JPS60179742A - Instrument for processing photosensitive lithographic plate - Google Patents

Abstract

PURPOSE:To suppress evaporation of a solvent, to ensure smooth flow-out of a photosensitive lithographic plate-processing agent even when a cap is left open and to facilitate operation by filling the agent contg. a fluorinated surfactant. CONSTITUTION:A photosensitive lithographic plate-processing agent contains a fluorinated surfactant, such as an anionic, cationic, or nonionic surfactant, preferably, an anionic one, and an especially preferable example is a fluoroaliphatic oligomer having fluoroaliphatic groups and polyoxyalkylene groups represented by general formula I or II in which Rf is a fluoroaliphatic group; OR is a polyoxyalkylene group; Q is a linking group for connecting both Rf and OR; A is a univalent terminal group; A' is A or a simple bonding group under the conditions that at least one of R combined with Q links to another Q; Q' is a bonding group for covalently bonding A or A' with R; m, n are each an integer >1; and x is an integer of >4.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is applicable to processing tools for photosensitive lithographic printing plates, particularly felt-tip pens in the writing industry. The present invention relates to a processing tool in which the outer container of a so-called felt-pentaino writing instrument, which is called an ink pen, marking pen, marker, or brush pen, is filled with a processing agent for photosensitive planographic printing plates.

[Prior art]

Various processing agents are applied to a photosensitive lithographic printing plate before it can be used as a printing plate by imagewise exposure and development. For example, when contact-printing an I-zi original film, the exposure at the film cut end is insufficient, and that part becomes ink-receptive. There is a method of applying a liquid and scattering light. After exposure and printing, the non-image areas (exposed areas for positive plates, unexposed areas for negative plates) are removed using a printing solution. At this time, unnecessary images such as cut edges of the film, dust on the film, register marks, etc. are removed using an "erasing liquid". There are two methods for erasing unnecessary images: one is to judge the color change during exposure and printing before development, and the other is to judge the formed image and erase it after development.

On the other hand, if pinholes etc. occur in the required image after development,
Additions and corrections will be made using ``Kamen Liquid''. After development, a "protective ink" is applied as necessary to protect the ink receptivity of the image area and/or to improve plate inspection for erasing work. Finally, a "protective gum" is applied to protect the non-image area from hydrophilic, and the printing plate is completed. At this time, if high printing durability is desired, burning may be performed using "r-burning surface preparation liquid". Also, if dirt occurs during printing, remove it with the R-Root Cleaner.

In this way, various processing agents are used when manufacturing printing plates from % photosensitive lithographic printing plates, but they can be classified into the following:
It can be divided into those used for the entire surface or large area and those used for partial or small area.

Processing agents used for the entire surface or large area include immersion or showering using a vat or automatic developing machine, developer used when soaked in a sponge, etc., and applied to the entire surface by hand,
Products include protective ink, protective gum, burning surface preparation liquid, and plate cleaner.

On the other hand, processing agents that are used locally include matte liquids, erasing liquids, and roofing liquids that are applied by brush or spatula, or filled into a felt-ben type container.

Feltven type treatment agents are superior in workability, as they do not require supply of liquid to a brush, compared to when applied with a brush, but they have the following drawbacks:

In other words, if the cap is left open and the solvent in the container evaporates, or if the amount of liquid in the container decreases due to long-term use, the processing agent may not flow well or the required amount may not reach the pen tip. As a result, sufficient treatment effects cannot be obtained.

Furthermore, if the liquid flow deteriorates, the pen tip becomes extremely dirty, which may prevent a sufficient treatment effect from being obtained.

[Purpose of the invention]

Therefore, it is an object of the present invention to suppress evaporation of the solvent, and to improve workability by allowing the processing agent to flow out smoothly and providing sufficient processing effects even when the cap is left open or used for a long time. The object of the present invention is to provide a good processing tool for photosensitive lithographic printing plates.

Another object of the present invention is to provide a processing tool for a photosensitive lithographic printing plate that has good one-time workability and can provide a sufficient surface treatment effect with less staining of the pen tip.

[Structure of the invention]

As a result of extensive research, the present inventors have found that the above object can be achieved by incorporating a fluorine-based surfactant into the processing agent.

The present invention consists of 1. This is a feltven type photosensitive lithographic printing plate processing tool filled with a photosensitive lithographic printing plate processing agent containing a fluorine-based surfactant.

In the present invention, anionic, cationic or nonionic surfactants can be used as the fluorosurfactant, and nonionic fluorosurfactants are particularly preferred. Particularly preferred examples of nonionic fluorosurfactants are represented by the following general formula (1) or (II). Examples include fluoroaliphatic oligomers having a fluoroaliphatic group and a polyoxyalkylene group.

(Rzu)mQ((OR)xQ'A)n, (1)[
(Rf)mQ((OR)xQ'A')n)z(E
l) where ■ represents a fluoroaliphatic group, and Q represents Rf
represents a linking group that covalently bonds and OR.

OR represents a polyoxyalkylene group, ^ represents a monovalent terminal organic group, and at least one is Q.
on the condition that the R bonded to is bonded to another Q.

A or a simple bonding group *Q'ldA or a bonding group covalently bonding A' and R; 1m represents an integer of 2 or more; %n represents an integer of 2 or more; Xtf represents an integer of 5 or more.

The above Rf includes a linear, branched, or cyclic saturated-valent aliphatic residue, and the fluoroaliphatic backbone chain may include an oxygen atom or a pentavalent heterosilicon atom bonded only to carbon atoms. Rf has 3 to 2 carbon atoms.

Most preferably selected from 6 to 12, of which 40 to
78% by weight, preferably 50 to 770 to 77% by weight of fluorine atoms bonded to l/l. The most preferred Rf is a perfluoroalkyl group, i.e. %CnF (where n is from 3 to 20%).

2n+1 Preferably it represents an integer of 6 to 12. ).

m represents an integer of 2 or more, and preferably the fluorine atoms bonded to the carbon atoms contained in Rf are 5 to 30% by weight, most preferably 10 to 30% by weight, based on the fluoroaliphatic oligomer.
It is an integer between 250 and 25% by weight.

The alkylene=R of the oxyalkylene represented by the general formula (1) or (OR in the illusion) has 2 to 4% carbon atoms.
More preferably, it represents 2 to 3 alkylenes, of which ethylene and propylene are most preferred.

Polyoxyalkylene: (OR) 0Rit in x
:, may be the same (i.e., polyoxyethylene or I-lioxynolopylene), or oxyethylene and oxypropylene may be randomly or! Although it may be contained in a lock form, block polymers of oxyethylene and oxypropylene are particularly preferred. Furthermore, in the polyoxyalkylene chain.

-CONH-C6H4-NHCO, -8'''%-CH2
-CH-CH2゜-coco- group and other groups are included.
You can. Such (OR) ) The molecular weight of x is 5oo ~
It is selected from a range of 2,500.

It is a bonding group that covalently bonds Q and Q'#'i, Rf%(OR)x, KA and AI to complete the ori f-f- of the general formula (Rimata #'iω). Q and ql
1 may be a bonding group such as a car that directly bonds Rf and (OR)x, for example, -CH2CH
< , -CH2-CH2-%-CH2CH(0M2-
2) Polyvalent aliphatic group 1 such as 2.4-)rylene.

Oxy, thio, carbonyl, sulfone, sulfonyl, phosphoxy & -P(OH)% amine (e.g., ttf1 〇-NH)-N(C2H5)-, etc.), as well as oxyalkylene, iminoalkylene, iminoarylene , sulfonamide, carbonamide, sulfonamide.

Alkylene, carbonamide alkylene, urethane (e.g. -CH2CH20CON H"1-NHC0NH2
-, acylalkylene [e.g.

co-co- (For example, -=CQOCH2-, etc.).

Appropriate ones can be selected from these reams and Tsumego based on their availability and ease of synthesis. Q and Ql
is preferably contained in the fluoro-oligomer molecule in an amount of 10% by weight or less in the graveyard of groups other than simple bonds.

A　Fis 7 full groups such as acetyl and benzoyl.

Methyl, hydroxyethyl, hydroxypropyl.

It includes alkyl groups such as merkanotethyl and aminoethyl, phenyl, chlorophenyl, /)xyphenyl, nonylphenyl, and hydroxyphenylnatonaryl groups.

The fluoroaliphatic oligomer represented by the general formula (ri or @) is an oligomer containing 3 to 50 monomer units) and is distinguished from a high molecular weight polymer having a molecular weight of 100,000 or more.

The fluoroaliphatic oligomer represented by general formula (1) or a (1) can be obtained by condensation polymerization, radical polymerization, or ionic polymerization using a solution polymerization method, suspension polymerization method, or bulk polymerization method. These include vinyl polymers such as /reesters, I-urethanes, polyoxides, polyamides, and I-reacrylates. A particularly preferred ground sesame polymer 1;j/reacrylate can be synthesized by copolymerizing an acrylate having a fluoroaliphatic residue and an acrylate having a dialkylene residue in polio.

The fluoroaliphatic ori f1- represented by the general formula (1) or (It) and its synthesis method are explained in detail in Japanese Patent Publication No. 57-54500 (corresponding to U.S. Patent No. 3,787,351). There is.

The fluorosurfactant used in the present invention can be obtained as a commercial product, and a specific example is FC-45
0, FC-431 (manufactured by 3M) Mega Fac F-1
41, same 142, same 142-D, same F-143s same F
-144゜F-144D, F 52a% F-17
0゜Same F-171%Same F-172%Same F-175゜Same F
-177, F-183, and F-1e4 (manufactured by Dainippon Ink & Chemicals Co., Ltd.). The amount of the fluorosurfactant added varies depending on the solvent and additives used, but is preferably 0.001-5% by weight, particularly preferably 0.01-2% by weight of the total weight of the processing agent.

If the amount added is small, the effect is weak; on the other hand, if the amount added is large, the drying properties become very poor, the adhesion of matte liquids and addition liquids decreases, and the stain prevention effect of eraser liquids decreases. . These fluorosurfactants may be used alone or in combination
The treatment agent according to the present invention can be used in combination with more than one species. Therefore, processing agents that can be used locally and exhibit the characteristics of a felt-ben type container are suitable, and matte liquids, erasing liquids, and writing liquids are particularly preferred. The composition is well known in the industry], many products are emissive, and there are many publications,
This is described in patents, etc., but will be briefly explained below.

The matte solution is usually mainly composed of a fine powder for one-element scattering, a binder and a solvent for fixing it, and a fluorine-based surfactant is added thereto. As the fine powder, fine particles of silicon dioxide, titanium dioxide, etc. having an average particle size of 1 μm to about 20 μm are preferably used. As the binder, phenol resin, acrylic resin, rosin, alkyd resin, etc. are used.The solvent must be able to dissolve the binder and disperse the fine powder well.
Ethanol, Inno Pro/f-Nol, Isotutanol,
Solvents such as methyl isobutyl ketone, methyl cellosorg, and ethyl cellosorte are used.

These solvents are generally used in appropriate combinations of those with high evaporation rates and those with low evaporation rates so as to obtain a good coating layer. Such a matte liquid is disclosed in Japanese Patent Application Laid-Open No. 52-15
The O eraser described in Japanese Patent No. 2505 usually contains an organic solvent for dissolving and removing the photosensitive layer,
An acidic substance is an essential component to promote the action of the erasing liquid and prevent staining, and in addition, a wetting agent, a viscosity agent, a coloring agent, a fine particle dispersion inorganic substance, a nonionic surfactant, Although it is composed of water and the like, a fluorine-based surfactant is added to it. Examples of organic solvents include lactones (commonly known as bicyclic intramolecular esters), glycols such as methoxy glycol and ethoxy glycol, ketones such as methyl-isobutyl ketone, ethyl-isobutyl ketone, and cyclohexanone, and 2-methoxyethyl acetate%2.
-Ethoxyethyl acetate.

Esters such as ethyl acetate and glutyl acetate, ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether, and special solvents such as dimethyl sulfoxide and dimethyl formamide can be used. Further, as the acidic substance, phosphoric acid, hydrogen fluoride; fluorine-containing compounds such as fluorinated zirconic acid, citric acid, retulic acid, lactic acid, etc. can be used. Details of the composition of such erasing liquid Fi1 Special Publication 1984-160
No. 47, No. 51-55442 and JP-A No. 55-121
It is explained in each publication of No. 447.

In addition to the binder and the solvent, the addition liquid contains a photosensitive diazo resin for maintaining printing durability, a photosensitive azide compound, a photosensitive resin having an unsaturated double bond in one molecule of the photopolymerizable composition, It consists of a coloring agent to make the added parts easier to see, and a fluorine-based surfactant is added to this. The binder and solvent used are those exemplified for the matte liquid.

In the present invention, the containers used to fill the processing agent are many used in the writing instrument industry.

As long as it is a so-called felt pen type, it may be of a l/if type. For example, containers that use cotton or felt for filling in the tank inside the container, knock-type containers that fill ink directly into a hollow tank and adjust the flow rate by opening and closing, and pens. Examples include brush pentaigs whose tip is similar to the tip of a brush.

Since these containers are already commercially available and well known, detailed description thereof will be omitted.

〔Effect of the invention〕

According to the present invention, even if the cab is left open or the pen is used for a long time, the processing agent can properly flow out and provide a sufficient processing effect. A felt pen type photosensitive lithographic printing plate processing tool with good workability and a slight stain on the tip <1 is obtained.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples.

Example 1 and Comparative Example i A matte liquid having the composition shown in Table 1 below was prepared and filled into a felt-tip pen container.

Table 1 To prepare the matte liquid, first add half of the solvent to Aerosil 380, grind it in a ball mill (volume 11) for 12 hours, and add the binder and FC-
This was done by adding and mixing a solution in which 450 was dissolved.

These matte liquid-filled felt tip pens were used to apply the matte liquid onto the base of the cut-out area of the laminated film. Comparative example a.
With the pen, smearing occurred in 5 to 6 minutes], and because there was insufficient liquid after processing a large amount, the film edge became an ink-receptive trap. In contrast, with the pen of Example 1, when the cap was opened under the same conditions, it took about 15 minutes before blurring occurred. The fact that the edge part becomes receptive to cows (<, good results were obtained.

Example 2 and Comparative Example An erasing liquid having the composition shown in Table 2 below was prepared and a fake brush was used!
filled into a container.

Table 2 This was used as an eraser before development.

In the case of the Comparative Suno pen, when it was left open for a long time (approximately 15 minutes) in a no-air condition at 25°C, 6o% Hb, the liquid became blurry and the amount of liquid was insufficient, resulting in incomplete erasing. When treated in large quantities, the liquid flow was poor, the dissolved photosensitive layer stained the tip of the brush, and erasability deteriorated.In contrast, Example 2
With this pen, good results were obtained, with no liquid smearing even when the cap was left open for 50 minutes or more, and the degree of staining of the tip of the brush was small even after processing a large amount.

Example 3 and Comparative Example C An erasing liquid having the composition shown in Table 3 below was prepared and filled into a felt pen type container to obtain an erasing pen for development.

#i: When using the pen of Comparative Example C in Table 3 and leaving the cap open for a long time (approximately 10 minutes) at 25°C, 60°C, and RH% without air, the liquid may become blurred or the liquid may be insufficient, resulting in incomplete erasing. ], and when large amounts of unnecessary images with large areas are processed, the liquid flow is poor and the dissolved photosensitive layer stains the pen tip, and in severe cases it can stain the felt inside. As a result, the erasability deteriorated and the outline of the liquid on the non-image area became smeared. On the other hand, with the pen of Example 3, there was no blurring even when the cap was opened for 60 minutes or more, and the liquid flow was good, so there was only a slight amount of dirt on the pen tip, and there was no chance of dirt on one outline. The erasability was good.

Example 4 and Comparative Example d Addition liquid having the composition shown in Table 4 below was prepared and filled into felt-in containers. While the pen of Comparative Example d, which did not contain the fluorosurfactant FC-450, caused smearing after 8 to 9 minutes, the pen of Example 4 did not smudge for about 20 minutes.

Table 4 Procedural Amendments Showa 9. Ro 16th 1, Incident Display 1981 Patent Temple No. 36951 2,
Title of invention Processing tool for photosensitive lithographic printing plates 3 Name of person making the amendment Name (520) Fuji Photo Film Co., Ltd. 5 Date of amendment order Voluntary 6 Subject of amendment Detailed explanation of the invention in the specification The description in the description is corrected as follows.

Claims (1)

[Claims] A felt pentaino photosensitive lithographic printing plate processing tool filled with a photosensitive lithographic printing plate processing agent containing a fluorine-based surfactant.