JPS62157055A - Original plate for printing - Google Patents

Abstract

PURPOSE:To obtain an original plate for printing having high moisture resistance by specifying the monomer components for forming a high-polymer compd. in a photoconductor layer of the original plate for printing per the weight of the photoconductor layer. CONSTITUTION:The monomer components for forming the high-polymer compd. in the photoconductor layer of the original plate for printing is specified to <=4.0wt% per the weight of the photoconductor layer. The original plate for printing is formed by a method for using the high-polymer compd. from which the remaining monomer for forming the high-polymer compd. is removed by refining as a binder for forming the photoconductor layer or removing the monomer for forming the high-polymer compd. by heating after coating the photoconductor layer on a base or making combination use thereof. The high-polymer compd. (resin) for the photoconductor layer which can be used includes a styrene/maleic anhydride resin, etc., and the photoconductive material includes a hydrazone compd., anthracene compd., etc., which may be used alone or in combination of >=2 kinds. The mixing ratio by weight of the resin and the photoconductive material in the photoconductor layer is adequately in a 1:1-10:1 range and the coating solvent for the photoconductor layer is not particularly limited as far as the solvent can dissolve the resin contained in the coating compsn.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention uses a photoconductive substance, and after forming a toner image by electrophotography, the photoconductive layer in the non-image area is treated with an alkaline substance/or alcohol. This invention relates to the improvement of a printing original plate that is made into a printing plate through a plate-making process in which the main component is removed using a solution.

[Conventional technology]

Many printing original plates of the type in which the photoconductor layer in non-image areas is removed after toner image formation are already known.

For example, Special Publication No. 37-17162, No. 38-6961
No. 38-7758, Japanese Unexamined Patent Publication No. 50-19509,
No. 50-19510, No. 52-2437, No. 54-
No. 134632, No. 54-145538, No. 55-1
No. 05254, No. 55-153948, No. 55-16
No. 1250, No. 56-146145, No. 56-190
No. 63, No. 56-29250, No. 57-161863
Examples include printing original plates described in No. 58-76843, No. 58-76844, No. 59-125751, and No. 59476756.

However, these printing original plates have the following drawbacks in common. In other words, it has poor resistance to humidity;
If a printing original plate is stored in a relatively high-humidity atmosphere with a relative humidity of about 80% or more, the charge acceptance and sensitivity will be lowered, and a normal image will not be obtained.

Further, even if a printing original plate is stored in a relatively dry atmosphere, a normal image cannot be obtained if plate making is performed in an atmosphere with relatively high humidity of about 80% or more.

As a result of intensive research with the main purpose of improving the moisture resistance of printing original plates, the present inventors have determined that the amount of monomer components for forming a polymer compound remaining in the photoconductor layer is related to the amount of monomer components remaining in the photoconductor layer. Is the resistance significantly improved by reducing the OiR amount to 4% or less based on the total weight of the conductor layer? It was discovered that the J properties were improved, leading to the present invention.

[Purpose of the invention]

An object of the present invention is to provide an indicia 1611 with improved moisture resistance.
The purpose is to provide the original version.

[Structure of the invention]

An object of the present invention is to provide a printing original plate in which a photoconductor layer is formed on a conductive support, and after forming a toner image, the photoconductor layer in the non-image area is removed to create a printing plate. This is achieved by a printing original plate characterized in that the monomer component for forming a polymer compound in the photoconductor layer of the printing original plate is 4.0 weight (11% or less) based on the amount of the photoconductor layer.

In order to prepare a printing plate according to the present invention, a polymer compound from which the remaining component (Motsumar for forming a hill compound) has been removed by purification is used as a binder for forming a photoconductor layer, or a support material - a polymer compound is used as a binder for forming a photoconductor layer. After coating a photoconductor layer, the monomer for forming a polymer compound is removed by heating, or the above method is used in combination.

In the present invention, the monomer for forming a polymer compound refers to a monomer for forming a polymer compound used as a binder for a photoconductor layer, which is described in the publications and publications listed in the prior art section. Typical examples include 1.1h CONHC21 (4011C00C2H401).

Examples of the photoconductor layer polymer compound (resin) that can be used in the present invention include JP-A-54-134632 and JP-A-55-105.
; No. 54, No. 55-153948, No. 55-161
250, 56-1!063, etc., styrene-anhydrous described in JP-A-37-171f2, 3g-6961, JP-A-50-19509, JP-A-50-1950, etc. Maleic acid resin, vinyl acetate-crotonic acid copolymer, vinyl acetate-maleinoic anhydride copolymer resin, JP-A-57-161863, JP-A-58-768
There are alkali-soluble resins such as acrylic acid resins described in No. 43 and No. 58-7H44.

Examples of photoconductive materials that can be used in the photoconductor layer of the present invention include JP-A-57-100435 and JP-A-57-100436.
No. 57-102635, No. 57-102637, No. 57-102638.

No. 57-102639, No. 57-138644, No. 57-138645, No. 57-138646, No. 5
hydrazone compounds described in JP-A-57-102641, JP-A-57-102659, JP-A-57-102660, JP-A-57-1022861, JP-A-57-101846, etc.;
Divinylbenzene compounds described in JP-A-57-102651, JP-A-54-104703, etc., JP-A-57-10
No. 2627, No. 57-102652, No. 57-102
Fluorenone compounds described in JP-A No. 653, JP-A No. 56-22437, etc., JP-A-57-102642, JP-A No. 57-10
No. 2643, 1 Diarylmethane compound described in No. 57-102650 etc., JP-A-57-124353
trisazo pigments described in Japanese Patent Publications No. 37-17162, Japanese Patent Publications No. 38-6961, Japanese Patent Publications No. 16125-1988, etc.; Pyrazolone compounds described in No. 56-80051 etc., JP-A No. 56-29586
pyrylium compounds, carbazole compounds and zinc oxide described in JP-A-47-30330, JP-A-56-5552, etc.; -30331, etc., bisbenzimidazole pigments described in JP-A-47-18543, etc., JP-A-47-18543, etc.
-18544, 55-98754, 55-12
Aromatic polyfused ring compounds described in Japanese Patent Publication No. 6254, No. 55-163543, etc., Japanese Patent Publication No. 44-16474, No. 48-
Azo pigments described in JP-A No. 30513, JP-A-56-321465, etc., JP-A-50-7434, JP-A-47-37
No. 5443, No. 55-11715, No. 56-1944
No. 56-9752, No. 56-2352, No. 56
-Disazo pigment described in No. 80050, etc., 1977-
No. 12671, No. 40-2780, No. 52-1667
No. 46-30035, No. 49-17535, JP-A No. 49-11136, No. 49-99142, No. 5
There are phthalocyanine pigments described in No. 1-109841, No. 57-2, No. 18745, etc., and these can be used alone or in combination of two or more.

Furthermore, in the present invention, a sensitizer can be used in combination for the purpose of adjusting the sensitivity or the sensitive wavelength range. Examples of these sensitizers include JP-A-47-30330, JP-A-47-30331, and JP-A-47-30331.
Electron-donating substances described in JP-A-47-30330 and JP-A No. 55-15
Electron-accepting substances described in No. 3948, etc.; xanthine dyes such as rose bengal, niosin S, fluorescein, and phloxine; phenolsulfocrein dyes such as bromophenol blue, bromcresol purple, and chlorophenol red; Alma azurin 2G , Pontan Lubrilliant Blue FCF, Acid Violet 6B, and other triphenylmethane dyes; Auramine and other diphenylmethane dyes; Acridine Yellow,
There are various dyes such as acridine dyes such as acrisin orange, and rhodamine dyes such as sulforhodamine B and acidion G. Among these, organic carboxylic acids such as benzoic acid, phthalic acid, maleic acid, fumaric acid, etc. Particularly preferred are their anhydrides.

The weight ratio of the resin to the photoconductive substance in the photoconductor layer of the present invention is suitably in the range of 1.1 to 10:1, and the coating solvent for the photoconductor layer is not contained in the coating composition. There is no particular restriction as long as it dissolves the resin to be used, such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as chlorohexanone; glycol ethers such as ethylene glycol monomethyl ether and 2-methyne ethyl acetate; esters such as butyl acetate and ethyl acetate; dioxane, trimethylformamide, etc. can be used.

Next, the support used in the printing original plate of the present invention is as follows:
Aluminum plate, zinc plate, iron plate with surface treatment such as chrome plating, or bimetallic temporary such as copper-aluminum plate, copper-stainless steel plate, chrome-copper plate, or chrome-copper-aluminum plate, chrome-lead-ei, chrome - A conductive substrate having a hydrophilic surface such as a tri-metal temporary such as a copper-stainless steel plate, a paper containing a conductive agent, or a three-layer plate in which a resin layer is sandwiched between metal plates such as aluminum can be used. Particularly preferred is an aluminum layer on at least the surface, the surface of the aluminum layer is grained, and the grained surface has a center line average roughness (Ra) of 0.2 to 0. The support is in the range of 8 μm. More preferably, it has an aluminum layer on at least the surface, and after the surface of the aluminum layer is sanded,
It has a surface that has been hydrophilized (for example, anodized) and sealed, and the center line average roughness (Ra) of this surface is 0.
．． The support ranges from 2 to 0.8 μm.

The grains on the surface of the aluminum layer include electrolytic polishing in an electrolytic solution such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc., or mechanical polishing methods such as ball polishing, blank polishing, press polishing, and honing polishing. be done. In addition, in the oxide film formation treatment that follows the grain chamber, the Ti of the oxide film is
O~50mg/dm2, more preferably 20~30m
g/dm" is preferable, and an aluminum plate subjected to pore sealing treatment with hot water, silicate, phosphate, fluorosilicate, etc. is preferable.

Here, center line roughness (Ra) is German standard DIN47
As shown in Figure 68, the roughness curve [is the arithmetic average of the absolute values of the distances from the center line in the J file to each point on the profile, with the horizontal center line as the X axis, and the vertical direction as When the point on the roughness profile is expressed as (X, Y) with the Y axis as For example, it can be measured using Perthometer S 5 P manufactured by Perthen.

In the case of aluminum temporary, the entire support does not necessarily need to be aluminum, as long as the surface of the support is aluminum temporary. For example, it may be a multi-layer board such as a two-layer board such as aluminum-paper or aluminum-resin, or a three-layer board such as aluminum-paper-aluminum or aluminum-resin base-aluminum, but in these cases, the paper or resin base It is desirable that the material contains a conductive agent.

The method of applying the photosensitive liquid (coating composition for photoconductor layer) to the support, the amount of application (thickness of the photoconductor layer), etc. may be in accordance with conventional methods. Applicator coating, wire bar coating, calendar coating, poller coating, etc. may be used, and the appropriate coating amount is 2 to 10 μm in film thickness after drying.

In order to make the printing original plate according to the present invention into a printing plate, an image area and a non-image area are formed by sequentially charging, exposing, and toner adhesion, and then, for example, an alkaline liquid is used to form a photoconductive area corresponding to the non-image area. Remove body layer. For this removal, it is preferable to immerse the plate in an alkaline solution and then lightly rub the plate surface with a sponge, bran, etc. while rinsing with water. After an image area is formed by this elution, it is dried to create a printing plate.
At this time, if the non-image area is removed and then heated, the resin of the photoconductor layer in the image area will be better cured, so that the resistance can be further improved.

As the alkaline solution, a solution in which an inorganic and/or organic alkaline substance is dissolved in water and/or an organic solvent can be used.

Inorganic alkaline substances include ammonia, alkali metal and alkaline earth metal hydroxides, such as ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide, or alkali phosphates, such as sodium phosphate. 11, potassium phosphate, or silicic acid-alkali salts, such as sodium silicate and potassium silicate.

Organic basic substances include primary, secondary and tertiary substances such as trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, isobutylamine, dibutylamine, tributylamine, diisobutylamine, octylamine, diethylamine. lower saturated amines such as piperidine, N-methylbiperinone, N-ethylpiperinone, morpoline, or amyl alcohols such as ethanolamine, jetanolamine, triethanolamine, N-methylethanolamine, N-ethyljetanolamine, Alternatively, diamines and polyamines such as ethylenediamine, diezirezitriamine, triethylene-tetramine, and lower substituted amides such as dimethylformamide may be mentioned.

Water and/or organic solvents are used as solvents for dissolving and diluting these alkaline substances. Examples of the organic solvent include ethers such as dibdel ether, ethyl butyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; acetone, methyl ethyl ketone,
Lower ketones such as dipropyl ketone; lower esters such as methyl acetate, edyl acetate, butyl acetate, methyl propionate, methyl butyrate, ethyl butyrate; and methanol, ethanol, propatool, isopropanol, isobutanol, Examples include those containing an alcohol group such as ethylene glycol, polyethylene glycol, glycerin, ethylene glycol monomethyl ether/Lz, and ethylene glycol monoethyl ether.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
This does not limit the embodiments of the present invention.

(Example = ■) 2 moles of phenol, 2 moles of m-cresol, 3.2 moles of formalin, and 0 sycholic acid in 2t2 triangular colbens.
．． 1 mol was added, placed in an oil bath, heated, and refluxed for 1 hour. Furthermore, after adding 0.1 mol of hydrochloric acid and refluxing for 30 minutes, the resin-like reactant was transferred to a 2Q eggplant-shaped rice bene.
The mixture was distilled off under normal pressure for 15 minutes while heating at 00°C, and then distilled off under reduced pressure using 14 g of 2 mm while heating at 100°C for 30 minutes. This material was poured into a pallet and cooled to room temperature, and a phenol resin having the following structure was synthesized.

(Synthesized polymer) m:n=I:1 Average molecular fit 3,500 Next, after dissolving 3 parts by weight of the synthesized resin in 15 parts by weight of ethylene glycol monoethyl ether acetate, 1 part by weight of ε-type copper phthalocyanine was added. Add and add 1 with glass peas.
A dispersion liquid for forming a photoconductive band was prepared by dispersing the mixture over time. The surface of this material is electrolytically polished to an average roughness Ra) of 0.5μ.
It was applied with a wire bar to a film thickness of 25 μm on a 0.3 mm thick aluminum plate that had been grained, anodized, and sealed with hot water, and left at room temperature for 3 hours, then 60°C for 24 hours. It was dried to prepare a printing original plate of Example-1.

(Example 2) 2 moles of purified styrene and 1 mole of mechacrylic acid
mol, maleic anhydride 1 mol, azohisisobutylene [1 nitrile 0.03 mol and purified tetrahydrofuran If
f was placed in a 2Q Kolben and reacted for 8 hours at a liquid temperature of 60°C under nitrogen substitution. After the reaction was completed, the mixture was diluted 4 times with acetone, poured into large Xi1 water, and thoroughly washed with water to synthesize the resin used in Example-2.

(Synthesized polymer) 9I! 3:Q:m=I:2:1 Average molecular weight 95,000 Next, 1 weight of the polymer synthesized here; W≦ and 0.855 weight of an organic photoconductive substance having the following structural formula and rhodamine B O, A photosensitive liquid for forming a photoconductor layer was prepared by dissolving 1 part by weight of 01 parts by weight in 7 parts by weight of a mixed solution of dichloroethane:ethylene glycol monoethyl ether=t:t.

This photosensitive solution is electrolytically polished to a grain roughness (Ra) of 0.
．． The surface was grained to 62 μm, and an oxide film of 25 mg/d+n” was formed by anodic oxidation, and then the membrane was dried to 5 μm using rf on an aluminum plate with a thickness of OJ mm, which was sealed with hot water at 90°C. The original printing plate of Example 2 was prepared by coating the original plate with a polymer so as to have the following properties and placing it in a dryer set at an internal temperature of 100° C. for 30 minutes.

(Organic photoconductive substance) UshiH3 (Comparative Example-1) After the synthesis reaction of phenol resin was completed using the same materials and under the same conditions as in Example-■, unreacted monomers were removed by atmospheric distillation for 30 minutes. . However, vacuum distillation was not performed. After taking out the resin in the same manner as in Example-1, a dispersion for forming a photoconductor layer was prepared using this resin in the same manner as in Example-1, and the dispersion liquid was prepared on an aluminum plate treated in the same manner as in Example-1. The original plate for printing of Comparative Example 1 was prepared by applying the same film thickness to the same thickness and drying in the same manner.

(Comparative Example-2) After completing the synthesis reaction using monomers with the same composition as in Example-2 and under the same conditions, the solvent was distilled off at normal pressure at 120°C, and the mixture was poured into a hot pallet. A polymer with the same composition was synthesized.

Using this resin, a photosensitive solution was prepared in the same manner as in Example-2, and it was applied to an aluminum plate with the same surface treatment as in Example-2 and dried in the same manner to form a comparative example-2.
The original printing plate was created.

(Example-3) The internal temperature of the Kawahara 4th edition created in Comparative Example-1 was 100°C.
The original plate for printing of Example 3 was prepared by placing it in a dryer set at .

(Example 4) The original printing plate prepared in Comparative Example 2 was placed in a dryer set at an internal temperature of 100° C. for 1 hour to prepare the printing plate marked 11 in Example 1.

(Practical Example 5) 1 part by weight of the phenol resin synthesized in Comparative Example 1 was dissolved in 2 parts by weight of acetonate, and poured into 1 part by weight of 15 parts by weight of water with stirring. After discarding the supernatant by decantation,
Collect the resin that has accumulated on the bottom and walls, and add acetone 1 again.
After dissolving in parts by weight, it was poured into 100 parts by weight of water with stirring. Similarly, the supernatant was discarded by decantation, and the resin accumulated on the bottom and walls was collected and dried.

Hereinafter, after preparing a dispersion liquid for forming a photoconductor layer using this IJ resin in the same manner as in Example-1, actual 1j color example-1 was prepared.
Coat it on the support in the same manner as above and dry it to obtain the fruit 1.1! , an original printing plate of Example-5 was prepared.

The amount of monomer components in the photoconductor layer of the printing original plate prepared above was measured by gas chromatography, and the results are shown in Table 1 below.

Note that the values in Table 1 are weight % based on the total photoconductor layer type jet.

Table 1 Next, when these printing master plates were plate-made using an electrophotographic plate-making machine in a room at a temperature of 23°C and a relative humidity of 48%, both Examples 1 to 5 and Comparative Examples 1 to 2 were normal. A toner image is obtained, and the photoconductor layer in the non-image area can be removed using an alkaline aqueous solution in the next step (Positive Ps plate developer 5DP-1, 7 times diluted by Konishiroku Photo Industry Co., Ltd.). A printing plate with a normal image was obtained.

Next, these printing plates were heated at a temperature of 23°C and a relative humidity of 90°C.
When plate making was carried out in the same manner in a room of
A normal image was obtained with the original printing plate, but Comparative Examples 1 and 2
All of the original printing plates did not have a sufficient amount of charge on the plate surface, and only toner images with an extremely small amount of toner were obtained. Developer solution for PS plate SDI) -
When the photoconductor layer in the non-image area was removed using a 1.7 times diluted solution, it flowed out and a normal image could not be obtained.

In addition, as another experiment, the printing original plates of Examples 1 to 5 and Comparative Examples 1 to 2 were placed in an air-conditioned room at a temperature of 23°C and a relative humidity of 80% for 7 days.
After storage for 2 hours, plate making was performed in the same manner as above in a room at a temperature of 23°C and a relative humidity of 48%. Normal images were obtained for the printing master plates of Examples 1 to 5, but for Comparative Examples 1 to 2. With the printing original plate of Toner Eat (7), only a small image was obtained, and when the non-image area was removed with an alkaline aqueous solution in the next step, the image leaked out.

〔Effect of the invention〕

According to the present invention, the humidity resistance of the printing original plate, that is, the reduction in charge acceptance and sensitivity caused by storing the printing original plate in an atmosphere of high humidity (relative humidity of approximately 80% or more), and the reduction in sensitivity caused by these, can be improved. This improves the drawback that a normal image cannot be obtained on a printing plate.

Further, the printing original plate of the present invention has the qualities described in the following items 1 to 0.

■ Excellent charge acceptance and high sensitivity.

■ Low residual potential and less scumming.

(2) The photoconductor layer in non-image areas (other than toner image areas) can be easily removed.

■ Excellent printability and high durability [II+1 properties].

■ Excellent stability over time.

(2) By selecting a photoconductive material (for example, copper phthalocyanine), it is possible to record with a low-power laser (for example, He--Ne laser light, semiconductor laser light, etc.).

Claims (1)

[Claims] In a printing original plate having a photoconductor layer on a conductive support, and after forming a toner image, removing the photoconductor layer in the non-image area to create a printing plate, the photoconductor of the printing original plate is The monomer component for forming a polymer compound in the body layer is 4% relative to the weight of the photoconductor layer.
．． A printing original plate characterized by having a content of 0% by weight or less.