JPS6389864A - Photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE:To improve the chemical resistance and sensitivity of a lithographic printing plate and to prevent the scumming thereof by incorporating an o- naphthoquinone diazide sulfonate, cyclic acid anhydride and specific high-polymer compd. into a photosensitive layer. CONSTITUTION:The photosensitive layer into which A): the o-naphthoquinone diazide sulfonate, B): the cyclic anhydride, and C): the high-polymer compd. contg. the structural unit expressed by formulas I-IV are incorporated is provided on a base consisting of anodically oxidized aluminum. In formulas I-IV, R1-R2 denote a hydrogen atom, alkyl, carboxylic group; R3 denote a hydrogen atom, halogen, alkyl group; R4 is a hydrogen atom, alkyl, phenyl, aralkyl group; X denotes an alkylene group; n denotes 0-10; Y denotes phenylene, naphthylene groups. Glutaric anhydride, tetrahydrophthalic anhydride, etc., are used as B): the cyclic acid anhydride. Since the compds. A), B), C) are used, the chemical resistance of the lithographic printing plate is improved, UV printing is permitted and development latitude is expanded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a positive-working photosensitive lithographic printing plate, and more specifically, the present invention relates to a positive-working photosensitive lithographic printing plate, and more specifically, the present invention relates to a positive-working photosensitive lithographic printing plate, and more specifically, the present invention relates to a positive-working photosensitive lithographic printing plate using an 0-naphthoquinone cyasito compound, a specific resin, and a cyclic The present invention relates to a positive-working photosensitive lithographic printing plate having a photosensitive layer based on a combination of acid anhydrides.

(Prior art) A positive planographic printing plate has an ink-receptive photosensitive layer on a wood-philic support, and this photosensitive layer is imagewise exposed and developed, leaving an image area and a non-printing area. The image is formed by removing the image area.

When printing on the front, the difference between the lipophilic properties of image areas and the hydrophilic properties of non-image areas is utilized.

Generally, the requirements for lithographic printing plates include printing durability,
These include chemical resistance, development latitude, ink receptivity, and sensitivity. Here, chemical resistance refers to suitability to various chemicals used during printing, such as isopropyl alcohol, inking ink, surface preparation liquid, plate cleaner, etc. In order to improve these, various studies have been made on both the photosensitive layer and the support.

As a photosensitive layer, a mixture of an 0-naphthoquinone cyacyto compound and a novolak resin is generally well known. 0
Examples of the naphthoquinone cyasito compound include examples using 0-naphthoquinone cyacitosulfonic acid ester of a polycondensation resin of pyrogallol and acetone, as described in Japanese Patent Publication No. 43-28403; As described in Japanese Patent Publication No. 76346, an example of controlling the developability using 0-naphthoquinone cyasitosulfonic acid ester of a polycondensation resin of a mixture of pyrogallol-resorcin and acetone, for example, JP-A No. 50-1
As described in Publication No. 044 and Publication No. 50-1045, examples are shown in which an attempt was made to improve developability and processing chemical resistance using a polycondensation resin of polyhydric phenol and benzaldehyde or acetaldehyde.

In addition, as a novolak resin, Tokuko Sho 56-54621
As described in the above publication, a mixed novolac resin of phenol and cresol is known.

The most suitable support is an aluminum plate, which is widely used or which has been subjected to various surface treatments for wood affinity, water retention, mechanical abrasion, or adhesion with the photosensitive layer. First, the aluminum plate is subjected to graining as a primary surface treatment.

As the graining method, electropolishing method, brush polishing, honing method, etc. are well known. The grained aluminum plate is then anodized with sulfuric acid, phosphoric acid, etc., and then, depending on the case, sealed with silicate or hot water to create a lithographic printing plate. Becomes a support.

(Problem to be solved by the invention) By the way, the photosensitive layer of a positive photosensitive lithographic printing plate usually contains 0-quinonediazide sulfonic acid ester as a photosensitive component and a relatively low molecular weight novolak resin as a binder. As a result, the film strength of the photosensitive layer in the image area was weak and the printing durability was inferior compared to negative photosensitive lithographic printing plates.

In particular, in UV printing that uses tJV ink (ink containing ultraviolet absorber), these weaknesses in chemical resistance are further magnified and become apparent, causing problems such as poor printing durability. There was.

A commonly used method for improving printing durability is to heat-treat at a high temperature after exposure and development. (Hereinafter referred to as the "burning process.") However, when the burning process is performed, background stains occur during printing due to the 7-mer component of the resin being attached to the non-image areas from the photosensitive layer in the image area during heating. The problem is that it's easy.

Therefore, the purpose of the present invention is to have extremely good chemical resistance, do not require burning treatment (can also be printed with UV ink,
An object of the present invention is to provide a positive type photosensitive lithographic printing plate having excellent printing durability.

In addition, higher sensitivity is desired from the viewpoint of workability, but when the additives for improving sensitivity shown above are used in the combination system of 0-quinonediazide sulfonic acid ester and novolac resin, the sensitivity can be increased. If you add as much as you can,
It was difficult to balance the development latitude, especially over-development or poor development.

Accordingly, a further object of the present invention is to provide a positive-working photosensitive lithographic printing plate which is highly sensitive, does not cause background smudge, and has a wide development latitude.

Therefore, as a result of intensive studies, the inventors of the present invention found that using a resin (having a specific structural unit) as a binder instead of a novolac resin has extremely good chemical resistance, and it is possible to print with UV ink without burning treatment. I found that.

Surprisingly, the inventors have also discovered that by combining a resin having a specific structural unit with an acid anhydride, sensitivity can be increased without any loss in development latitude, and the present invention has been achieved.

[Means for solving problems]

That is, to summarize the present invention, the present invention relates to a positive photosensitive lithographic printing plate, in which the following (A), (
B) and (C) components: (A) o-naphthoquinone cyatosulfonic acid ester CB) cyclic acid anhydride (C) polymer compound (1) containing at least one structural unit of the following formulas (I) to (r7) ): (■) Knee ((:R, R2-CR, + C00-(X+T-Y-01() and R2 is a hydrogen atom, an alkyl group or a carboxylic acid group, R3 is a hydrogen atom, a halogen atom or an alkyl group, R4 is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group, and X is a nitrogen atom or an oxygen atom and an aromatic carbon atom an alkylene group that may have a substituent that connects them, n is O to 10, Y represents a phenylene group that may have a substituent, or a naphthylene group that may have a substituent) It is characterized by having a photosensitive layer containing.

The present invention will be explained in detail below.

The 0-naphthoquinone cyacytosulfonic acid ester used in (A) of the present invention is an ester compound of a polycondensation resin of phenols, ketones or aldehydes, and 0-naphthoquinonecyacytosulfonic acid.

As the phenol, phenol, cresol, catechol, (methyl)resorcin, hydroquinone, pyrogallol, phloroglucin, etc. are preferably used. Further, more preferred is pyrogallol. As the ketone or aldehyde, acetone, formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde, etc. are preferably used, and acetone is more preferable.

Generally known methods are applied to synthesize the FF111 resin of phenols and ketones or aldehydes.
Phenols are dissolved in ketones or aldehydes, or if necessary in a suitable solvent, and polycondensation is caused in the presence of a suitable acid such as hydrochloric acid, phosphorus oxychloride, oxalic acid, etc. to obtain a polycondensate. As for the polycondensation conditions, a synthesis method in which a polycondensation reaction is carried out at a high temperature from the initial stage of polymerization is preferably used compared to known methods. For example, a catalyst such as hydrochloric acid, M, oxalic acid, or phosphorous oxychloride is mixed with a phenol and a ketone or aldehyde compound, and an optional solvent 1, such as dioxane, methanol, ethanol, tetrahydrofuran, or water. Preferably, a formulation is used which brings the solution to a steady state of reflux at the same time as it is added dropwise.

The molecular weight of the above-mentioned phenolic polymer compound obtained by these methods is determined by gel permeation chromatography (hereinafter abbreviated as GPC) (polystyrene standard) number average molecular weight Mn is 3.00XIO" to 2.0OXIO"
3. Weight average molecular weight Mw is 5.0OXIO2 to 4.0
OxlO' is used, more preferably Mn is 4.0O
x102~1.50x 10', Mw or 7.0Ox1
02-3.00x l O', more preferably Mn5
．． 0OxlO' ~ 1.10xlO: l, Mw is 8.0
0xlO” to 2.OOx 103.

A preferred example of a polycondensate of phenols that satisfies both appropriate developability and processing chemical resistance is the above molecule R.
They are resorcin benzaldehyde resin, methylresorcin benzaldehyde, and pyrogallol acetone resin in group a, more preferably pyrogallol acetone resin.

O-naphthoquinone cyatosulfonic acid esters of polycondensates of these phenols can be obtained by the following synthesis method.

It is synthesized by dissolving a polycondensate of phenols in a suitable solvent such as dioxane, adding 0-naphthoquinone cyatosulfonyl chlorite thereto, and adding Ra alkali dropwise to the equivalence point for esterification.

OH,l of this esterified product. - The actual condensation rate of naphthoquinone diacid sulfonyl chlorite (% based on one OH group) is preferably 10 to 50%, more preferably 10 to 40%, and even more preferably 15 to 35%.
It is. If it exceeds 50x, the erasability will be poor regardless of the molecular weight, and if it is less than 10%, it will likely result in over-developability or poor image area loss.

The molecular weight of this esterified product may vary slightly depending on the condensation rate of OH groups, but in general, for esterified products with an actual condensation rate of OH groups of 10 mol% to 50 mol%, Mn is 5.0
OxlO" ~ 3.60x10' and Mw is 7.OOx
10" to 5.80x10:l is preferable, more preferably Mn is 6.00x102 to 2.40xlO'3,
Mw is 9.00xlO" to 4.0xlO3. More preferably Mn is 7.0xlO2 to 2.10x10
Mw is 1. OOx 103~3.60x10'.

Mn is greater than 3.60xlO" and MW is 5.80
When an 0-naphthoquinone cyacytosulfone ester of a polycondensate of phenols with a size larger than xlO'' is used, the under-developability becomes poor, background smear tends to occur, and erasability becomes poor.

On the other hand, Mn is smaller than 5.0OxlO2 and Mw is 7
．． 0 of polycondensates of phenols smaller than 00x102
- When naphthoquinone siacitosulfone ester is used, over-developability becomes poor, leading to disappearance of the image area, and the processing chemical resistance of the image area tends to deteriorate, which is not preferable.

The content of this esterified product in the photosensitive layer varies depending on the type thereof, but is generally preferably 5 to 40% by weight, more preferably 10 to 30% by weight.

Examples of the cyclic acid anhydride used in (B) of the present invention include glutaric anhydride, tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, 3,6-nindooxy-△4-tetrahydrophthalic anhydride, and tetrachloroanhydride. Examples include phthalic acid, maleic anhydride, chloromaleic anhydride, and pyromellitic acid. The amount of these cyclic acid anhydrides added is 1 to 20% by weight of O in the total composition, preferably 0.
It is 2 to 10% by weight. If the amount is less than 0.1% by weight, the effect will hardly be recognized, and if it is more than 20% by weight, it will adversely affect the development acceptability.

The polymer compound used in (C) of the present invention is characterized in that it has at least one of the structural units represented by the following general formulas (1) to (IV) in its molecular structure, and A homopolymer type having a repeating structure of the structural unit, or a combination of the structural unit and one or more structural units having a structure in which the unsaturated double bonds of other vinyl monomers are cleaved. It has a copolymer-type structure with a repeating structure.

(1) Knee (CRIR2-CR:I+ C0NR4-(-X), -Y-OH (n) Knee+CR1R2-CR:l+ COO-(X)--Y -OH (■) Knee ecRIR2-CR) Masuden -0H (■): OH (In the formula, R1 and R2 are one hydrogen atom, an alkyl group or a carboxylic acid group, R3 is a hydrogen atom,)\Rogen atom or an alkyl group, R4 is a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group group; Represents a naphthylene group which may have a substituent. ) In the polymer compound (C) of the present invention, the above (I) to (I
V) In combination with the structural unit shown in 1. The following monomers can be cited as representative examples of structural units that can be used.

■ →CRIR2-CR:+h N ■ +(:R+Rz-(:Rz+ Coo(X), -0H (tsu -(-(:RLR2-(:R:++f(:RL
R, -(:RUTE -(CR1R2-CHR:I+) R3 is a hydrogen atom, a 710gen atom or an alkyl group, R4 is a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group; n is an optionally substituted alkylene group, n is O-10, Z is a phenyl group or a naphthyl group which may have a substituent) Among the above monomers, the monomers shown in ■ to ■ are particularly preferably used. It will be done.

More preferred are methyl methacrylate, acrylonitrile, methacrylic acid, ethyl acrylate, and 2-hydroxyethyl methacrylate, and more preferred are methyl methacrylate, acrylonitrile, and ethyl acrylate.

Typical specific examples of the polymer compound (C) of the present invention will be given below. In the following exemplified compounds, Mw is the weight average molecular weight, Mn is the number average molecular weight, and s and k are the weight average molecular weight.

1, m, and n represent the mole percent of the respective structural units.

(Hereafter, blank space) C) Iyu CH3 (Mw-3300
0,My/Mn=3.1H CRyu C)l:l (M
Snoring 3:10 (10, motor/condylar F O (:Hz (M
w=4Q口00, Mw/'tn=:l-5(Mw=
:15000, Mw/Mn-7,9n:n:l:to:5-20:15:30:33:2)H3 old m:n:1-30:30:40 H3 H3 6Hm:n:I- (0:35:35) The composition of the present invention may contain a known alkali-soluble polymer compound. Novolak resins such as phenol formaldehyde resins, cresol formaldehyde resins, phenol-modified xylene resins, etc. may be mentioned, and such alkali-soluble polymeric compounds are used in an amount of 70% by weight or less of the total composition.

When the present invention is supplied as a positive-working photosensitive lithographic printing plate, an exposure visible image imparting agent and a dye are generally added. As the exposure visible image imparting agent, a substance that generates an acid upon exposure to light is generally used, and as the dye, a compound that forms a salt with this acid is generally used.

As a compound that generates an acid upon exposure to light, the following general formula 1 is used.
Or, a trihaloalkyl compound or a diazonium salt shown in (1) is preferably used.

(X a is a trihaloalkyl group having 1 to 3 carbon atoms,
W is N, S, Se, P, Z is O, N, S, Se, P, Y
represents a group having a chromophore group and consisting of a group of nonmetallic atoms necessary to cyclize W and Z; A r -N2X
=-...EI (Ar is an aryl group, X is a counter ion of an inorganic compound) Specifically, for example, the trihaloalkyl compound of formula I is a compound represented by the following general formulas 1, 2, or 2. or included.

! Xa (wherein, Xa is a trihaloalkyl group having 1 to 3 carbon atoms, B is hydrogen or a methyl group, A is a substituted aromatic or unsubstituted aryl group or a heterocyclic group, and n is 0, 1 or 2
) Specific example compounds include oxadiazole compounds having a benzofuran ring such as ○ for the general formula (■);
2-trichloromethyl-5-(p-methoxystyryl)-1, which is described in JP-A-54-74728,
Examples include 3,4-oxadiazole compounds.

In addition, as compounds of general formulas ① and ②, JP-A-53-3
4-(2,4-dimethoxy-4-styryl)-6-dolichloromethyl-2-pyrone compound, 2,4-bis-(trichloromethyl)-6 described in Publication No. 6223
-p-methoxystyryl-3-)-riazine compound, 2
, 4-bis-(trichloromethyl)-6-p-dimethylaminostyryl-5-)-lyazine compounds, and the like.

On the other hand, the diazonium salt compound is preferably a diazonium salt that generates a strong Lewis acid upon exposure to light, and the counter ion moiety is preferably a counter ion of an inorganic compound. Specific examples include aromatic diazonium salts that are the anion portion of diazonium salts or at least one of phosphorous fluoride ions, arsenic fluoride ions, antimony fluoride ions, antimony chloride ions, tin chloride ions, bismuth chloride ions, and zinc chloride ions. Preferably, it is a diazophenylamine salt.

The amount of the exposure visible image imparting agent contained in the total photosensitive layer composition is 0.01 to 20% by weight, preferably 0.1 to 20% by weight, and more preferably 0.2 to 10% by weight.

When these compounds having a trihaloalkyl group are added to the photosensitive layer, the change in erasability due to the change in the molecular weight of the polyhydroxy resin becomes more pronounced than when the compound is not added, which is interesting. However, the causal relationship is not clear.

On the other hand, as the dye, any generally known compound that forms a salt with an acid can be used, such as triphenylmethane dyes, cyanine dyes, diazo dyes, styryl dyes, and the like. Specifically, Victoria Pure Flu BO) (Ethyl Violet, Crystal Violet, Brilliant Clean, Paysic Tsukushin, Eosin, Phenolphthalein, Xylenol Blue, Congo Red, Malachite Green, Oil Flu #603, Oil Pink #312, Examples include cresol red, auramine, 4-p-diethylaminophenylimino naphthoquinone, leucomalachite green, leuco crystal violet, etc. The amount of this dye added is preferably about 0.01 to 10% by weight based on the total composition of the photosensitive layer. , more preferably 0.05 to 8% by weight.

Various other additives may be added to the photosensitive layer composition of the positive-working photosensitive lithographic printing plate of the present invention depending on various purposes. For example, to improve coating properties, surfactants such as cellulose alkyl ethers, fluorine surfactants, and silicone compounds are used, and phosphate esters, phthalate esters, polyvinyl butyl ether, etc. are used as physical property improvers of the coating film. Plasticizers, etc., and various additives having hydrophobic groups, such as p-octylphenol formalin novolak resin, p-t-butylphenol formalin novolak resin, p-t- Modified novolak resins such as butylphenol benzaldehyde resin and rosin-modified novolak resin are used, and 0-naphthoquinone cyasitosulfonic acid esters (esterification rate of OH groups: 20 to 70 mol%) of these modified novolac resins are added. be able to. The content of these additives varies depending on their type and purpose, but the amount added is generally from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, based on the total composition of the photosensitive layer. The photosensitive layer of the photosensitive lithographic printing plate of the present invention generally has a solid content of 0.5 to 0.0, although it varies depending on the use.
3.0g/m2 or moderate.

The photosensitive layer composition is a coating material dissolved in various solvents, such as cellosolves such as methyl (ethyl) cellosolve and methyl (ethyl) cellosolve acetate, coating solvents such as dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, and trichloroethylene. It is formed by coating and drying it on a grained and anodized aluminum plate support as described below.

When using the positive-working photosensitive lithographic printing plate thus obtained, a known method is applied, in which a positive-working film is adhered and exposed with an ultra-high pressure mercury lamp, metal halide lamp, etc.
It is developed with an alkaline aqueous solution of sodium metasilicate, potassium metasilicate, phosphorous soda, caustic soda, etc., and then supplied as a printing plate. Burning treatment is also applied if necessary. The lithographic printing plates produced in this way are sheet-fed,
Used for off-wheel printing presses.

The support provided with the photosensitive layer using the photosensitive composition of the present invention is an aluminum plate. When an aluminum plate is used as a support, it is preferably subjected to surface treatments such as graining, anodizing, and, if necessary, sealing. Known methods can be applied to these treatments.

Examples of the method for grain molding include a mechanical method and an electrolytic etching method. Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a puff polishing method.

The various methods described above can be used alone or in combination depending on the composition of the aluminum material. Preferred is electrolytic etching.

Electrolytic etching uses phosphoric acid! It is carried out in a bath containing one or a mixture of two or more inorganic acids, such as &ugly, salty, salty, and salty acids. After the sand grain treatment, if necessary, a desmut treatment is performed using an aqueous alkali or acid solution to neutralize the material, followed by washing with water.

The anodic oxidation treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The amount of anodic oxide film formed was 1 to 50 mg/
d m2 is suitable, preferably 10-40 m
g/d m2. Anodized skin 1BLTk is
For example, an aluminum plate is immersed in a phosphoric acid chromic acid solution (phosphoric acid 85% solution: 35 m), chromium oxide (prepared by dissolving 1:20 g in 1 l of water) to dissolve the oxide film, and the film on the plate is dissolved. It is determined by measuring changes in weight before and after.

Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

First, a synthesis example of the photoreceptor and binder used in the present invention will be described.

(Synthesis of photoreceptor) Synthesis Example 1> After putting 3 heads in a pyrogallo router bath and blowing in nitrogen gas to perform nitrogen substitution, phosphorus oxychloride 5
g was added to carry out a polycondensation reaction.

After keeping the reaction temperature at 20'C and allowing it to react overnight, 15% of water was added.
+Q while stirring vigorously to precipitate the formed polycondensate.

The precipitated resin is collected by filtration and washed with water until the pH becomes approximately neutral (7). The filtered material is dried at 40°C or less. In this way, 50 g of light brown resin was obtained.

The molecular weight of this resin was determined by GPC (Hitachi model 635, column
Shodex A 8 0 4, A8
03, A302 in series) with polystyrene as the standard. Mn and Mw were calculated by the method described by Tsuge et al., Journal of the Chemical Society of Japan, 1972 (April issue), page SOO, by smoothing out the peaks of the desired oligomer region (connecting the centers of the peaks and valleys). went. As a result, Mn is 2.
OOXIO”, Mw was 3.40×10”.

Next, 60 g of this resin was dissolved in 720 ml of dioxane, 70 g of 1,2-naphthoquinone cyato-5-sulfonyl chloride was added, and after dissolving, an aqueous potassium carbonate solution (13
After dropping 60 g of the mixture (% by weight) and carrying out the linear combination reaction at 40 to 50°C for about 1 hour, the reaction solution was poured into a large amount of dilute hydrochloric acid water (salt f4 13 m, water 3! l). The precipitated resin was filtered and dried. A yellow powder resin containing 56 g of 1,2-naphthoquinone cyato-5-sulfonic acid ester of pyrogallol acetone resin was obtained. As a result of analysis, OH
The condensation rate of the groups was 20%. When the molecular weight of the ester was measured in the same manner as the polyhydroxy resin, Mn was 2.
30xlO'', Mw was 3.03x10''''.

<Synthesis Example 2> 43.6 g of resorcin and 130 g of methanol were put into a three-headed colben set in a water bath, and after dissolving the resorcin, 39 g of benzaldehyde was added, and then 0.25 m of hydrochloric acid was added, and about 10 Heating is controlled so that methanol is refluxed. Approximately 2 hours after the start of reflux, the reaction mixture is dropped into approximately 2 volumes of water, filtered, washed with water, and dried to room temperature. Light brown powdered resin 5
6g was obtained. Molecule m by GPC in the same manner as Synthesis Example 1
As a result of Rill determination, Mn is 7.80x10,
Mw was 1.32XLO'''.

Next, 66 g of this resin was dissolved in 720 mi of dioxane, 90 g of 0-naphthoquinone cyato-5-sulfonyl chloride was added, and after dissolving, 213 g of an aqueous potassium carbonate solution (13% by weight) was added dropwise, and the mixture was heated at 40 to 50°C to approx. After reacting for 1 hour, it was poured into a large amount of diluted hydrochloric acid in the same manner as in Synthesis Example 1.
It was collected by filtration to obtain 132 g of 0-naphthoquinone cyasitosulfonic acid ester of resorcinol benzaldehyde resin. As a result of analysis, the condensation rate of OH groups was 23%.

As a result of molecular weight measurement by GPC, Mn is 1.55xlO
3.Mw was 1.78×10 pieces.

(Synthesis of Binter) <Synthesis Example 1> [Mix 400 g of col-hydroxyaniline corresponding to (b) above, 4 g of hydroquinone monomethyl ether, 4 g of acetone and 360 g of pyridine,
It was cooled from the outside using a cryogen, and when the internal temperature had fallen to -10°C, 420 g of methacrylic acid chloride was added dropwise with stirring. Adjust the dropping temperature so that the reaction temperature is below O'C, and after the completion of 'a', stir at O~3°C for about 2 hours. Then, after stirring at 25°C for 2 hours, the reaction solution was reduced to 1/3 Add 10 g of dilute hydrochloric acid (pH approx. 1.0) until the
The resulting precipitate was suction filtered to obtain a white solid. Dissolve this white solid in two methanol mixtures while heating.
Further, two portions of a 5% aqueous sodium carbonate solution were added, and the mixture was stirred at 40°C for 30 minutes. This dark red solution was then poured into 8 volumes of 5% aqueous hydrochloric acid to form a large amount of precipitate, which was filtered with suction and dried to obtain a pale pink solid. This was recrystallized from a mixed solvent of ethanol and water with a melting point of 155-1
450 g of colorless needle-like crystals of p-hydroxymethacrylanilide were obtained at 56°C.

53.2 g of P-hydroxymethacrylanilide (HyPMA) obtained above, acrylonitrile (AN)
15.9g, methyl methacrylate (MMA) 40.0
g and α・α′-azobisisobutyronitrile 0.8
2g in acetone:ethanol (1:2) mixed solvent 1
A polymer solution was obtained by dissolving the solution in 90 ml of nitrogen gas and heating at 65°C. This polymer solution was poured into three portions of a 5% HC aqueous solution, and the resulting white precipitate was filtered and dried to obtain 70 g of a white polymer. When the molecular weight was measured by GPC, the Mn was 3.2 x 10" and the Mw was 2.
It was 2xlO'.

<Synthesis Example 2> [Equivalent to (e) above] Dissolve 350 g of cohydroquinone in 2.51 g of acetone and 500 g of lysine, cool from the outside using a cryogen, and when the internal temperature drops to 0°C, dissolve methacrylic acid. Chloride 3
13.5 g was added dropwise while stirring. The dropwise addition rate was controlled so that the reaction temperature was 0 to 5°C, and after the completion of the dropwise addition, the mixture was stirred at the same temperature for 3 hours, and then stirred for an additional 1 hour at room temperature, after which acetone was distilled off from the reaction solution under reduced pressure. After adding water to this residue, acidifying it with hydrochloric acid (pH about 4), extracting with ether, separating the ether layer, washing it with 5% aqueous sodium bicarbonate solution, water, and anhydrous sodium sulfate. After drying for a day and night, the ether was distilled off to obtain a white solid. This was recrystallized from water to give 423 g of colorless needle-like crystals of hydroquinone monomethacrylate with a melting point of 120.5 to 121.5°C.
I got it.

36 g of this hydroquinone monomethacrylate, 1 g of acrylonitrile, 60 g of methyl methacrylate,
1.64 g of α・α′-azobisisobutyronitrile was added to 600 mL of a mixed solvent of acetone/methanol (l:1).
A polymer solution was obtained by dissolving the polymer in 1 ml of nitrogen gas and heating at 65° C. for 30 hours. This was poured into 5 fL of water, the white precipitate formed was filtered and dried, and the polymer 5
Obtained 0g. The weight average molecular weight of this polymer measured by GPC method was about 40,000.

(The following is a blank space) <Synthesis Example 3> [Equivalent to (k) above] 40.0 g of col-hydroxystyrene, 20.0 g of acrylonitrile, 40 g of styrene, and 1 g of α・α′-azobisisobutyronitrile were mixed with acetone:ethanol (1
A polymer solution was obtained by dissolving in 600 ml of the mixed solvent of :l), purging with nitrogen gas, and heating at 68° C. for 10 hours. This was poured into 5 cups of water, and the resulting white precipitate was filtered and dried to obtain 70 g of a polymer. The weight average molecular weight of this polymer measured by GPC method was 47,000.

Synthesis Example 4> [The Japanese name for (i) is copolyvinyl alcohol (Nippon Gosei Kagaku Co., Ltd. NL-05=
Disperse 22 g of viscosity 4.6 to 6 CPS, degree of saponification 98.5%) in 300 ml of glacial acetic acid, and add 38 g of vanillin and p-
After adding 38 g of methylbenzaldehyde, 20% H
2SO-25m was added and reacted at 50°C for 3 hours. After cooling, it was dropped into water to obtain 40 g of polymer.

<Comparative Synthesis Example 1> The p-hydroxymethacrylanilide of Synthesis Example 1 was converted into 2-
It was synthesized in the same manner except that hydroxyethyl methacrylate was used instead. When the molecular weight was measured by GPC, the Mn was 2.3xlO, and the Mw was 1.5xlO'.

<Comparative Synthesis Example 2> 90 g of m-cresol, 56 g of p-cresol, 54 g of phenol, 105 g of 37% formaldehyde aqueous solution,
Then, 2.5 g of oxalic acid was put into a three-headed kolben set in an oil bath, and the temperature was raised while stirring. It foams violently at around 90℃, cools down temporarily, and then rises again to bring the internal temperature to 1.
After reacting for about 3 hours at 05°C, the temperature was further raised to 175°C and water was distilled off.

After 2 hours, the temperature was raised to 200° C., and the pressure was reduced to 100 mmHg to distill off the residual sludge. After 10 minutes, the reaction was stopped, and the reaction product was poured into Teflon and solidified. The molecular weight of this resin was measured by GPC using polystyrene as a standard.

Calculation of Mn and Mw was performed as described above. As a result, Mn
was 1350, and Mw was 6750.

(Example 1) An aluminum plate with a thickness of 0.24 °C and 1 m was degreased in a 5% aqueous sodium hydroxide solution, and then heated in a 0.3 molar nitric acid aqueous solution at a temperature of 30 °C and a current density of 50 A/dm. ”
An electrolytic etching treatment was performed under conditions of treatment time: 30 seconds. Next, a desmut treatment was performed with a 5% aqueous sodium hydroxide solution, and then an anodization treatment was performed in a sulfuric acid solution. When the amount of anodic oxide film was measured using the method described above, it was found to be 2.
It was 0 mg/dm2. Next, it was immersed in a hot aqueous solution at 90°C for pore sealing treatment.

Subsequently, a photosensitive coating solution having the following composition was applied to the aluminum support using a spin coating machine, and dried at 100°C for 4 minutes to form a photosensitive lithographic printing plate with a film thickness of 24 mg/dm2. Obtained.

<Photosensitive liquid 1-2. Comparative photosensitive liquids 1 to 4> The obtained photosensitive lithographic printing plate was heated in a 3KW ultra-high pressure mercury lamp 6
The plate was exposed for 30 seconds from a distance of 0 cm, and then developed for 145 seconds at 25°C using a 7-fold dilution of the positive developer for PS plates "5DP-1" (manufactured by Konishiroku Photo Industries Co., Ltd.). .

Table 1 shows the sensitivity, chemical resistance, and development latitude of the lithographic printing plate obtained.

(The following is a blank space) *Chemical resistance After immersion in each chemical, visually judge the degree of discoloration in the printed area (out of 10 points) From Table 1, the printing plate of the present invention has extremely good chemical resistance (including UV ink suitability). It can be seen that it has high sensitivity and excellent development latitude.

Further, using the developed printing plates of Example 1 and Comparative Example 3, printing with UV-ink and printing with oil-based ink were performed under the following printing conditions.

(Printing conditions using UV ink) Printing machine: Huff Duster CDX-900 Printing ink:
Toyo Flash Try-0L-Red Ap (manufactured by Toyo Ink Co., Ltd.) Register user: Toyo Flash Dry Reducer o
p (manufactured by Toyo Ink Co., Ltd.) Plate cleaner: Toyo Flash Dry Plate Cleaner (manufactured by Toyo Ink Co., Ltd.) Paper: High-quality paper Printing speed: 7000 sheets/hour (printing conditions with oil-based ink) Printing a: Heidel GTO Printing ink: Toyo King New Prite Beni (manufactured by Toyo Ink Co., Ltd.) Paper: High quality paper Printing speed: 500 sheets/hour The printing plate of Comparative Example 3 disappeared soon after being imprinted, whereas the printing plate of Example 1 printed 40,000 copies. However, good prints were obtained.

(Comparative Example 5) The binder of Example 1 was changed from Synthesis Example 1 to Comparative Synthesis Example 2, that is, the 2-hydroxymethacrylanilite (HyPMA) unit of the monomer was changed to a 2-hydroxyethylmethacrylate unit, A photosensitive lithographic printing plate was obtained with the same composition as in Example 1 except for the above. It can be seen that either exposure and development were performed in the same manner as in Example 1, or that no development was possible at all, indicating that the phenolic hydroxyl group is essential.

(Example 3, 4.5) After degreasing an aluminum plate with a thickness of 0.24 mm in a 5% aqueous sodium hydroxide solution, it was degreased in a 0.3 molar nitric acid aqueous solution at a temperature of 30°C and a current density of: 50A/dm2. Electrolytic etching treatment was performed under conditions of treatment time = 30 seconds. Next, a desmut treatment was performed in a 5% aqueous sodium hydroxide solution, and then an anodization treatment was performed in a phosphoric acid solution.

When the amount of anodic oxide film was measured using the method described above, it was found that 20m
g/d m''.Next, it was immersed in a hot aqueous solution at 90°C for pore sealing treatment.

Subsequently, a photosensitive coating solution having the following composition was applied to the aluminum support using a spin coating machine, and dried at 100°C for 4 minutes to form a photosensitive lithographic printing plate with a film thickness of 24 mg/dm''. Obtained.

<Photosensitive liquid 3.4> A printing plate obtained by exposure and development in the same manner as in Example 1 was exposed and developed under the same conditions as in Example 1, and after every 500 sheets, it was washed with Toyo Flash Dry Plate Cleaner (manufactured by Toyo Ink Co., Ltd.). After printing 10,000 copies, we were able to obtain good quality prints.

(Effects of the Invention) As explained in detail above, the photosensitive lithographic printing plate of the present invention has improved chemical resistance, can be printed with UV ink even without burning treatment, has high sensitivity, and has high development latitude. It has a spacious and calming effect.

Claims (2)

[Claims] (1) The following (A), (B) and (C) components are placed on a support made of anodized aluminum material: (A) o-naphthoquinonediazide sulfonic acid ester (B) cyclic acid anhydride (C) Polymer compound containing at least one structural unit of the following formulas (I) to (IV) (I): ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (II): ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups or carboxylic acid groups, R_3 is hydrogen atom, halogen atom or alkyl group, R_4 is a hydrogen atom, alkyl group, phenyl group or aralkyl group, X is a nitrogen atom or an alkylene group which may have a substituent connecting the oxygen atom and the aromatic carbon atom, n is 0 to 10, Y represents a phenylene group which may have a substituent, or a naphthylene group which may have a substituent.) Lithographic printing plate. (2) In the polymer compound of (C) above, (I) to
The photosensitive lithographic printing plate according to claim 1, wherein the structural units used in combination with the structural unit represented by (IV) are the following [1] to [13]. [1]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [2]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [3]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [4]▲There are mathematical formulas, chemical formulas, tables, etc. Yes▼ [5]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [6]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [7]-(CR_1R_2-CHR_3)- [8]▲There are mathematical formulas, chemical formulas, tables, etc. ▼ [9] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [10] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [11] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [12] ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼ [13] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups, or carboxylic acid groups, R_3 is hydrogen atoms, halogen atoms, or alkyl groups, R_4 is hydrogen atoms, an alkyl group, a phenyl group or an aralkyl group; phenyl group or naphthyl group which may have