituted or substituted alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, Tertiary amyl group, n-pentyl group, n
-hexyl group, 1,1,3,3-tetramethylbutyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, undecyl group, dodecyl group, hydroxymethyl group,
Trifluoromethyl group, trifluoroethyl group, cyanomethyl group, methoxycarbonylmethyl group, acetoxymethyl group or benzyl group.

3) the group -OR6 (where R6 is a hydrogen atom, an alkyl group or an aryl group such as a naphthyl group or preferably a phenyl group or a phenyl group substituted with a halogen atom, an alkyl group or an -O-alkyl group;
Alternatively, it represents a cycloalkyl group, an aralkyl group, or a non-basic heterocyclic group having 5 or 6 carbon atoms. )
In the definition of R6, the alkyl group may contain the number of carbon atoms specified as preferred in 2) above. Representative examples of R6 include: methyl, ethyl, n-propyl, isopropyl, trifluoroethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl group, α- or β-naphthyl group, cyclohexyl group, benzyl group, thienyl group or pyranylmethyl group.

4) -SR6 group (wherein R6 has the same meaning as defined in 3) above) Typical representative examples of R6 include: methyl group, ethyl group,
n-propyl group, isopropyl group, phenyl group, o-,
m- or p-chlorophenyl group, o-, m- or p
- methylphenyl, α- or β-naphthyl, cyclohexyl, benzyl, thienyl or pyranylmethyl group.

5) Cyano group.

6) A group represented by the formula: -COOR3 (where R3 has the same meaning as defined in 2) above. R
Examples of 3 include: methyl, ethyl, isopropyl, tert-butyl, n-butyl, phenyl, benzyl or furfuryl.

7) Formula: -COR6 (where R6 is the above 3
) has the same meaning as defined in ). R6
Examples include: methyl, ethyl, tert-butyl, phenyl, o-, m- or p-
Chlorphenyl group, o-, m- or p-methylphenyl group or α- or β-naphthyl group.

8) Formula: -NR7COR3 (where R3 has the same meaning as defined in 2) above, R7 is a hydrogen atom, an alkyl group, an aryl group such as a naphthyl group, or preferably a phenyl group, a halogen atom, an alkyl group or a phenyl group substituted with an -O-alkyl group, or a cycloalkyl group having 5 or 6 carbon atoms, an aralkyl group or a group -COR6, and two groups (
-COR6 can also represent a heterocycle formed together with a nitrogen atom. ). In the definition of R7, the alkyl group may contain the number of carbon atoms specified as preferred in 2) above. Representative examples include: acetylamino group, propionylamino group, butyrylamino group, benzoylamino group, p-chlorobenzoylamino group, p-methylbenzoylamino group, N-methylacetylamino group, N-methyl benzoylamino group, N-succinimide group or N
-phthalimide group.

9) Formula: -NR6COOR3 (where R3
and R6 have the same meanings as defined in 2) and 3) above, respectively. ). A typical example is the group -NHCO
OCH3, NHCOOC2H5 or NHCOOC6H
It is 5.

10) Formula: -NR6CONR4R5 (where R6, R5 and R4 have the same meanings as defined in 3) and 2) above. ). Representative examples are: ureido group, N-methylureido group, N
-phenylureido group or N,N-2',4'-dimethylphenylureido group.

11) Formula: -NHSO2R6 (where R6
has the same meaning as defined in 3) above. Representative examples are: methanesulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or β-naphthylsulfonylamino.

12) Formula: -SO2R3 or SOR3 (
Here R3 has the same meaning as defined in 2) above)
A group represented by Representative examples are: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.

13) A group represented by the formula: -SO2R3 (where R3 has the same meaning as defined in 2) above. Representative examples of R3 include: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl,
α- or β-naphthyl group.

14) Formula: -CONR4R5 (where R4
and R5 each have the same meaning as defined in 2) above. Examples of R4 and R5 include: carbamoyl group, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-phenylcarbamoyl group, N,N-dimethylcarbamoyl group, N-
Methyl-N-phenylcarbamoyl group, N-α-N-naphthylcarbamoyl group or N-piperidylcarbamoyl group.

15) Formula: SO2NR4R5 (where R4
and R5 each have the same meaning as defined in 2) above. Representative examples include: sulfamoyl group, N-methylsulfamoyl group,
N-ethylsulfamoyl group, N-phenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group or N-morpholylsulfamoyl group.

16) Represented by the formula: -N=N-R8 (where R8 represents a coupling component group or a phenyl group that is unsubstituted or substituted with a halogen atom, an alkyl group, or an O-alkyl group). Base. In the definition of R8, the alkyl group may contain the number of carbon atoms specified as preferred in 2) above. Examples of R8 include: acetoacetoarylide, pyrazolyl, pyridonyl, o- or p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or p-N,N -dimethylaminophenyl group.

17) A group represented by the formula: -OCOR3 (where R3 has the same meaning as defined in 2) above. Examples of R3 include: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

18) Formula: -OCONHR3 (where R3
represents the meaning defined in 2) above. ). Examples of R3 include: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

The substituent which does not impart water solubility represented by each of R1 and R2 in the general formula [1] is, for example, a straight chain or branched chain, saturated or unsaturated, having 1 to 18 carbon atoms, most preferably is an alkyl group having 1 to 12 carbon atoms. These groups may be unsubstituted or substituted with a hydroxy group, halogen atom, alkoxy group, acyloxy group, alkylmercapto group, alkoxycarbonyl group or cyano group. Examples of such groups include methyl, ethyl, n-propyl,
Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, methylbutyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group, hydroxymethyl group, Examples include trifluoromethyl group, trifluoroethyl group, cyanoethyl group, methoxycarbonylmethyl group, and acetoxymethyl group.

R1 and R2 may each be an aryl group, preferably unsubstituted or a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 1 carbon atoms.
2 alkoxy group, an alkylmercapto group having 1 to 12 carbon atoms, a phenyl group substituted with a trifluoromethyl group or a nitro group.

As the compound represented by the general formula [1], a compound in which R1 and R2 are each a hydrogen atom is particularly preferred. Similarly, compounds in which A and B are each the same or different groups represented by the following general formula [2] are preferred.

[0045]

[Formula 9] (wherein, X, Y and Z each independently represent a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group, a carbon atom number 1
an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylmercapto group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a dialkylamino group having 2 to 6 carbon atoms, or each represents a phenoxy group, a phenylmercapto group or a phenoxycarbonyl group which is unsubstituted or substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;
, Y and Z represent a hydrogen atom. )

X, Y and Z are preferably located in the ortho, meta or para position, preferably in the meta or para position relative to the dithioketopyrrolopyrrole group or diketopyrrolopyrrole group.

Particularly preferred compounds represented by the general formula [1] include those represented by the following general formula [1] where A and B are the same or different;
3].

[0048]

[Formula 10] (wherein, one of X1 and Y1 is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a cyano group, an N,N-dimethylamino group, an N,N-diethylamino group, and the number of carbon atoms represents an alkoxy group having 1 to 12 carbon atoms, an alkylmercapto group having 1 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 4 carbon atoms, and the other substituent of X1 and Y1 represents a hydrogen atom.)

X1 and Y1 are preferably located in the ortho-, meta- or para-position, preferably in the meta- or para-position relative to the dithioketopyrrolopyrrole or diketopyrrolopyrrole group.

The quinacridone compound used in the photopolymerizable composition of the present invention is represented by the general formula [4].

In the general formula [4], R1 represents a hydrogen atom or an alkyl group, preferably a straight chain alkyl group, and R2 represents an alkyl group or a perhalogenated alkyl group, preferably a straight chain alkyl group or a perhalogenated straight alkyl group. Represents a chain alkyl group.

The alkyl group represented by R1 and R2 in the general formula [4] can be straight chain or branched chain, saturated or unsaturated, preferably straight chain and having 1 to 18 carbon atoms. For example, methyl group, ethyl group,
n-propyl group, n-butyl group, n-pentyl group, n-
Examples include hexyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. R2
The perhalogenated alkyl group represented by can be straight chain or branched, saturated or unsaturated, preferably straight chain and having 1 to 18 carbon atoms, for example trifluoromethyl group, Examples include pentachloroethyl group, heptabromo-n-propyl group, and nonaiodo-n-butyl group.

The azo compound used in the photopolymerizable composition of the present invention is represented by the above general formula [5] or [6].

In the general formula [5] or [6], R
The alkyl group represented by 1 is a straight chain or branched chain,
Can be saturated or unsaturated, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl,
Examples include n-pentyl group and n-hexyl group.

The alkyl group represented by R2 can be straight chain or branched, saturated or unsaturated. Examples of such groups include methyl, ethyl, n-
Propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, methylbutyl group, n-heptyl group, stearyl group, hydroxymethyl group, trifluoromethyl group, trifluoroethyl group, cyanoethyl group, methoxy Examples include carbonylmethyl group and acetoxymethyl group. Even if these groups are unsubstituted, hydroxy groups,
It may be substituted with a halogen atom, an alkoxy group, an acyloxy group, an alkylmercapto group, an alkoxycarbonyl group, or a cyano group.

The photopolymerization initiator of the present invention contains a pyrrolopyrrole compound represented by the general formula [1] and an azozo compound represented by the general formula [5] or [6] in the photopolymerizable composition based on the solid content. In the case of compounds, 0.1 to 20% by weight, general formula [
4] in the case of a quinacridone compound represented by 0.1
The content is preferably 30% by weight.

Examples of the synthesis of the photopolymerization initiator of the present invention are shown below.

Synthesis Example-1 [Pyrrolopyrrole Compound-1] 400 mg of sodium and 20 mg of sodium salt of sulfosuccinic acid bis-2-ethylhexyl ester are stirred at reflux temperature in 15 ml of tertiary-amyl alcohol until the reaction is completed. . To this clear solution, 1.58 mg of terephthalonitrile is added, and 1.68 g of pyrrolinon represented by the following structural formula is added little by little over 20 minutes. At this time, the temperature is maintained at 85°C.

[0059]

embedded image The dark red reaction mixture is stirred at 85° C. for 30 minutes and then acidified by adding 8 ml of glacial acetic acid dissolved in 20 ml of tertiary-amyl alcohol. After boiling at 100°C for 1.5 hours, filter at 70°C. The filter cake was washed with methanol until colorless and washed in vacuo for 6 minutes.
When dried at 0°C, 80% of the compound represented by the following structural formula
isolated with a yield of .

[0060]

[Formula 12] Absorption spectrum in DMF: λmax [nm]: 271
,310,485,520 C15H11N3O2 Calculated value: C 72.8
4%; H 3.54%; N 13.41% Actual value: C 72.15%; H 3.64%; N
13.40%

Synthesis Example-2 [Pyrrolopyrrole Compound-2] 100 g of diethyl benzoylsuccinate and 111 g of ammonium acetate were boiled under reflux for 16 hours in 300 ml of glacial acetic acid. Pour the reaction mixture into 3 liters of cold water. A crystalline precipitate forms,
The precipitate is filtered with suction and washed with 500 ml of water. When the obtained crude product is recrystallized from methylene chloride, 48.9 g of a compound represented by the following structural formula is isolated in the form of crystals.

[0062]

[Chemical Formula 13] Meanwhile, 1.55 g of sodium and the sodium salt of sulfosuccinic acid bis-2-ethylhexyl ester (emulsifier) were mixed with tertiary-amyl alcohol 2 until the reaction was completed.
Stir in 7 ml at reflux temperature. To this clear solution, 6 g of p-tolnitrile is added at 100 DEG C., and then 5.1 g of the compound represented by the above structural formula is added little by little over 30 minutes.

The reaction mixture is stirred at 100° C. for 1 hour and then poured into 200 ml of cold water. The reaction mixture is stirred for 1 hour at reflux temperature and then steam is introduced for 1 hour to remove the organic solvent. The suspension of the compound thus obtained is filtered and the filter cake is dried in vacuo at 80° C., the compound having the following structural formula is isolated in a yield of 49%.

[0064]

[Chemical formula 14] UV/VIS (NMP, λmax), 307 (1400
0), 312 (14000) 472 (23000), 5
07 (35600) C19H14N2O2 Calculated value: C 75.48%; H 4.67%; N 9
．． 27% Actual value: C 75.30%; H 4.70%; N
9.23%

Synthesis Example-3 [Pyrrolopyrrole Compound-3] Tetrahydrofuron 15
A solution of 9.3 g (0.05 mol) of allylzinc bromide in 0 ml was dissolved in ethyl β in 50 ml of tetrahydrofuran.
-Aminocinnamate 9.55g (0.05mol) solution and the mixture was reacted at 10°C for 3 hours. The solvent was then distilled off under vacuum and the resulting salt was dissolved in benzonitrile 5
8.35 g (0.05 mol) of ethyl bromoacetate was added to this solution. The mixture was stirred at 120° C. for 8 hours, then the red suspension was cooled, diluted with 50 ml of acetone and further diluted with 10 ml of acetone.
Stir for a minute. The batch was filtered, the residue washed with acetone and purified by boiling in 25 ml of glacial acetic acid at reflux temperature for 4 hours. The product was isolated by filtration, washed again with acetone, and dried under vacuum at 80° C. to yield 3.2 g of a compound with the following structural formula.

[0066]

embedded image Next, 2.89 g of the compound represented by the above structural formula and 2,4
-bis(4-methoxyphenyl)-1,3-dithia-2
, 4-diphosphetane 2,4-disulfide (Lawe
sson reagent), and then the compound,
Cover with 60 ml of xylene mixture and 25 ml of hexamethylphosphoric triamide. The mixture is stirred vigorously and then heated to 133° C. under reflux. After boiling for 7 hours, the mixture is cooled to about 90°C. The resulting product was isolated by filtration, washed with warm xylene and then with a small amount of acetone.
Finally, after washing with methanol and drying at 90° C. under reduced pressure, 3.04 g of a compound represented by the following structural formula is obtained as a blackish blue crystalline powder.

[0067]

[Formula 16] Absorption spectrum in DMF: λmax [nm]: 500
,589,622

Synthesis Example-4 [Quinacridone Compound-1] p-hexylaniline (II) was prepared from aniline and hexyl alcohol, and (
Compound (IV) was synthesized by condensing II) and diethyl succinylsuccinate (III) with hydrochloric acid in ethanol. This was dissolved in di-n-butyl phthalate at 150°C for 2 hours.
A mixture of compound (V) and compound (VI) was obtained by performing thermal ring closure with stirring for a period of time. By sublimating this mixture under reduced pressure, quinacridone compound-1 represented by structural formula (VI) was isolated in a yield of 56%. Absorption spectrum in H2SO4: λmax [nm]: 3
05,396,559,606

[0069]

[Chemical formula 17]

Synthesis Example-5 [Quinacridone Compound-2] According to the method shown in Synthesis Example-4, a mixture of compound (V) and compound (VI) was obtained. This mixture was N-alkylated by reacting with octyl bromide using a phase transfer catalyst to obtain quinacridone compound-2 represented by structural formula (VII) in a yield of 11%. Absorption spectrum in CHCl3: λmax [nm]: 3
03,500,535

[0071]

[Chemical formula 18]

Synthesis Example-6 [Quinacridone Compound-3] p-Perfluorohexylaniline (VIII) was synthesized from p-iodoaniline and perfluorohexyl iodide, and (VIII) and diethyl succinyl succinate (III) were synthesized. was condensed with hydrochloric acid in ethanol to synthesize compound (IV). This was stirred in di-n-butyl phthalate at 150°C for 2 hours to perform thermal ring closure to form compound (X) and compound (XI).
A mixture of was obtained. By sublimating this mixture under reduced pressure, quinacridone compound-3 represented by structural formula (XI) was isolated in a yield of 34%. Absorption spectrum in H2SO4: λmax [nm]: 2
99,385,547,591

[0073]

[Chemical formula 19]

Synthesis Example-7 [Azo Compound-1] Acenaphthene (III) is nitrated, oxidized, ethylimidated, and then reduced to yield 4-amino-N-ethyl-1,8-naphthalene dicarboximide (IV). Compound (V) was obtained by diazotizing (IV) by the nitrosyl sulfuric acid method. Compound (V)
and 4-methyl-1-naphthol (VI) were coupled in alkaline conditions at 5±1°C for 3 hours to obtain the structural formula (V
Azo compound-1 represented by II) was obtained with a yield of 73%. Absorption spectrum in DMF: λmax [nm]: 493

[0075]

[C20]

Synthesis Example-8 [Azo Compound-2] Compound (V) was obtained according to the method shown in Synthesis Example-7. Compound (V) and 3,6-diethyl-
1-naphthol (VIII) in an alkaline condition at 5±1°C.
After coupling for 3 hours, azo compound-2 represented by structural formula (IX) was obtained in a yield of 54%. Absorption spectrum in DMF: λmax [nm]: 500

[0077]

[C21]

Synthesis Example-9 [Azo Compound-3] Acenaphthene (III) is nitrated, oxidized, propylimidated, and then reduced to form 4-amino-
N-propyl-1,8-naphthalene dicarboximide was synthesized, and this was further diazotized by the nitrosyl sulfuric acid method to obtain compound (X). Compound (X) and 8-ethyl-1-naphthol (XI) were heated under alkaline conditions at 5±1°C.
Coupling was performed for 3 hours, and azo compound-3 represented by structural formula (XII) was obtained in a yield of 38%. Absorption spectrum in DMF: λmax [nm]: 512

[0079]

[C22]

In the present invention, the photopolymerization initiator of the present invention and other photopolymerization initiators can be used together.

Photopolymerization initiators that can be used in combination with the photopolymerization initiator of the present invention include, for example, J. Written by Kosar “Light
Carbonyl compounds, organic sulfur compounds, perfusates, as described in Chapter 5 of “Sensitive Systems”
Examples include redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes. More specifically, it is disclosed in British Patent No. 1,459,563.

For example, benzoin methyl ether, benzoin isopropyl ether, α,α-dimethoxy-α-
Benzoin derivatives such as phenylacetophenone, benzophenone derivatives such as benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone , thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone, 2-chloroanthraquinone,
anthraquinone derivatives such as 2-methylanthraquinone,
Acridone derivatives such as N-methylacridone and N-butylacridone, α,α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds,
Examples include halogen compounds.

Furthermore, various known polymers can be used as the binder resin used in the photopolymerizable composition of the present invention. Details of the specific binder are described in U.S. Pat. No. 4,072,527, and more preferably monomers having an aromatic hydroxyl group as described in JP-A-54-98613. , for example N-
(4-hydroxyphenyl)acrylamide, N-(4
-hydroxyphenyl) methacrylamide, o-, m-
or copolymers of p-hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate, etc., with other monomers, as described in U.S. Pat. No. 4,123,276. Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit, natural resins such as shellac, rosin, polyvinyl alcohol, polyamides such as those described in U.S. Pat. No. 3,751,257. resins, linear polyurethane resins as described in U.S. Pat. No. 3,660,097, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, cellulose acetate, cellulose acetate phthalate. These include celluloses such as.

[0084] The above binder resin is included in the photopolymerizable composition.
It is contained in an amount of 20 to 80% by weight based on the solid content.

The photopolymerizable composition of the present invention contains a fat-sensitizing agent,
Additives such as surfactants, sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, and pigments such as dyes and pigments can be included. The amount of these additives added to the composition varies depending on the type, but in general, the amount of these additives added to the composition is 0.
．． 01-20% by weight, preferably 0.05-10% by weight
Contains.

The use of the photopolymerizable composition of the present invention is not particularly limited, but it is preferably used as a plate-making material. This plate-making material includes, for example, a lithographic printing plate such as a PS plate and a photosensitive lithographic printing plate that does not require dampening water, and is particularly preferably used in a photosensitive lithographic printing plate that does not require dampening water.

This photosensitive lithographic printing plate that does not require dampening water is one in which a support is coated with a photosensitive layer, an ink repellent layer (for example, a silicone rubber layer), and an optional protective layer in this order. A primer layer is provided between the body and the photosensitive layer.

[0088] After development, the photosensitive lithographic printing plate that does not require dampening water
A type in which only the silicone rubber layer in the image area is removed is also used, but a type in which the photosensitive layer in the image area is removed after development and the primer layer in the image area is exposed is preferable.

[0089] In the method for producing the plate material described above, it is necessary to photocure the primer layer provided on the support, and then apply the photosensitive layer and the ink repellent layer in this order.

Examples of the primer layer include polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer,
Examples include vinyl acetate copolymers, phenoxy resins, polyurethane resins, polycarbonate resins, polyacrylonitrile butadiene, and polyvinyl acetate. Further, as the anchor agent constituting the primer layer, for example, a silane coupling agent, a silicone primer, etc. can be used, and organic titanates and the like are also effective.

[0091] The thickness of the above primer layer is preferably 6 μm or more, particularly preferably 6 μm to 50 μm.
It is. If the thickness of the primer layer is 6 μm or less,
If the silicone rubber layer is subjected to an impact with a hard object or rubbed with a developing brush, cloth, etc., the silicone rubber layer will be damaged. On the other hand, if the thickness is 6 .mu.m or more, the above-mentioned impact or rubbing is alleviated (cushioning effect) by the primer layer, making it less likely to be damaged.

The support is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the load applied during printing, such as aluminum, zinc, copper,
Metal plates such as steel, metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper, plastic films and glass plates, resin coated paper,
Examples include paper covered with metal foil such as aluminum.

Among these, preferred is an aluminum plate.

[0094] The treatment for the support itself to improve the adhesiveness is not particularly limited, and includes various surface roughening treatments.

When the photopolymerizable composition of the present invention is used in a photosensitive lithographic printing plate that does not require dampening water, the thickness of each layer constituting the plate material is as follows. That is, the support is 50 to 40
0 μm, preferably 100 to 300 μm, and the photosensitive layer has a thickness of 0.0 μm.
05-10μm, preferably 0.5-5μm, silicone rubber layer 0.1-10μm, preferably 0.5-2μm
It is m.

The photopolymerizable composition of the present invention is sensitive to a low-power visible light laser, and examples of the laser beam used in the present invention include He-Ne, He-Cd, etc.
, argon, krypton, etc., which are capable of continuous oscillation. Considering output energy, laser tube life, oscillation efficiency, etc., argon laser (output 0.1 to 5 W) is recommended.
is preferred.

[0097]

[Examples] The present invention will be explained in more detail below with reference to Examples.

Example 1 A recording material was obtained by applying the following photosensitive composition to a coating amount of 2 g/m 2 using a whirler on a grained and anodized aluminum plate.

[Photosensitive composition] Copolymer of 2-hydroxyethyl methacrylate, N-(4-hydroxyphenyl) methacrylamide, and methacrylic acid in a molar ratio of 40/57/3

14 parts by weight Pentaerythritol triacrylate
50 parts by weight pyrrolopyrrole compound-1

5 parts by weight methyl ethyl ketone

400 parts by weight toluene

400 parts by weight This recording material is irradiated with an argon ion laser at an output of 2.5 W and a beam diameter of 1.25 mm, and developed with the developer shown below. The time was measured. Table 1 shows the results of calculating the laser irradiation energy.

[Developer] β-anilinoethanol
0.5
Part by weight Propylene glycol

1.0 parts by weight p-tert-butylbenzoic acid

1.0 parts by weight Potassium hydroxide

1.0 parts by weight polyoxyethylene lauryl ether
0.1 parts by weight Potassium sulfite

2.0 parts by weight Potassium metasilicate
3.0
Weight part Water

91 parts by weight

Example 2 A recording material was prepared in the same manner as in Example 1, except that the following photopolymerizable composition was used, and the material was irradiated with a laser and developed. Table 1 shows the results.

[Photosensitive composition] Molar ratio of 2-hydroxyethyl methacrylate, N-(4-hydroxyphenyl)methacrylamide, acrylonitrile, and methyl methacrylate 40/30/10/20
Copolymer of: 14 parts by weight Trimethylolpropanetriethoxytriacrylate 40 parts by weight 2-ethylanthraquinone
2 parts by weight pyrrolopyrrole compound
2
2 parts by weight methyl ethyl ketone

200 parts by weight toluene

200 parts by weight

Example 3 A recording material was prepared in the same manner as in Example 1, except that the following photopolymerizable composition was used, and the material was irradiated with a laser and developed. Table 1 shows the results.

[Photosensitive composition] Copolymer with a styrene/methacrylic acid molar ratio of 80/20 34 parts by weight pentaerythritol triacrylate
100 parts by weight Michler's ketone

10 parts by weight pyrrolopyrrole compound-3

10 parts by weight methyl ethyl ketone

1000 parts by weight toluene

1000 parts by weight

[
0105]

[Table 1] All of Examples 1 to 3 showed practically sufficient recording sensitivity.

Example 4 Pyrrolopyrrole compound-1 was converted into quinacridone compound-1
A recording material was produced in the same manner as in Example 1, except that the material was changed to , and was irradiated with a laser and developed. The results are shown in Table 2.

Example 5 Pyrrolopyrrole compound-2 was converted into quinacridone compound-2
A recording material was produced in the same manner as in Example 2, except that the material was changed to , and was irradiated with a laser and developed. The results are shown in Table 2.

Example 6 Pyrrolopyrrole compound-3 was converted to quinacridone compound-3
A recording material was produced in the same manner as in Example 3, except that the material was changed to , and was irradiated with a laser and developed. The results are shown in Table 2.

[0109]

[Table 2] All of Examples 4 to 6 showed practically sufficient recording sensitivity.

Example 7 A recording material was prepared in the same manner as in Example 1 except that pyrrolopyrrole compound-1 was changed to azo compound-1, and the material was irradiated with a laser and developed. The results are shown in Table 3.

Example 8 A recording material was prepared in the same manner as in Example 2 except that pyrrolopyrrole compound-2 was changed to azo compound-2, and the material was irradiated with a laser and developed. The results are shown in Table 3.

Example 9 A recording material was prepared in the same manner as in Example 3, except that pyrrolopyrrole compound-3 was replaced with azo compound-3, and the material was irradiated with a laser and developed. The results are shown in Table 3.

[0113]

[Table 3] All of Examples 7 to 9 showed practically sufficient recording sensitivity.

[0114]

EFFECTS OF THE INVENTION As described above in detail, the present invention makes it possible to provide a photopolymerizable composition that is highly sensitive, sensitive to low-power visible light laser, and usable for plate making printing plates.

Claims (5)

[Claims] 1. At least an ethylenically unsaturated compound,
A photopolymerizable composition comprising a binder resin and a pyrrolopyrrole compound represented by the following general formula [1]. [Formula 1] (wherein A and B represent the same or different alkyl group, aralkyl group, cycloalkyl group, or carbocyclic or heterocyclic aromatic group, and R1 and R2 are each a hydrogen atom or a water-soluble Represents a substituent that does not have E
represents a sulfur atom or an oxygen atom. ) [Claim 2] In the general formula [1] according to claim 1, A and B are each the same or different, and the following general formula [2]
The photopolymerizable composition according to claim 1, which is a group represented by: [Formula 2] (wherein, X, Y and Z each independently represent a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group, or a carbon atom number of 1
an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylmercapto group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a dialkylamino group having 2 to 6 carbon atoms, or Each represents a phenoxy group, a phenylmercapto group, or a phenoxycarbonyl group which is unsubstituted or substituted with a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group, and the substituents X, Y and Z At least one of them represents a hydrogen atom. ) [Claim 3] In the general formula [1] according to claim 1, A and B are each the same or different, the following general formula [3]
The photopolymerizable composition according to claim 1, which is a group represented by: [Formula 3] (wherein, one of X1 and Y1 is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a cyano group, an N,N-dimethylamino group, an N,N-diethylamino group, and the number of carbon atoms represents an alkoxy group having 1 to 12 carbon atoms, an alkylmercapto group having 1 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 4 carbon atoms, and the other substituent of X1 and Y1 represents a hydrogen atom.) 4. At least an ethylenically unsaturated compound,
A photopolymerizable composition comprising a binder resin and a quinacridone compound represented by the following general formula [4]. embedded image (wherein, R1 represents a hydrogen atom or an alkyl group, and R
2 represents an alkyl group or a perhalogenated alkyl group. ) 5. A photopolymerizable composition containing at least an ethylenically unsaturated compound, a binder resin, and an azo compound represented by the following general formula [5] or [6]. (In the formula, R1 represents an alkyl group, and R2 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a carboxyl group, a hydroxy group, an acyloxy group, an alkylmercapto group, or an alkoxy (Represents a carbonyl group.)