JP2003177527A - Photopolymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable composition which cures under visible light or infrared laser with high sensitivity, is useful as a photosensitive layer of a negative original plate for a planographic printing plate capable of direct recording from digital data of a computer or the like and attains excellent aging stability, high-quality image formation and high printing and chemical resistances. <P>SOLUTION: The photopolymerizable composition comprises (A) a polymerizable compound having at least one radical-polymerizable ethylenically unsaturated double bond per molecule and a cohesive energy density of ≥500 J/cm<SP>3</SP>, (B) a radical polymerization initiator and (C) and a binder polymer and cures when exposed to light. If the photopolymerizable composition further contains (D) a compound which generates heat upon exposure to IR, it cures when exposed to infrared laser. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to ultraviolet light, visible light,
The present invention relates to a photopolymerizable composition that can be cured by exposure to infrared rays, and more particularly to a photopolymerizable composition suitable as a photosensitive layer of a negative lithographic printing plate precursor.

[0002]

2. Description of the Related Art Conventionally, various systems for making a plate directly from digital data of a computer have been developed. For example, an argon laser is used as a photopolymerization type image forming material which is exposed by using a laser that emits blue or green visible light. The photosensitive layer of the lithographic printing plate is sensitive to, for example, high-sensitivity direct plate making using a photopolymerization initiation system, and can achieve high printing durability due to the toughness of the coating film cured by photopolymerization. Is being watched as. For example, as a laser printing plate using a photopolymerization initiation system sensitive to a visible laser such as an argon laser, a compound containing an ethylenic double bond capable of addition polymerization and a photopolymerization initiator are provided on an aluminum plate as a support. Further, a photopolymerizable composition layer comprising an organic polymer binder, a thermal polymerization inhibitor, and the like, which are optionally used, is provided, and an oxygen blocking layer for inhibiting polymerization is further provided thereon. In these photopolymerizable lithographic printing plates, a desired image is imagewise exposed to polymerize and cure the exposed portion, and the unexposed portion is removed (developed) with an aqueous alkaline solution to obtain an image.

The development of lasers in recent years has been remarkable,
In particular, as solid-state lasers and semiconductor lasers that emit infrared rays having a wavelength of 760 nm to 1200 nm, high-power and small-sized ones are easily available. These lasers are very useful as a recording light source when making a plate directly from digital data of a computer or the like. Therefore, in addition to many practically useful photosensitive recording materials having a photosensitive wavelength of 760 nm or less in the visible light range as described above, materials recordable by these infrared lasers are desired. As disclosed in Japanese Patent Application Laid-Open No. 2000-187322, it has an infrared absorber, a photo or thermal polymerization initiator, and a functional group capable of being polymerized or crosslinked as a negative image recording material. A photopolymerizable composition containing a compound has been used as a photosensitive layer.

The photopolymerizable composition, whether it is curable by visible light or infrared, is basically a polymerization initiator such as a radical generator, a monomer having a polymerizable functional group, and further a photosensitive material. It contains a binder polymer for improving the film property of the layer, and upon exposure or heating, radicals are generated from the initiator in the exposed (heated) region, and the radical causes the polymerizable compound to undergo a polymerization / crosslinking reaction, resulting in a photosensitive layer. The curing reaction is performed to form an image portion. Such a photopolymerizable composition contains a large amount of polymerizable compounds, and these are often relatively low molecular weight compounds such as monomers or oligomers.

The lithographic printing plate precursor is usually light-shielded and packed, and is transported and stored under various environments. As a negative-type photosensitive layer, a photopolymerizable composition of a type curable by exposure, when stored at a high temperature for a long time, the polymerizable compound undergoes dark polymerization, and an unexposed portion is insolubilized. There was a problem that image failure occurred. In particular, in an image-forming material which is directly developed without being heated after exposure and irradiation with an infrared laser, there is a problem in compatibility between sensitivity and storage time.

[0006]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-187322

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems in the prior art, that is, to cure with high sensitivity by visible light or infrared laser and to record directly from digital data of a computer or the like. It is useful as a photosensitive layer of a possible negative negative lithographic printing plate precursor, and
It is an object of the present invention to provide a photopolymerizable composition capable of achieving excellent temporal stability, high-quality image formation, high printing durability, and chemical resistance.

[0008]

Means for Solving the Problems The present inventor has paid attention to a polymerizable compound contained in a large amount in a photopolymerizable composition, and as a result of intensive studies, as a result of using a polymerizable compound having specific structural properties, The inventors have found that the object can be achieved, and have completed the present invention. That is, the present invention is as follows. (1) (A) a polymerizable compound having at least one radically polymerizable ethylenically unsaturated double bond in the molecule and having a cohesive energy density of 500 J / cm ³ or more, (B) a radical polymerization initiator, and (C) A photopolymerizable composition containing a binder polymer, which is cured by exposure. (2) In addition to the components (A), (B) and (C),
(D) contains a compound that generates heat when exposed to infrared rays,
The photopolymerizable composition as described in (1) above, which is cured by exposure to infrared laser. (3) The photopolymerizable composition as described in (1) or (2) above, wherein the binder polymer is a binder polymer having an ethylenically unsaturated double bond in a side chain.

In the present invention, as the polymerizable compound having a radically polymerizable ethylenically unsaturated double bond,
Molecules having a cohesive energy density of 500 J / cm ³ or more are used. Molecules having a high cohesive energy density have a strong interaction between the same molecules, and are therefore considered to exist as aggregates of a certain size in the photosensitive layer of the lithographic printing plate precursor. As a result, the mobility of the molecule is suppressed, the polymerization is suppressed even in the presence of a slight amount of active species generated during storage, and the stability over time becomes excellent. On the other hand, for example, when exposed by infrared exposure, the cohesive energy sharply decreases due to the temperature rise of the exposed portion, and the intermolecular interaction is weakened. As a result, the mobility of the molecules is increased and it is possible to contribute to the polymerization, and it is possible to form an image with excellent image quality. As described above, the photopolymerizable composition of the present invention is useful as a photosensitive layer of a negative type lithographic printing plate precursor which can be directly recorded from digital data of a computer or the like, which is cured with high sensitivity by visible light or infrared laser. And, even when stored at high temperature for a long time, dark polymerization of the polymerizable compound is suppressed, and light that can achieve excellent aging stability, high-quality image formation, high printing durability, and chemical resistance can be achieved. A polymerizable composition can be provided.

The cohesive energy density of the present invention is Fendors.
The value calculated by the method proposed by.
For the calculation method of the cohesive energy density by Fendors, see, for example, RFFedors, Polym.Eng.Sci., 14, 147 (197
4) Or by DW Krevelen, Properties of Polymers,
Third Edition, Elsevier (1997), p. 189-200.

In this method, the cohesive energy of a molecule is calculated as the sum of constituent atoms or atomic groups. That is, cohesive energy Ecoh (J / mol) = Σ (ni × Ei) where ni is the number of moles of each atom or atomic group constituting one mole of the monomer, and Ei is the cohesive energy contribution constant J / of each atom or atomic group. mol. The cohesive energy density is calculated by dividing the cohesive energy by the total volume of each atom or atomic group constituting 1 mol of the monomer. That is, it is given by Σ (ni × Ei) / Σ (ni × Vi). Here, Vi is the volume of each atom or atomic group that constitutes 1 mol of the molecule.
cm ³ / mol. The following table shows examples of cohesive energy contribution constants and volume values for each atom or atomic group.

[0012]

[Table 1]

For example, in the case of a monomer having the following structure

[0014]

[Chemical 1]

The cohesive energy density of this molecule is 448 J / cm ^3.
Is calculated.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable composition of the present invention will be described in detail below. The photopolymerizable composition of the present invention is characterized by using a compound having a cohesive energy density of 500 J / cm ³ or more as a polymerizable compound together with an initiator and a photosensitizer optionally added. The constituent components of the photopolymerizable composition of the present invention will be sequentially described.

(A) having at least one radically polymerizable ethylenically unsaturated double bond in the molecule, 500 J /
Polymerizable compound having a cohesive energy density of cm ³ or more (hereinafter, appropriately referred to as a polymerizable compound) As the polymerizable compound that can be preferably used in the present invention, the cohesive energy density is at least 500 J / cm ³ or more, and more preferably Is preferably 700 J / cm ³ or more. The radical polymerizable compound is selected from known radical polymerizable compounds having at least one ethylenically unsaturated double bond. These have a chemical form such as a monomer, a prepolymer, an oligomer, or a mixture thereof or a copolymer thereof. Examples of the monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably unsaturated carboxylic acids. Esters of acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds are used. Further, a hydroxyl group, an amino group, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a mercapto group, an amide and a monofunctional or polyfunctional isocyanate, an addition reaction product of an epoxy,
A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and halogens. A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving group such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. Further, as another example, it is also possible to use a compound group in which unsaturated phosphonic acid, styrene or the like is substituted for the above unsaturated carboxylic acid.

Specific examples include the following compounds, but the present invention is not limited thereto. For example, tris (acryloyloxyethyl) isocyanurate (cohesion energy density 739 J / cm ³ ), tris (methacryloyloxyethyl) isocyanurate (714 J / c
m ³ ), bis (acryloyloxyethyl) hydroxyethyl isocyanurate (921 J / cm ³ ), tris (hydroxyethyl) isocyanurate dimethacrylate (906 J / c)
m ³ ), 1,3,5-tris (2-acryloxyethylaminocarbonyl) benzene (677 J / cm ³ ), 1,3,5
-Tris (2-methacryloxyethylaminocarbonyl) benzene (639J / cm ³ ), 1,2-benzenedicarboxylic acid bis [2-hydroxy-3 [(1-oxo-2-propenyl)]
Oxy] propyl] ester (713J / cm ³ ), N, N'-methacryloylhexamethylenediamine (539 J / cm ³ ), N, N'-
Acryloylhexamethylenediamine (570 J / cm ³ ), p
-Acrylates and methacrylates such as bis (acryloylamino) benzene (747 J / cm ³ ); N, N'-bis (styrylcarbonyl) hexamethylenediamine (584J / c
m ³ ), N, N′-bis (styrylcarbonyl) 1,4-cyclohexylenediamine (647J / cm ³ ), 1,3,5-tris (2-styrylcarbonylaminoethoxycarbonyl) benzene (681J / cm ³ ), 1,3,5-Tris (2-
Examples thereof include styrenes such as styrylcarboxylethylaminocarbonyl) benzene (708 J / cm ³ ).

These have a cohesive energy density of at least
500 J / cm ³ or more, as long as more preferably those having 700 J / cm ³ or more, for example, a monomer, a prepolymer, namely, dimer, trimer or oligomer, or mixtures thereof and copolymers thereof, It may have a chemical form such as. If the cohesive energy density is less than 500 J / cm ³ , the mobility of individual molecules is activated due to the decrease in the interaction between polymerizable compounds during storage at high temperature during transport and storage, and the attack from the radical-initiated species generated in a small amount. It becomes easy to receive. This is not suitable because dark polymerization is likely to occur at high temperature storage and development failure in non-image areas occurs during image formation. The upper limit of the cohesive energy density is practically 3500 J / cm ³ .
Further, when the heat generated by the infrared laser is used, the lower part of the image forming layer is absorbed by the infrared absorbent,
The curing of the image forming layer cannot be said to be sufficient due to the fact that light does not reach or heat diffusion occurs to the substrate with high thermal conductivity.Therefore, when it is used as a printing plate, film strength and ink strength against stress applied during printing Chemical resistance against dampening water, cleaners and other chemicals is required. The polymerizable compound of the present invention causes little reduction in film strength due to addition, and is also effective for image forming property, printing durability and chemical resistance during printing of the plate after plate making. The polymerizable compound may be used alone or in combination of two or more, if desired. The polymerizable compound is contained in the photopolymerizable composition of the present invention in a solid content of preferably 5 to 80% by mass, and more preferably 10 to 60% by mass.

(B) Radical Polymerization Initiator The radical polymerization initiator preferably used in the present invention is selected from compounds capable of generating radicals upon application of energy such as light, heat and radiation, and is used for expressing polymerization. Depending on the wavelength of the light source, various photoinitiators known in patents, literatures, etc., or a combination system of two or more photoinitiators (photoinitiator system) can be appropriately selected and used.
For example, when ultraviolet light of 400 nm or less is used as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone and the like are widely used.

When a visible light of 400 nm or more, an argon laser, or a YAG-SHG laser is used as a light source,
Various photoinitiating systems have been proposed, for example, certain photosensitive dyes described in U.S. Pat. No. 2,850,445 and complex initiation systems of dye and amine (Japanese Patent Publication No. 44-20189).
No.), a system using a combination of a hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Laid-open No. Sho. 54-155292), a system of cyclic cis-α-dicarbonyl compounds and dyes (JP-A-48-84183), a system of substituted triazines and merocyanine dyes (JP-A-54-15).
1024), a system of 3-ketocoumarin and an activator (JP-A-52-112681, JP-A-58-15503),
Biimidazole, styrene derivative, thiol system (JP-A-59-140203), organic peroxide and dye system (JP-A-59-140203, JP-A-59-1893).
40), a system of a dye having a rhodanine skeleton and a radical generator (JP-A-2-244050), a system of titanocene and a 3-ketocoumarin dye (JP-A-63-221110), a titanocene-xanthene dye and further an amino group or a urethane group. A system in which an addition-polymerizable ethylenically unsaturated compound containing a compound is combined (Japanese Patent Laid-Open No. 221958/1992)
219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061), and the like.

In the case of exposure with infrared rays having a wavelength of 760 nm or more, onium salts are preferable from the viewpoint of sensitivity. Specific examples of onium salts include iodonium salts, diazonium salts, and sulfonium salts.
These onium salts also have a function as an acid generator, but in the present composition, since they are used in combination with the solid radically polymerizable compound, they function as an initiator for radical polymerization. The onium salt preferably used in the present invention is an onium salt represented by the following general formulas (III) to (V).

[0023]

[Chemical 2]

In the formula (III), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms which may have a substituent. When the aryl group has a substituent, preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an alkyl group having 12 or less carbon atoms. An aryloxy group is mentioned. Z ¹¹ — represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, preferably a perchlorate ion and a hexafluorophosphate ion. An ion and an aryl sulfonate ion.

In the formula (IV), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred substituents include halogen atoms, nitro groups, alkyl groups having 12 or less carbon atoms, alkoxy groups having 12 or less carbon atoms, aryloxy groups having 12 or less carbon atoms, and those having 12 or less carbon atoms. Alkylamino group, dialkylamino group having 12 or less carbon atoms, 1 carbon atom
Examples thereof include an arylamino group having 2 or less or a diarylamino group having 12 or less carbon atoms. Z ^{21 -} is Z ^11-
Represents a counter ion having the same meaning as.

In the formula (V), R ³¹ , R ³² and R ³³ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

In the present invention, specific examples of onium salts that can be preferably used include onium salts represented by the general formula (III) ([OI-1] to [OI-10]) and general formula (IV). Onium salt represented by ([ON-1] to [O
N-5]), an onium salt represented by the general formula (V) ([O
S-1] to [OS-5]), but the invention is not limited thereto. .

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

The polymerization initiator used in the present invention is
The maximum absorption wavelength is preferably 400 nm or less,
Further, it is preferably 360 nm or less. By thus setting the absorption wavelength in the ultraviolet region, the lithographic printing plate precursor can be handled under a white light.

These polymerization initiators may be used alone or in combination of two or more. These polymerization initiators are used in an amount of 0.1 to 50 relative to the total solid content of the photopolymerizable composition.
It can be added in a proportion of% by mass, preferably 0.5 to 30% by mass, particularly preferably 1 to 20% by mass. If the addition amount is less than 0.1% by mass, the sensitivity becomes low, and 5
When it exceeds 0% by mass, for example, when this composition is used as a photosensitive layer of a lithographic printing plate, stains are likely to occur on a non-image area during printing. These polymerization initiators may be added to the same layer as other components, or may be added to another layer provided separately.

(C) Binder polymer In the photopolymerizable composition of the present invention, since a solid compound is used as the polymerizable compound, a binder polymer for holding the solid polymerizable compound and for forming a film is used. Added. It is preferable to use a linear organic polymer as the binder. Such a "linear organic polymer"
Any of these may be used. When the photopolymerizable composition of the present invention is used as a photosensitive layer of a lithographic printing plate, a linear organic compound soluble or swellable in water or alkaline water is used to enable development with water or alkaline water. It is preferred to select the polymer. The linear organic polymer is selected and used not only as a film-forming agent for forming a photosensitive layer but also as a developability improver with water, weak alkaline water or an organic solvent. For example, water development becomes possible by using a water-soluble organic polymer. As such a linear organic polymer, a radical polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615 and JP-B-54-34327.
No. 58-12577 / 54-2595
7, JP-A-54-92723, and JP-A-59-538.
36, JP-A-59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial Examples include esterified maleic acid copolymers. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in its side chain. In addition to these, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group.

Of these, a (meth) acrylic resin having an ethylenically unsaturated double bond such as an allyl group, a (meth) acryloyl group or a (meth) acrylamide group and a carboxyl group in its side chain is particularly preferable. It has an excellent balance of sensitivity, developability and is suitable.

Further, Japanese Patent Publication No. 7-120040, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Unexamined Patent Publication No. 63-287944, Japanese Unexamined Patent Publication No. 63-287947, Kaihei 1-271741
The acid group-containing urethane-based binder polymers described in Japanese Patent Application No. 10-116232 and the like are very excellent in strength and are advantageous in terms of printing durability and low exposure suitability.

In addition to these, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured film.

The weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, further preferably. Is in the range of 2000 to 250,000. The polydispersity (mass average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10.

These polymers are random polymers,
It may be either a block polymer or a graft polymer, but a random polymer is preferable.

The binder polymers used in the present invention may be used alone or as a mixture. These polymers are added in a proportion of 20 to 95% by mass, preferably 30 to 90% by mass, based on the total solid content of the photopolymerizable composition.
If the addition amount is less than 20% by mass, the strength of the image area will be insufficient when an image is formed. If the addition amount exceeds 95% by mass, no image is formed. The mass ratio of the compound having a radically polymerizable ethylenically unsaturated double bond and the linear organic polymer is preferably 1/9 to 7/3.

(D) Compound that Generates Heat by Infrared Exposure When the photopolymerizable composition of the present invention is used for recording with a laser that emits infrared rays, a compound that generates heat by infrared exposure (hereinafter, appropriately, It is preferable to add an infrared absorbing agent). The infrared absorber has a function of converting the absorbed infrared rays into heat, and the heat generated at this time causes the radical generator to decompose and generate radicals. The infrared absorbent used in the present invention has a wavelength of 7
It is a dye or pigment having an absorption maximum from 60 nm to 1200 nm.

As the dyes, commercially available dyes and known dyes described in documents such as "Handbook of Dyes" (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples thereof include dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, and metal thiolate complexes. Preferred dyes are, for example, JP-A-58-125246.
JP-A-59-84356 and JP-A-59-2028.
29, JP-A-60-78787, and other cyanine dyes, JP-A-58-173696, and JP-A-5-173966.
8-181690, methine dyes described in JP-A-58-194595, and JP-A-58-112793.
JP-A-58-224793, JP-A-59-481
87, JP-A-59-73996, JP-A-60-52.
940, naphthoquinone dyes described in JP-A-60-63744, etc., squarylium dyes described in JP-A-58-112792, UK Patent 43
Examples thereof include cyanine dyes described in No. 4,875.

Further, the near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and the substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also used. Pyrylium salt, JP-A-57-142645
Trimethine thiapyrylium salt described in U.S. Pat. No. 4,327,169, JP-A Nos. 58-181051, 58-220143, 59-41363 and 59-11363.
-84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranium compounds described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fair 5-13
Pyrylium compounds disclosed in Japanese Patent Nos. 514 and 5-19702 are also preferably used. Another preferred example of the dye is US Pat. No. 4,756,993.
The near infrared absorbing dyes described as formulas (I) and (II) in the specification can be mentioned. Of these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes. Further, a cyanine dye is preferable, and a cyanine dye represented by the following general formula (I) is most preferable.

[0044]

[Chemical 7]

X in the general formula (I)¹Is a halogen atom,
X²-L¹Or NL²L³Indicates. Where X²Is oxygen source
Child or sulfur atom, L¹Has 1 to 1 carbon atoms
2 represents a hydrocarbon group, L²And L³Each independently charcoal
A hydrocarbon group having 1 to 12 elementary atoms is shown. R¹And R
²Are each independently a hydrocarbon having 1 to 12 carbon atoms.
Indicates a group. From the storage stability of the photosensitive layer coating liquid, R¹and
R²Is a hydrocarbon group having 2 or more carbon atoms
Preferably, further, R¹And R²And are bonded to each other
Alternatively, it is particularly preferable to form a 6-membered ring. Ar
¹, Ar²Can be the same or different,
The aromatic hydrocarbon group which may have a substituent is shown.
Y¹, Y²Can be the same or different,
Yellow or dialkylmethylene having 12 or less carbon atoms
Group. R ³, R^FourAre the same or different
20 carbon atoms, which may or may not have a substituent
The following hydrocarbon groups are shown. The preferred substituent is charcoal.
An alkoxy group having 12 or less elementary atoms, a carboxyl group,
Examples thereof include a sulfo group. R^Five, R⁶, R⁷And R⁸Is that
They may be the same or different, and each may be a hydrogen atom or charcoal.
A hydrocarbon group having 12 or less elementary atoms is shown. Raw material availability
Therefore, it is preferably a hydrogen atom. Also, Z^1-Is a
Indicates Nion. However, R¹~ R⁸A sulfo group
Z is replaced by Z^1-Is not necessary. Preferred Z
^1-Is a halogen ion because of the storage stability of the photosensitive layer coating solution.
Ion, perchlorate ion, tetrafluoroborate ion,
Hexafluorophosphate ion, and sulfonic acid
Ions, particularly preferably perchlorate ion, hex
Safurophosphate ion, and arylsulfo
It is a nitrate ion.

In the present invention, the following [IR-1] to [IR-12] can be mentioned as specific examples of the cyanine dye represented by formula (I) which can be preferably used. Is not limited to these.

[0047]

[Chemical 8]

[0048]

[Chemical 9]

[0049]

[Chemical 10]

The pigment used in the present invention includes:
Commercial pigment and color index (CI) handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
The pigments described in 1. can be used.

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer bound dyes may be mentioned. Details of these pigments are described in paragraph No. [005 of JP-A-10-39509.
2] to [0054], which are also applicable to the present invention. Preferred among these pigments is carbon black.

The content of the above-mentioned dye or pigment in the photopolymerizable composition is preferably 0.01 to 50% by mass, and preferably 0.1 to 10% by mass, based on the total solid mass of the composition. More preferably, in the case of a dye, 0.5 to
10% by mass is most preferable, and in the case of a pigment, 1.0 to
Most preferred is 10% by weight. If the content is less than 0.01% by mass, the sensitivity may be lowered, and if it exceeds 50% by mass, stains may occur on the non-image area in the lithographic printing plate precursor.

[Other Components] In the present invention, various compounds other than these may be added, if necessary.
For example, a dye having a large absorption in the visible light region can be used as a colorant for images. Further, pigments such as phthalocyanine-based pigments, azo-based pigments, carbon black and titanium oxide can also be preferably used. These colorants are added for the purpose of making it easier to distinguish between image areas and non-image areas after image formation when the composition of the present invention is used as a photosensitive layer of a lithographic printing plate. The added amount is 0.01 to 10 mass% with respect to the total solid content of the composition.

In addition, the composition of the present invention contains a small amount of thermal polymerization in order to prevent unnecessary thermal polymerization of the compound having an ethylenically unsaturated double bond capable of radical polymerization during preparation or storage of the coating solution. It is desirable to add an inhibitor. Suitable thermal polymerization inhibitors include hydroquinone and p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl) −
6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01 mass% to about 5 mass% with respect to the weight of the entire composition. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The amount of higher fatty acid derivative added is about 0.
1% to about 10% by weight is preferred.

Further, in the composition of the present invention, in order to broaden the stability of processing under developing conditions, JP-A-62-251
740 and nonionic surfactants described in JP-A-3-208514, JP-A-59-121044.
And an amphoteric surfactant as described in JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride and polyoxyethylene nonylphenyl ether.

Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N. , N-betaine type (for example,
Examples of the brand name include Amogen K, manufactured by Daiichi Kogyo Co., Ltd.

The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive layer coating liquid is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

Further, a plasticizer is added to the composition of the present invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate and the like are used.

In the photopolymerizable composition of the present invention, the radical initiator is decomposed by the energy locally applied in the exposed area to generate radicals. The acid or heat generated at that time melts the solid polymerizable compound, which is presumed to exist in the form of an aggregate or microcrystal, and becomes reactive, and the radical acts on the polymerizable functional group to cure it. The reaction proceeds. At this time, in the case of performing visible light or infrared light exposure, since a dye or pigment having a photothermal conversion ability is present in the initiator system, the polymerizable compound is rapidly melted by heat, and the reaction proceeds, The photopolymerizable composition of
From the viewpoint of sensitivity, it is preferable to use for visible light or infrared exposure accompanied by heat generation due to exposure, and in particular, since it is used in combination with an infrared absorber, it can be suitably used for recording by infrared laser exposure where local high energy heat generation occurs. .

When the photopolymerizable composition of the present invention is used as a photosensitive layer of a lithographic printing plate precursor, each component constituting the above photopolymerizable composition is usually dissolved in a solvent as a photosensitive layer coating solution. The photosensitive layer may be formed by dispersing and coating on a suitable support. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone,
Methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide,
N, N-dimethylformamide, tetramethylurea,
Examples thereof include N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyl lactone, toluene and water, but are not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1-5.
It is 0 mass%.

The feeling on the support obtained after coating and drying
The coating amount (solid content) of the optical layer depends on the application,
Generally speaking about 0.5 to 5.0 g for printing plate
/ M ²Is preferred. As the amount applied decreases
Photosensitive layer that performs the function of image recording, although the sensitivity of
The coating characteristics of the are deteriorated. There are various coating methods.
Although a method can be used, for example, a bar coater coating method is used.
Cloth, spin coating, spray coating, curtain coating, dip
Coating, air knife coating, blade coating, roll coating, etc.
Can be mentioned.

[Support] As a support to which the photosensitive layer can be applied in the lithographic printing plate precursor to which the composition of the present invention can be applied, it is dimensionally stable and has desired strength and durability. There is no particular limitation as long as it is a plate-like material, and examples include paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), metal plate (for example,
Aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate,
Polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic film laminated or vapor-deposited with the above metals. A preferable support includes a polyester film or an aluminum plate.

As the support used in the lithographic printing plate precursor according to the invention, it is preferable to use an aluminum plate which is lightweight and has excellent surface treatment property, processability and corrosion resistance. The aluminum material used for this purpose is JIS 1
050 material, JIS 1100 material, JIS 1070 material,
Al-Mg alloys, Al-Mn alloys, Al-Mn-M
g-based alloys, Al-Zr-based alloys. Examples thereof include Al-Mg-Si alloys.

The aluminum plate may be subjected to a surface treatment such as a surface roughening treatment and then coated with a photosensitive layer to prepare a lithographic printing plate precursor. The surface roughening treatment includes mechanical surface roughening, chemical surface roughening, and electrochemical surface roughening, either alone or in combination. In addition, it is also preferable to perform anodizing treatment for ensuring the scratch resistance of the surface and treatment for increasing the hydrophilicity.

The surface treatment of the support will be described below. Prior to roughening the aluminum plate, if necessary, for example, a surfactant for removing rolling oil on the surface,
Degreasing treatment with an organic solvent or an alkaline aqueous solution may be performed. In the case of alkali, a treatment such as neutralization and smut removal with an acidic solution may be performed next.

Next, in order to improve the adhesion between the support and the photosensitive layer and impart water retention to the non-image area, a so-called graining treatment for roughening the surface of the support is performed. As a concrete means of this graining method, there is a mechanical graining method such as sandblasting, and there is a chemical graining method in which the surface is roughened with an etching agent composed of an alkali, an acid or a mixture thereof. . In addition, an electrochemical graining method, a method of roughening the surface by adhering a granular material to a support material with an adhesive or a method having its effect, or a continuous band or roll having fine unevenness is used as a support. A known method such as a surface-roughening method in which unevenness is transferred by pressure bonding to a material can be applied.

A plurality of such roughening methods may be performed in combination, and the order, the number of repetitions and the like can be arbitrarily selected. Since smut is generated on the surface of the support obtained by the above-mentioned roughening treatment, that is, graining treatment, appropriate treatment such as washing with water or alkali etching should be performed to remove the smut. Are generally preferred.

In the case of the aluminum support used in the present invention, after the pretreatment as described above, the support is usually anodized in order to improve abrasion resistance, chemical resistance and water retention. An oxide film is formed on.

As the electrolyte used for the anodizing treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film. Generally, sulfuric acid,
Phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because it varies depending on the electrolyte used, but generally the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., the current density is 5 to 60 A / dm ^2. , Voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are suitable. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. If the anodic oxide film is less than 1.0 g / m ² , printing durability is insufficient, or the non-image area of the lithographic printing plate is easily scratched, and ink adheres to the scratched portion during printing. "Scratch dirt"
Is likely to occur.

Such an aluminum support can be used by treatment with an organic acid or a salt thereof after anodizing treatment or by applying an undercoat layer for coating a photosensitive layer.

An intermediate layer may be provided to enhance the adhesion between the support and the photosensitive layer. To improve the adhesion,
Generally, the intermediate layer is made of a diazo resin, a phosphoric acid compound that is adsorbed on aluminum, or the like. The thickness of the intermediate layer is arbitrary, and must be such that it can undergo a uniform bond forming reaction with the upper photosensitive layer when exposed. Normal,
A dry solid coating rate of about 1-100 mg / m ² is good,
5-40 mg / m ² is particularly good. The proportion of the diazo resin used in the intermediate layer is 30 to 100%, preferably 60 to 100%.

A preferable characteristic of the support for a lithographic printing plate is a center line average roughness of 0.10 to 1.2 μm. If it is less than 0.10 μm, the adhesiveness to the photosensitive layer is lowered,
This causes a marked decrease in printing durability. If it is larger than 1.2 μm, the stain resistance during printing deteriorates. Further, the color density of the support is 0.15 as the reflection density value.
If it is 0.65 and is whiter than 0.15, halation during image exposure is too strong to hinder image formation, and if it is blacker than 0.65, the image is difficult to see in the plate inspection work after development, The plate inspection property is remarkably poor.

As described above, a lithographic printing plate precursor using the photopolymerizable composition of the present invention as a photosensitive layer can be prepared. This lithographic printing plate precursor can be recorded with various light sources having wavelengths compatible with the polymerization initiator. Further, thermal recording with an ultraviolet lamp and a thermal head is also possible. Examples of the light source of actinic rays used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Radiation includes electron beams, X-rays, ion beams, far infrared rays, and the like. Also, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are used. Examples of the laser beam include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, and KrF excimer laser. In the present invention, image exposure is preferably carried out by a solid-state laser or a semiconductor laser which emits infrared rays having a wavelength of 760 nm to 1200 nm, particularly in a system using an infrared absorber in combination. The laser output is preferably 100 mW or more, and it is preferable to use a multi-beam laser device in order to shorten the exposure time. The exposure time per pixel is preferably within 20 μsec. The energy applied to the recording material is preferably 10 to 300 mJ / cm ² .

As the developing solution and the replenishing solution used for the development and plate making of the lithographic printing plate according to the present invention, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium, sodium triphosphate, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, Examples thereof include inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium.
Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Ethyleneimine, ethylenediamine,
Organic alkaline agents such as pyridine are also used. These alkaline agents may be used alone or in combination of two or more. Among these alkaline agents, a particularly preferable developer is an aqueous silicate solution such as sodium silicate or potassium silicate. The reason is that the developability can be adjusted by the ratio and concentration of silicon oxide SiO ₂ which is a component of silicate and alkali metal oxide M ₂ O. For example, JP-A-54-62004, An alkali metal silicate as described in JP-B-57-7427 is effectively used.

Further, in the case of developing using an automatic processor, an aqueous solution (replenisher) having a higher alkaline strength than the developing solution is used.
It is known that a large amount of PS plate can be processed by replacing the developing solution in the developing tank for a long period of time without adding the developing solution to the developing solution. Also in the present invention, this replenishment system is preferably applied. If necessary, various surfactants and organic solvents may be added to the developing solution and the replenishing solution for the purpose of accelerating or suppressing the developing property, dispersing the development residue and enhancing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, in the developing solution and the replenishing solution, if necessary, a reducing agent such as a sodium salt or potassium salt of an inorganic acid such as hydroquinone, resorcin, sulfurous acid, and bisulfite, an organic carboxylic acid, a defoaming agent, and a water softener. It can also be added. The printing plate developed using the above-mentioned developing solution and replenishing solution is post-treated with washing water, a rinse solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As the post-treatment when the image recording material of the present invention is used as a printing plate, various combinations of these treatments can be used.

In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate, each processing liquid tank and a spraying device, which conveys an exposed printing plate horizontally while pumping it up with each pump. The processing liquid is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid for processing. In such automatic processing, it is possible to perform processing while supplementing each processing solution with a replenishing solution according to the processing amount, operating time, and the like. Further, a so-called disposable processing method of processing with a substantially unused processing liquid can be applied.

The planographic printing plate obtained as described above,
If desired, the desensitized gum may be applied and then subjected to a printing step. The lithographic printing plate precursor having the photopolymerizable composition of the present invention as a photosensitive layer is subjected to image formation through the predetermined steps as described above to obtain a lithographic printing plate. This planographic printing plate is set on an offset printing machine or the like and used for printing a large number of sheets.

Further, the photopolymerizable composition of the present invention contains UV
It is cured with high sensitivity by exposure to light, visible light, and infrared laser, and the cured coating does not cause plastic flow, and can suppress adhesion, deformation, scratches, etc. when stored repeatedly, and it is uniform. In addition to the photosensitive layer of the lithographic printing plate precursor described above in detail, since it has a stable film and excellent image forming property, for example, various applications such as flexographic printing plates, color proofs, dry lith films, photoresists, color filters, etc. Can be suitably used.

[0080]

[Example 1]

[Creation of support] 0.30 mm thick aluminum plate
(Material 1050) was washed with trichlorethylene and degreased
After that, nylon brush and 400 mesh pumice stone-
Grain the surface with a water suspension and wash well with water.
It was This plate was immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C.
Immerse for 9 seconds, etch, wash with water, and then add 2% H
NO ₃It was soaked in water for 20 seconds and washed with water. Graining at this time
Surface etching rate is about 3g / m²Met. Then this
Plate 7% H₂SO_FourCurrent density of 15 A / dm
²At 3 g / m²After providing the DC anodized film of
did.

[Undercoating] Next, the following undercoating solution was applied to the aluminum support with a wire bar and dried at 90 ° C for 30 seconds using a warm air dryer. The coated amount after drying was 10 mg / m ² .

[0082] <Undercoat liquid>   ・ Ethyl methacrylate and 2-acrylamido-2-methyl-1-     0.1 g of a copolymer of propanesulfonic acid sodium salt with a molar ratio of 75:25   ・ 2-Aminoethylphosphonic acid 0.1 g   ・ Methanol 50g   ・ Ion-exchanged water 50g

[Photosensitive layer] Next, the following photosensitive layer coating liquid P-1
Was prepared and applied to the above-mentioned undercoated aluminum plate with a wire bar and dried at 115 ° C. for 45 seconds in a warm air dryer to form a photosensitive layer. The lithographic printing plate precursor [P-1 ] Was obtained. The coating amount after drying is 1.25 ± 0.0
It was within the range of 5 g / m ² .

<Photosensitive layer coating liquid P-1> Bis (acryloyloxyethyl) hydroxyethyl isocyanurate ...... 1.0 g (cohesive energy density 921 J / cm ³ polymerizable compound, hereinafter referred to as polymerizable compound M-1)) ・ Infrared absorber (structure below) ・ ・ ・ ・ ・ ・ ・ ・ 0.08 g ・ Polymerization initiator (structure below) ) ... 0.25 g-Allyl methacrylate and methacrylic acid-1.0 g Copolymer with a molar ratio of 80:20 (weight average molecular weight 130,000)・ Copper phthalocyanine pigment colorant ・ ・ ・ ・ 0.1g ・ Surfactant ・ ・ ・ ・ 0.02g Fuck F-475, manufactured by Dainippon Ink and Chemicals, Inc. ・ Methyl ethyl ketone ... · · · · · · · 10 g · Methanol ···················· 5 g · 1-Methoxy-2-propanol ········· 12 g

[0085]

[Chemical 11]

[0086]

[Chemical 12]

[Evaluation of stability over time] As a means for evaluating the stability over time of the obtained lithographic printing plate precursor, it was left in a constant temperature drying box at 60 ° C. for 3 days. After standing, the insolubilization rate and image forming property of the unexposed area were evaluated by the following methods. The evaluation results are shown in Table 3. (Insolubilization Rate) The lithographic printing plate precursor is immersed in a mixed solution of dimethyl sulfoxide / methyl ethyl ketone in an equal volume for 5 minutes, and the eluted film mass (g / m ² ) is calculated. The film mass of the original photosensitive layer measured in advance (g / m ² ) and the film mass eluted (g / m ² ).
The insolubilization rate% was calculated from m ² ). That is, insolubilization rate% = (original film mass-eluted film mass)
X100 / original film mass This value allows dark polymerization to be evaluated with higher sensitivity than the developability with an apparent developer, which differs depending on the type of developer, and is preferably as close to 0% in the unexposed area.

(Image Formability) The obtained lithographic printing plate precursor was Creo equipped with a water-cooled 40 W infrared semiconductor laser.
Exposure was carried out with a Trendsetter 3244VFS manufactured by the same company at a plate surface energy of 200 mJ / cm ² . Next, Fuji Photo Film Co., Ltd. automatic processor Stablon 900NP
The following composition [G] as a developer and a 1: 1 aqueous solution of FP-2W manufactured by Fuji Photo Film Co., Ltd. as a gum solution were added to the above to develop and gum the exposed lithographic printing plate precursor. It was pulled.

[0089] <Developer [G]> ・ Potassium sulfite: 0.05 mass% ・ Potassium hydroxide: 0.1 mass% ・ Potassium carbonate ・ ・ 0.2 mass% -Ethylene glycol mononaphthyl ether --- 4.8 mass% ・ 4Na salt of EDTA ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.13% by mass ・ Silicone type surfactant ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.02 mass% ・ Water: 94.7% by mass

Example 2 Bis (acryloyloxyethyl) hydroxyethyl isocyanurate of Example 1 was converted to 1,2-benzenedicarboxylic acid bis [2-hydroxy-].
3 [(1-oxo-2-propenyl) oxy] propyl] ester (cohesive energy; 713 J / cm ³ (hereinafter, the polymerizable compound M-2
A coating liquid P-2 was prepared in the same manner except that the lithographic printing plate precursor was changed to (). The coating amount after drying was within the range of 1.25 ± 0.05 g / m ² . The obtained lithographic printing plate precursor [P-2] was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0091]

[Chemical 13]

Example 3 Bis (acryloyloxyethyl) hydroxyethyl isocyanurate obtained in Example 1 was replaced with N,
A similar coating liquid P-3 was prepared, except that N′-methacryloylhexamethylenediamine (coagulation energy density 539 J / cm ³ (hereinafter referred to as polymerizable compound M-3)) was used,
Similarly, a lithographic printing plate precursor was obtained. The coating amount after drying is 1.
It was within the range of 25 ± 0.05 g / m ² . The obtained lithographic printing plate precursor [P-3] was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0093]

[Chemical 14]

Comparative Example 1 Bis (acryloyloxyethyl) hydroxyethyl isocyanurate of Example 1 was added to pentaerythritol tetraacrylate (cohesive energy density 448 J / cm ³ (hereinafter referred to as polymerizable compound M-4)). A coating liquid P-4 was prepared in the same manner except that it was changed, and a lithographic printing plate precursor was similarly obtained. The coating amount after drying is 1.25 ±
It was within the range of 0.05 g / m ² . The obtained lithographic printing plate precursor [P-4] was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0095]

[Chemical 15]

Comparative Example 2 The bis (acryloyloxyethyl) hydroxyethyl isocyanurate of Example 1 was converted into 4,4′-bis (2-hydroxyethoxy) biphenyl diacrylate (cohesive energy density 484 J / cm ³ (hereinafter, A coating solution P-5 was prepared in the same manner except that the polymerizable compound M-5 was changed to ()) to obtain a lithographic printing plate precursor. The coating amount after drying was within the range of 1.25 ± 0.05 g / m ² . The obtained lithographic printing plate precursor [P-5] was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0097]

[Chemical 16]

[0098]

[Table 2]

Example 4 The following undercoat liquid was applied to the aluminum support prepared in Example 1 with a wire bar,
It dried at 90 degreeC for 30 second using the warm air type dryer. The coated amount after drying was 20 mg / m ² .

[0100] <Undercoat liquid>   -Methacryloyloxyethyl sulfonic acid 0.2 g   ・ Methyl acrylate and styrene sulfonic acid sodium salt       0.2 g of a copolymer having a molar ratio of 75:25   ・ Calcium nitrate 0.2g   ・ Methanol 20g   ・ Ion-exchanged water 80g

[Photosensitive layer] The following photosensitive layer coating liquid P-6 was coated on the support having the undercoat layer formed thereon with a wire bar,
A recording layer is formed by drying at 120 ° C. for 45 seconds in a warm air dryer, and the following overcoat layer coating solution is applied using a slide hopper.
After drying at 0 ° C. for 75 seconds, the lithographic printing plate precursor [P
-6] was obtained. The coating amount of the photosensitive layer was 2.0 g / m ² and the coating amount of the overcoat layer was 2.3 g / m ² .

[0102] <Photosensitive layer coating liquid P-6>   ・ Titanocene type radical generator 0.1g     (CGI-784, manufactured by Ciba Specialty Chemicals Co., Ltd.)   -Polymerizable compound (M-1) 0.80 g   ・ Light absorber (VR-1) 0.10 g   ・ Polymer (PB-1) 1.20 g   ・ Copper phthalocyanine pigment 0.04g   ・ Fluorosurfactant 0.03g       (Megafuck KF309, manufactured by Dainippon Ink and Chemicals, Inc.)   ・ Methyl ethyl ketone 10g   ・ Γ-Butyrolactone 5 g   ・ Methanol 7g   ・ 1-Methoxy-2-propanol 5g

The structure of the visible light absorber and the like used in the preparation of the coating liquid for photosensitive layer is as shown below. Moreover, the polymer (PB-1) was synthesized by synthesizing a copolymer of methacrylic acid, N-isopropylacrylamide and ethyl methacrylate, and then reacting it with 1,2-epoxy-3-methacryloyloxymethylcyclohexane. The composition molar ratio was 15: 30: 20: 35, and the mass average molecular weight was 120,000.

[0104]

[Chemical 17]

[0105]

[Chemical 18]

[0106] <Coating liquid for overcoat layer>   ・ Polyvinyl alcohol 3.0g       (Saponification degree 98.5 mol%, degree of polymerization 500)   ・ Nonionic surfactant 0.05g       (EMEREX NP-10, manufactured by Nippon Emulsion Co., Ltd.)   ・ Ion-exchanged water 96.95g

The means for evaluating the temporal stability of the obtained lithographic printing plate precursor was the same as in Example 1 except for the evaluation of the image forming property shown below. The evaluation results are shown in Table 4.

(Evaluation of Image Formability) The obtained lithographic printing plate precursor was used with a 30 mW semiconductor laser which emits 405 nm violet light, laser beam diameter was 12 μm, and plate surface energy was 50.
Scanning exposure was carried out under an exposure condition of μJ / cm ² , and a developer composition of the following composition was charged in the development processing tank of an automatic developing machine (LP-850P2) manufactured by Fuji Photo Film Co., Ltd. and kept at 30 ° C. Tap water was charged in the second bath of the automatic processor, and FP-2W (manufactured by Fuji Photo Film Co., Ltd.) in the third bath:
A finishing gum solution diluted with water = 1: 1 was charged.

[0109] <Developer composition>   ・ Sodium hydrogen carbonate 26g   ・ Ethylene glycol mononaphthyl ether       Sodium monosulfate salt 30g   ・ Ethylene glycol monododecyl ether 20g   ・ Sodium sulfite 3g   ・ Ethylenediaminetetraacetic acid tetrasodium 1g   ・ Water 920g

[Comparative Example 3] Polymerizable compound M- of Example 4
A photosensitive layer coating liquid P-7 was prepared in the same manner except that 1 was changed to the polymerizable compound M-4, and an overcoat layer was similarly coated to obtain a lithographic printing plate precursor [P-7]. The coating amount of the photosensitive layer was 2.0 g / m ² , and the coating amount of the overcoat layer was 2.3 g / m ² . The obtained lithographic printing plate precursor was evaluated in the same manner as in Example 4. The evaluation results are shown in Table 4.

[0111]

[Table 3]

Example 5 Bis (acryloyloxyethyl) hydroxyethyl isocyanurate of Example 1 was replaced with a polymerizable compound M-6 (cohesive energy density 8
66 J / cm ³ ) and the binder polymer was changed from a copolymer of allyl methacrylate and methacrylic acid to the binder polymer (BP-1) shown below.
A coating liquid P-8 was prepared in the same manner as in Example 1, and a lithographic printing plate precursor [P-8] was obtained in the same manner. The coating amount after drying is 1.
It was within the range of 25 ± 0.05 g / m ² . The lithographic printing plate precursor thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 5.
Shown in.

[0113]

[Chemical 19]

(Synthesis of Binder Polymer BP-1) 1
70 g of N, N-dimethylacetamide was placed in a 000 ml three-necked flask and heated to 70 ° C. under a nitrogen stream. 33.5 g of compound (A-1) having the following structure, 6.8 g of methacrylamide, 12.0 g of methyl methacrylate, 6.9 g of methacrylic acid, azo polymerization initiator V-59 (manufactured by Wako Pure Chemical Industries, Ltd.) A solution of 0.538 g of N, N-dimethylacetamide in 70 g was added dropwise over 2.5 hours. After completion of the dropping, the mixture was heated to 90 ° C. and further stirred for 2 hours. After cooling the reaction solution to room temperature, it was poured into 3.5 L of water to precipitate a polymer compound. The precipitated polymer compound is collected by filtration,
After washing with water and drying, 48.5 g of a polymer compound was obtained. The mass average molecular weight of the obtained polymer compound was 124,000 as measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The acid value was determined by titration to be 1.30.
It was meq / g (calculated value 1.35 meq / g), and it was confirmed that the polymerization was normally performed.

Into a 200 ml three-necked flask, 26.0 g of the obtained polymer compound and 0.1 g of p-methoxyphenol were placed and dissolved in 60 g of N, N-dimethylacetamide.
After dissolution, the mixture was cooled in an ice bath containing ice water. After the temperature of the mixed solution became 5 ° C. or lower, 30.4 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU)
Was added dropwise over 1 hour using a dropping funnel. After completion of dropping, the ice bath was removed and the mixture was further stirred for 8 hours. The reaction solution was poured into 2 L of water in which 17 ml of concentrated hydrochloric acid was dissolved, and the polymer compound (P
-1) was deposited. The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 18.2 g of a polymer compound. When the H-NMR of the obtained polymer compound was measured, it was confirmed that 100% of the side chain group derived from the compound (A-1) was converted into an ethylene methacrylate group. The mass average molecular weight was 114,000 as measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Furthermore, when the acid value was determined by titration, it was 0.9 meq / g (calculated value 0.8 m
eq / g).

[0116]

[Chemical 20]

[0117]

[Chemical 21]

(Comparative Example 4) Polymerizable compound M- of Example 5
6 to dipentaerythritol hexaacrylate (M-
Coating liquid P- was prepared in the same manner as in Example 5 except that the composition was changed to 7).
9 was prepared, and a lithographic printing plate precursor [P-9] was similarly obtained.
The coating amount after drying was within the range of 1.25 ± 0.05 g / m ² . The lithographic printing plate precursor thus obtained was evaluated in the same manner as in Example 5. The results are shown in Table 5.

[0119]

[Chemical formula 22]

[0120]

[Table 4]

Further, as an evaluation of printing durability and cleaner resistance, the plates of Examples 1 to 5 and Comparative Examples 1, 2 and 4 obtained by exposure and development were printed using a printing machine Lithlon manufactured by Komori Corporation. did. It is possible that good prints were obtained and that good prints were obtained when the image area was wiped with a plate cleaner (CL-1) manufactured by Fuji Photo Film Co., Ltd. every 5000 sheets. The results of the number of sheets are shown in Table 6.

[0122]

[Table 5]

Example 6 The copolymer of allyl methacrylate and methacrylic acid used as the binder polymer in Example 1 is shown below as a binder polymer (B
Coating liquid P-10 was prepared in the same manner as in Example 1 except that P-2) was used, and the planographic printing plate precursor [P-1 was prepared in the same manner.
0] was obtained. The coating amount after drying is 1.25 ± 0.05 g /
It was within the range of m ² . The lithographic printing plate precursor thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 7.

(Synthesis of Binder Polymer BP-2) The compound (A
-1) 33.5 g of compound (A-2) 22.
A binder polymer (BP-2) was obtained by the same method except that the amount was changed to 6 g. When the H-NMR of the obtained polymer compound was measured, it was confirmed that 100% of the side chain group derived from the compound (A-2) was converted into an ethylene methacrylate group. In addition, a gel permeation chromatography method using polystyrene as a standard substance (G
As a result of measuring the mass average molecular weight by PC), 98,
It was 000. Furthermore, the acid value determined by titration was 0.9 meq / g (calculated value 0.8 meq / g).

[0125]

[Chemical formula 23]

[0126]

[Chemical formula 24]

[Comparative Example 5] A coating solution P-11 was prepared in the same manner as in Example 6 except that dipentaerythritol hexaacrylate (M-7) was used as the polymerizable compound in Example 6, and the lithographic printing plate was prepared in the same manner. A printing plate precursor [P-11] was obtained. The coating amount after drying was within the range of 1.25 ± 0.5 g / m ² . The lithographic printing plate precursor thus obtained was evaluated in the same manner as in Example 6. The results are shown in Table 7.

[0128]

[Table 6]

Further, as evaluations of printing durability and cleaner resistance, the plates of Examples 1 to 5 and Comparative Examples 1, 2 and 4 obtained by exposure and development were printed using a printing machine Lithrone manufactured by Komori Corporation. did. It is possible that good prints were obtained and that good prints were obtained when the image area was wiped with a plate cleaner (CL-1) manufactured by Fuji Photo Film Co., Ltd. every 5000 sheets. The results of the number of sheets are shown in Table 8.

[0130]

[Table 7]

As is clear from Tables 3, 4, 5 and 7,
The lithographic printing plate precursor using the photopolymerizable composition of the present invention as a photosensitive layer, even when stored at high temperature for a long time, dark polymerization of the polymerizable compound is suppressed, and excellent stability with time and high stability. It was confirmed that a high quality image could be obtained. Also,
As is clear from Tables 6 and 8, it was confirmed that the lithographic printing plate precursor using the photopolymerizable composition of the present invention as the photosensitive layer was excellent in printing durability and chemical resistance during printing.

[0132]

As described above, the photopolymerizable composition of the present invention is a negative-working lithographic printing plate precursor which is hardened by visible light or infrared laser with high sensitivity and can be directly recorded from digital data of a computer or the like. Which is useful as a photosensitive layer of, and even when stored at high temperature for a long time,
It is possible to provide a photopolymerizable composition in which dark polymerization of a polymerizable compound is suppressed and which can achieve excellent stability over time, high-quality image formation, and high printing durability and chemical resistance.

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Claims (3)

[Claims] 1. (A) 500 J / cm ³ having at least one radically polymerizable ethylenically unsaturated double bond in the molecule,
A polymerizable compound having the above cohesive energy density,
A photopolymerizable composition comprising (B) a radical polymerization initiator and (C) a binder polymer, which is cured by exposure. 2. In addition to the components (A), (B), and (C), it further comprises (D) a compound that generates heat upon exposure to infrared light, and is cured by exposure to infrared laser light. The photopolymerizable composition according to claim 1. 3. The photopolymerizable composition according to claim 1 or 2, wherein the binder polymer is a binder polymer having an ethylenically unsaturated double bond in a side chain.