JPS6322302B2 - - Google Patents

Description

Detailed Description of the Invention The present invention relates to a method for producing a lithographic printing plate that does not require dampening water, and more specifically to a method for producing a lithographic printing plate that has excellent properties in terms of resolution, printing durability, etc. It is intended for the purpose of providing.

In lithographic printing, a plate is used that does not have clear heights on the plate surface like letterpress or intaglio, and has a printed area and a non-printed area on the same plane in appearance.This printing method involves the following process. It will be held in That is, since water and fat repel each other, first of all, the non-image areas are made hydrophilic by chemical or mechanical treatment, and the image areas are transferred to a fatty resin or photographed. The printing plate is made lipophilic by baking or the like, and then water is transferred to this printing plate so that the water adheres only to the hydrophilic non-image areas, and then ink is further transferred to this printing plate. In this way, this ink does not adhere to the non-print areas where water is present, but only to the lipophilic print areas, so this ink is then transferred to the printing substrate to create the desired print. This is done through the process of obtaining .

However, in this lithographic printing method, for example, the transfer of the dampening water to the ink roller causes the ink to emulsify on the ink roller, which not only causes soil stains but also covers the dampening water. Transfer to printed matter also causes a change in the dimensions of the printed material, which has a major drawback, especially in multicolor printing, in that the printed image becomes unclear. In addition, in this planographic printing method, in order to obtain printed matter with a constant color tone, it is necessary to maintain a constant balance between the amount of dampening water and the amount of ink.
It is very difficult to maintain a constant balance between these two amounts, which has the disadvantage of causing variations in the color tone of printed matter.

For this reason, attempts have been made to develop printing plates for lithographic printing that do not require dampening water in order to improve the above-mentioned disadvantages, but none of the plates known to date are sufficiently satisfactory for practical use. They are not yet able to show the characteristics they should have.

For example, a diazo photosensitive layer made of a diazo type photosensitive composition and a dimethylpolysiloxane rubber layer are formed on a substrate such as an aluminum plate, and then a positive film is further laminated thereon and then exposed. A method of insolubilizing the diazo photosensitive layer in the exposed areas, removing the diazo photosensitive layer in the non-exposed areas by development treatment, and then peeling off the dimethylpolysiloxane rubber layer in the non-exposed areas (Tokuko Sho)
44-23042), or on a substrate such as an aluminum plate, a diazo photosensitive layer, an adhesive layer, and a silicone rubber layer are sequentially formed, and then a negative film is superimposed on this layer and exposed. A method of obtaining a printing plate for lithographic printing by developing the photosensitive layer using photodecomposition and then peeling off the silicone rubber layer in the exposed area (Japanese Patent Publication No. 1973-
16044) is known.

However, in all of these methods, a non-photosensitive silicone rubber exists between the diazo photosensitive layer and the positive or negative film, so it is difficult to accurately reproduce the pattern appearing on the positive or negative film. Furthermore, since the silicone rubber layer is peeled off by utilizing changes in the solvent solubility of the photosensitive layer, the edges of the image formed by the silicone rubber layer after peeling off are poor. It has the serious disadvantage that it is not sharp, and its fabrication requires only 2 to 3
Since the process involves sequentially stacking layers, exposing to light, and developing, the process is complicated.

As a method to eliminate the above-mentioned drawbacks in the development operation, there are methods of destroying the silicone layer by electron beam, laser light, electric discharge, etc. (see Japanese Patent Publication No. 42-21879), and by scanning the silicone layer with glow or corona beam. How to make it lipophilic
8207) is known. According to this, by destroying the silicone layer with an electron beam, laser beam, electric discharge, etc., or processing it with a corona beam, offset printing can be performed without any developing operation and without dampening water. However, high energy is required to destroy the dimethylpolysiloxane that is the ink repellent layer and produce low molecular weight dimethylpolysiloxane, and the manufacturing equipment becomes large-scale. Furthermore, when patterning the silicone layer, the silicone is thermally destroyed with high energy, which causes the edges of the image to swell, resulting in a loss of sharpness of the image, resulting in a reduction in resolution and print quality. Also,
When using a corona beam, the printing plate takes a long time to form an image by scanning the ink repellent layer, and special equipment is required.

The inventors of the present invention have comprehensively studied material selection and manufacturing methods, taking into account the above-mentioned drawbacks of conventional lithographic printing plates that do not require dampening water.
By subjecting the organopolysiloxane cured film layer to corona treatment or flame treatment, the ink-philic resin will firmly adhere to the treated surface, and this ink-philic resin layer will become the image area. By providing a protective layer in a pattern on the siloxane cured film layer, corona treatment or flame treatment can be selectively applied, and by removing the protective layer together with the resin layer above it, the non-image areas of the printing plate can be removed. The present invention was completed by discovering that it is possible to form the following.

The present invention will be explained in detail below.

First, the present invention will be explained based on the drawings.
The figure is a partially enlarged cross-sectional view schematically illustrating the structure of the lithographic printing plate of the present invention. 2 (non-printing area), an organopolysiloxane cured film layer 2' whose surface has been corona-treated or flame-treated in a pattern, and an ink-philic resin layer 4 (printed area) formed thereon. Department).

Next, a method for producing a printing plate for lithographic printing according to the present invention will be explained. As shown in FIG.
After that, a protective layer (such as a photosensitive resin layer) 3 is provided in a pattern on the organopolysiloxane cured film layer 2, as shown in FIG. Next, corona treatment or flame treatment is applied to the entire surface, as shown in Figure 3.
A surface-treated organopolysiloxane cured film layer 2' is formed in the area not covered with the protective layer 3.

Next, as shown in FIG.
is applied to the entire surface, and after curing, both the protective layer 3 and the resin thereon are removed to form the lithographic printing plate shown in FIG.

It is possible to make the surface of organopolysiloxane lipophilic to some extent by corona treatment or flame treatment alone, thereby making it possible to use it as a printing plate. However, the lipophilic layer produced by corona treatment and flame treatment lacks mechanical strength and wears out quickly, making it impossible to use as a practical printing plate. Also, fairly aggressive processing is required to create a layer that is oleophilic enough to be suitable for printing.

The treatment referred to in the present invention is for improving the adhesion of the ink-philic resin, and a very weak treatment is usually sufficient. If the treatment is more intense than that, the structure of the organopolysiloxane cured film layer itself will be damaged, and the printing durability of the printed area will likely be reduced.

Various metal plates with good dimensional stability are suitably used as the material for the substrate 1, but if dimensional stability is not required, various polymer films, paper, etc. alone or laminated materials thereof can also be used.

Examples of metal plates include copper plates, aluminum plates, stainless steel plates, zinc plates, iron plates, nickel-plated copper plates or iron plates, and chrome-plated iron plates. Examples of polymer films include polyester, nylon, stretched polypropylene, and other single or laminated films. Examples include films laminated with aluminum foil or the like.

The organopolysiloxane used to form the organopolysiloxane cured film layer on the substrate is desirably one with excellent strength and abrasion resistance, good printing durability, and strong ink repellency, and which has dimethylpolysiloxane as the main component. Various thermosetting silicones are preferably used. There are two types of thermosetting silicone, one-component type and two-component type.
This is due to a catalytic crosslinking reaction between siloxanes having reactive groups such as -CH= _CH2 , and crosslinking reactions such as dehydration condensation, dealcoholization condensation, dehydrogenation condensation, and addition polymerization occur. One-component curing involves reacting with moisture in the air to cause a condensation curing reaction, and includes deacetic acid type, deamine type, dealcohol type, and deoxime type. These are dissolved in a suitable solvent such as benzene or toluene, applied by spin coating, dipping, reverse roll coating, dripping, etc., and heated and dried to form an organopolysiloxane cured film layer. can get.

More specifically, among those that crosslink and cure at room temperature or by heating after coating to become an ink-repellent silicone rubber elastic body, highly polymerized organometallic materials in which 90 mol% or more of all organic groups bonded to silicon atoms are methyl groups It is best to use polysiloxane (which has excellent ink repellency) as its main component, which includes (1) a polymer in which 90 mol% or more of the organic groups, both ends of which are blocked with hydroxyl groups, are methyl groups; Highly polymerized diorganopolysiloxane, methylhydrodiene polysiloxane or ethyl polysilicate as a crosslinking agent, and organic metal salt as a condensation catalyst; (2) Highly polymerized diorganopolysiloxane containing vinyl groups (organic (90 mol% or more of the groups are methyl groups), methylhydrodienepolysiloxane as a crosslinking agent, and a platinum-based catalyst as an addition reaction catalyst; Highly polymerized diorganopolysiloxane in which 90 mol% or more is methyl groups,
Examples of crosslinking agents include silanes or low polymerization degree siloxane compounds having three or more hydrolyzable groups such as acetoxy groups, amino groups, oxime groups, or propenoxy groups in one molecule. In the present invention, the types exemplified in (1) or (2) above are particularly suitable.

In addition, organic groups other than methyl groups in the above generally include aryl groups such as phenyl groups, alkenyl groups such as vinyl groups, alkyl groups such as ethyl groups and propyl groups, and halogen-substituted alkyl groups such as trifluoropropyl groups. Illustrated.

In the compositions exemplified in (1), (2) and (3) above, if necessary, ordinary diorganopolysiloxane such as dimethylpolysiloxane may be added to improve the properties of the cured coating film in order to further improve ink repulsion. It is permissible to add a small amount of reinforcing filler, such as fine silica powder, to the extent that it does not cause any adverse effects, and for the purpose of improving printing durability.

In order to form a uniform film of the cured organopolysiloxane film layer, the surface of the substrate is cleaned in advance by an appropriate method, and if necessary, the surface is roughened.
It is desirable to improve the adhesion with the coating.
In addition, it is advisable to apply a primer to the surface of this substrate in advance to improve adhesion with the film. Examples of this primer include vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltritri Methoxysilane, 3-methacryloxypropyltrimethoxysilane, N-(3-
(trimethoxysilylpropyl) ethylenediamine, 3-aminopropyltriethoxysilane, etc. alone or mixtures thereof, as well as their partial hydrolysates or partial co-hydrolysates, are used, and these can be applied by spin coating or rod coating. It is applied by conventional methods such as , brushing, spraying, etc.

After forming a cured film layer of organopolysiloxane on a substrate as described above, a protective layer is formed in a pattern on this layer. Materials available.

The photosensitive resin used in this case may be any conventionally known photosensitive resin, including cinnamic acid photosensitive resins (TPR manufactured by Tokyo Ohka Co., Ltd., KPR manufactured by Kodatsu Co., Ltd.).
etc.), cyclized rubber-based photosensitive resin (manufactured by Tokyo Ohka Co., Ltd.)
OMR, Fuji Pharmaceutical Co., Ltd. FSR, etc.), azide photosensitive resins (Fuji Pharmaceutical Co., Ltd. FPER, etc.), and diazo photosensitive resins (Supure Co., Ltd. AZ, Tokyo Ohka Co., Ltd. OFPR, Fuji Pharmaceutical Co., Ltd. FPPR, etc.), etc. Commercially available photoresists and many photosensitive resins and coatable photosensitive materials can be used. In the case of a commercially available product, it is patterned by a normal photoresist plate making method. The photoresist image can be formed by applying the photoresist solution directly onto the cured organopolysiloxane film layer using a normal coating method, or by applying it once onto a film of polyethylene, polypropylene, etc., drying it, and then applying heat and pressure. , a method of transferring onto an organopolysiloxane cured film layer can be applied,
After that, patterning is performed.

When these photoresists are applied to the surface of the organopolysiloxane cured film layer, the photoresist may be repelled by the organopolysiloxane surface. At this time, coating suitability can be improved by adding a surfactant, silicone resin, or silicone oil to the photoresist solution. Surfactants that can be used include fluorine-based and silicone-based surfactants, such as FC-431 manufactured by 3M.

Various organopolysiloxanes can be used as the silicone resin that can be added to the photoresist, including silicone rubber (KS774, KS705F, etc. manufactured by Shin-Etsu Chemical Co., Ltd.), silicone varnish (KR271, etc. manufactured by Shin-Etsu Chemical Co., Ltd.), Examples of the silicone oil include dimethylpolysiloxane oil (KF-96 manufactured by Shin-Etsu Chemical Co., Ltd.), and further examples include various photosensitive silicones.

Specific examples of the photosensitive silicone include:
Organopolysiloxane having a siloxane unit bonded to a maleimide group or a maleimide group containing a substituent atom or group (JP-A-51-120804
No. 51-125277, No. 52-13907, No. 52-
105002, 52-116304, etc.), organopolysiloxanes having siloxane units to which acryloxy groups or acryloxy groups containing substituent atoms or groups are bonded (Japanese Patent Application Laid-open No. 16991/1986, 48
-No. 19682, No. 48-21779, No. 48-23880, No. 48-23880, No.
No. 48-47997, No. 48-48000, No. 48-83722,
No. 51-34291, No. 51-52001, No. 52-105003
No. 52-105004, No. 52-113805, No. 52-
113801, etc.), mixtures of organopolysiloxanes having mercapto group-containing siloxane units and organopolysiloxanes having vinyl group-containing siloxane units (see JP-A-53-17405), organopolysiloxanes having vinyl group-containing siloxane units. Mixtures of siloxanes and organohydrodiene polysiloxanes (see JP-A-53-15907, etc.);
139504, etc.), a mixture of an organopolysiloxane having an acryloxy group-containing siloxane unit and an organopolysiloxane having a vinyl group-containing siloxane unit (see JP-A-52-139505, etc.)
Examples include.

Examples of mixtures of silicone and photosensitive substances include mixtures of organopolysiloxanes and photosensitive substances such as azide compounds, p-quinonediazide compounds, cinnamic acids, acrylic acids, and acrylates (Japanese Patent Application Laid-open No. 49-1989-1). No. 68803, 49-
Examples include various silicones such as No. 86102, No. 49-121601, No. 51-134204, etc.).

The photocurable organopolysiloxane for forming the protective layer 3 needs to have good wettability to the cured film layer 2, and for this purpose, it is preferable that the surface tension is approximately equal to that of the cured film layer 2. Conventionally known photocurable organopolysiloxanes can be used as appropriate for the purpose. This surface tension is 18 to 25 dyn/cm, preferably 20 to 23 dyn/cm.

The silicone-added photoresist is applied onto the organopolysiloxane cured film layer by conventional spin coating, brushing, rod coating, etc. methods. Incidentally, these patternings are performed by a normal photoresist plate making method and development with a solvent such as trichlorethylene.

The resist layer can also be formed into a pattern by screen printing using an ink containing ethyl cellulose, ethyl hydroxy cellulose, acrylic resin, or the like. In this case as well, there are direct printing and transfer methods, but the transfer method is preferable because addition of a thinner reduces printability. Furthermore, the resist layer can also be formed by electrostatic printing using electrostatic photographic toner or the like as a resist material. In this case, since the organosilicone layer is an insulator, it is possible to form a good electrostatic latent image and toner image. More simply, a film-forming resin liquid may be hand-painted or transferred by an appropriate printing means.

In flame treatment, a metal substrate such as aluminum is coated with an organopolysiloxane layer, and a protective layer is placed on top of the layer, which is then floated on the surface of water to prevent destruction of the organopolysiloxane layer due to localized heating. The treatment can be carried out by applying a flame from a burner or the like to the surface of the organopolysiloxane and moving it uniformly.

For the corona treatment, commercially available equipment can be used, such as the corona surface treatment machine RS-8 manufactured by ENI Power Systems.

Next, as a method for forming an ink-friendly resin layer on the flame-treated or corona-treated surface, for example, a resin solution or emulsion is coated on the entire surface by Whaler, dried and hardened, and then an adhesive tape or the like is applied on top of it. This can be done by peeling it off, but since the adhesive force between the protective layer and the organopolysiloxane is weak, the patterned protective layer and the resin layer above it will harden together with the organopolysiloxane. It is peeled off from the surface of the membrane. On the other hand, the resin layer is firmly adhered to the treated surface that has been corona-treated or flame-treated, so even if the adhesive tape is removed, the resin layer in this area will not be affected in any way and the organopolysiloxane cured film will remain intact. It is stuck to. As a result, a lithographic printing plate is obtained.

On the other hand, the following method may also be used. That is, a resin solution or emulsion is applied to a thermoplastic resin film such as polypropylene, polyethylene, polyester, etc. by a method such as whaler coating, roll coating, or bar coating.
After drying, dry lamination is performed on the surface of the organopolysiloxane cured film provided with the protective layer. Heat and cure under pressure to prevent the film from peeling off. When the film is then peeled off, the protective layer and the resin on the protective layer are peeled off together with the film, but on the other hand, the resin of the film transfers to the areas that have been corona-treated or flame-treated and firmly adheres.
A lithographic printing plate is obtained.

The ink-philic resin used here is preferably a thermosetting resin, including one or two of thermosetting resins such as melamine, epoxy, alkyd, phenol, urea, and polyester.
A mixture of more than one species is exemplified.

The thickness of the ink-friendly resin layer to be formed is usually 0.5~
It is desirable to set it to 10μ.

The lithographic printing plate thus produced has extremely high printing durability and good ink receptivity, and since the image area is plano-convex, it is possible to obtain excellent printed matter with good ink coverage and transfer. In particular, the difference in ink repulsion in non-image areas and ink receptivity in image areas is greater than in other types of waterless lithographic plates, so there is an advantage that there is a wide tolerance range when designing ink supply.

Moreover, this type of printing plate can be used for offset printing, offset rotary printing, die lithography, letterpress printing, and live printing, and the benefits obtained are large.

Next, specific examples will be given.

Example 1 A 1% isopropyl alcohol (IPA) solution of KBP-41 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied as a primer on a degreased and cleaned aluminum plate, and after drying dimethylpolysiloxane (Shin-Etsu Chemical Co., Ltd. KS705F) was applied as a primer. After drying and curing, apply a surfactant (manufactured by 3M Co., Ltd.) to a film thickness of 10μ.
A photoresist solution (FPER100 manufactured by Fuji Pharmaceutical Co., Ltd.) containing 1% by weight of FC-431) was applied by spin coating and dried (dry film thickness: 3 μm).

Next, a resist image (protective layer) was formed on the polysiloxane by attaching a predetermined positive original plate, followed by exposure and development. Next, the above surface was subjected to corona treatment at a speed of 4 m/min using a corona surface treatment machine PS-8 (output 500 W, using a roll electrode) manufactured by ENI Power Systems Co., Ltd., and this was performed four times.

12 Adhesive Takerak A-310 manufactured by Takeda Pharmaceutical Co., Ltd.
(parts indicate parts by weight, the same applies hereinafter), 1 part of Takenate A-3, and 120 parts of ethyl acetate, and a coating solution prepared by diluting 8 times with ethyl acetate was applied to the treated surface by Whaler. After curing at 100℃ for 1 hour, adhesive tape is applied to the cured resin surface and peeled off. The protective film and the cured resin on the protective layer are adhered to the adhesive tape and peeled off, while the cured resin in the corona-treated area is dimethylpolysiloxane. A lithographic printing plate was obtained by firmly adhering to the top and remaining as it was.

When this printing plate was used for printing with a KOR printing machine (manufactured by Heidelberg) without supplying dampening water, it showed good printing durability of over 20,000 sheets.

Example 2 The same procedure as in Example 1 was carried out, except that instead of the corona treatment, an aluminum plate with a dimethylpolysiloxane cured film was floated on the water surface, and the surface of the dimethylpolysiloxane cured film was subjected to flame treatment by applying the flame of a gas burner. When a lithographic printing plate was manufactured using the same method, it showed a printing life of over 20,000 sheets.

Example 3 A 1% IPA solution of a mixture of equal amounts of γ-glycidoxypropyltrimethoxysilane and n-butyl orthotitanate was spin-coated on a degreased and cleaned aluminum plate, and after drying, dimethylpolysiloxane ( The film thickness after drying Shin-Etsu Chemical KS774) is
It was coated to a thickness of 15μ, dried, and cured by heating. Next, a photosensitive resin (TPR101-P manufactured by Tokyo Ohka Co., Ltd.) coating film (film thickness 5 μm) was formed on the stretched polypropylene film (OPP), and this photosensitive resin coating was pressed onto the previously cured organopolysiloxane film and heated. Then, the photoresist film was transferred. Next, after a predetermined positive original plate was closely attached, a resist image was formed on the dimethylpolysiloxane cured film by exposure and development.

Next, corona treatment was performed in the same manner as in Example 1. 12 copies of Takeratsuku A-310, Takenate A-
A coating solution prepared by mixing 1 part of 3 and 120 parts of ethyl acetate and further diluting 16 times with ethyl acetate was spin-coated onto an untreated OPP film (film thickness: 15μ), and immediately applied to the dimethylpolysiloxane coated surface. Dry laminated. After curing this at 100℃ for 1 hour
When the OPP film is peeled off, the thermosetting resin adheres only to the corona-treated organopolysiloxane surface and is transferred from the OPP film to form the image area. The thermosetting resin on the protective layer was peeled off together with the film, and the protective layer was also removed at the same time. A portion of the protective layer remained, but it was removed using adhesive tape.

When this printing plate was subjected to the same printing test as in Example 1, it showed a printing durability of 20,000 sheets or more.

Example 4 Same as Example 3 except that the same flame treatment as in Example 2 was performed instead of the corona treatment.
When a lithographic printing plate was produced in the same manner as above, it showed a printing life of over 20,000 sheets.

Example 5 The surface of a polyester film (100 μm thick) whose back side was reinforced with a 300 μm thick aluminum plate was degreased and cleaned, and a mixture of equal amounts of γ-glycidoxypropyltrimethoxysilane and n-butyl orthotitanate was applied with IPA. A primer solution diluted with water and adjusted to 1% was applied and dried. On top of this, organopolysiloxane (KS773 manufactured by Shin-Etsu Chemical Co., Ltd.) is applied to the film thickness after drying.
It was applied to a thickness of 10μ, dried, and cured by heating.

A photosensitive resin liquid (manufactured by Tokyo Ohka Co., Ltd.) is applied on this cured film.
OMR83) with organopolysiloxane KS774 5
After adding % by weight and drying, a positive original was adhered, exposed and developed with xylene.

Next, after performing the same corona treatment as in Example 1, 15 parts of acrylic polyol resin (Acryto 6416MA manufactured by Taisei Kako Co., Ltd.) and 10 parts of Takenate A-3 were added.
A coating solution prepared by mixing 125 parts of ethyl acetate and 125 parts of ethyl acetate and further diluting 4 times with ethyl acetate was spin-coated onto the surface of the organopolysiloxane coating and cured at 100°C for 1 hour. Thereafter, the resin on the non-image areas was removed using an adhesive tape in the same manner as in Example 1 to produce a lithographic printing plate.

When this printing plate was subjected to the same printing test as in Example 1, it showed good printing durability of 10,000 sheets or more.

Example 6 A lithographic printing plate was produced in the same manner as in Example 5 except that the same flame treatment as in Example 2 was performed instead of the corona treatment. It showed printing durability.

Example 7 Toyo Ink's Adkoat 76P1 and the company's hardening agent ADFJ were applied on a 100μ thick polyester film.
A 10:1 mixture was applied, laminated with 14μ aluminum foil, and dried and cured at 60°C for one week to obtain a laminated film of aluminum and polyester. After polishing and cleaning the aluminum surface of the laminated film, a cured film layer of organopolysiloxane (KS774) was formed on the aluminum foil in the same manner as in Example 3.

Next, after dissolving 260 parts of dimethyldichlorosilane and 50 parts of phenyltrichlorosilane in 1000 parts of toluene, this solution was poured into 1100 parts of water at a temperature
The mixture was added dropwise to carry out cohydrolytic condensation while maintaining the temperature at 25° C. or lower, followed by washing with water, neutralization, and dehydration to obtain a toluene solution with a siloxane concentration of 15% by weight. To 1000 parts of this toluene solution, 50 parts of 3-aminopropyltriethoxysilane was added, and 0.2 parts of dibutyltin dioctoate was added to perform a deethanol reaction.
A toluene solution of a 3-aminopropyl group-containing organopolysiloxane corresponding to the following formula was obtained.

(Me ₂ SiO) ₂₀₀ (PhSiO _1.5 ) ₂₄ (H ₂ NC ₃ H ₆ SiO _1.5 ) _2.2 Me: methyl group, Ph: phenyl group Next, α- Phenylmaleic anhydride was added at a ratio of 1 mole to 1 mole of 3-aminopropyl group (3.94 parts of α-phenylmaleic anhydride was added to 10 parts of dimethylformamide).
ml was added dropwise at a temperature of 20°C), 25
When the reaction was carried out at 110°C for 1 hour and then at 110°C for 4 hours (the reaction was allowed to proceed while removing water generated from the reaction from the reaction system), a maleimide group-containing organopolysiloxane corresponding to the following formula was obtained. (confirmed by infrared absorption spectrum analysis).

(Me ₂ SiO) ₂₀₀ (PhSiO _1.5 ) ₂₄ (QC ₃ H ₆ SiO _1.5 ) _2.2 This substance is solid at room temperature (softening point 110-120
℃).

Photopolymerizable organopolysiloxane obtained above
...50 parts Toluene ...950 parts The above composition was roll coated onto the cured organopolysiloxane film so that the film thickness after drying was 3μ, and after drying, a 12μ OPP film was dry laminated to form a positive master plate. After close exposure, the OPP film was peeled off and developed with trichlorethylene.
An image was formed.

After performing the same corona treatment as in Example 1, polyester polyol resin XU-
10 copies of 534, 5 copies of Takenate A-3, MEK135
A solution diluted 8 times with MEX was spin-coated and cured by heating, and then a lithographic printing plate was produced using an adhesive tape in the same manner as in Example 1.

1800CD manufactured by Tokyo Aircraft Instruments using this printing version
When printing was carried out using a lightweight offset printing machine without supplying dampening water, it showed a printing life of over 20,000 sheets.

Example 8 A lithographic printing plate was produced in the same manner as in Example 7 except that the same flame treatment as in Example 2 was performed instead of the corona treatment. It showed printing durability.

Example 9 247 parts of a 15% toluene solution of dimethylpolysiloxane (siloxane polymerization degree 500) with both molecular chain ends capped with hydroxyl groups and 60 parts of a 15% toluene solution of a hydrolysis product of phenyltrichlorosilane were mixed, To this, 0.25 part of 3-methacryloxypropyltrimethoxysilane, 0.01 part of dibutylhydroxytoluene and 0.1 part of dibutyltin dilaurate.
A condensation reaction was carried out at the reflux temperature of toluene, and the reaction was allowed to proceed for 8 hours while removing the produced water. A copolymer with a viscosity of 28.5 centistokes (silicone concentration 15%) was obtained.

Photopolymerizable organopolysiloxane obtained above
...50 parts 4-trimethylsilylbenzophenone ...2.5 parts Toluene ...950 parts Primer C-20 was applied to a laminated film of aluminum foil and polyester film similar to that used in Example 7.
After coating and drying a 1% IPA solution of (manufactured by Shin-Etsu Chemical), a cured film layer of organopolysiloxane (KE77, manufactured by Shin-Etsu Chemical) was formed on top of this, and then the above composition was applied on top of this to achieve a film thickness of 1% after drying. After drying, a 12μ OPP film was laminated and an image was formed in the same manner as in Example 7.

Next, after corona treatment was performed in the same manner as in Example 1, 100% of Ciel Petrochemical's epoxy No. 1009 was applied.
A coating solution prepared by mixing 5 parts of Takenate A-3 and 135 parts of ethyl acetate and further diluting 4 times with ethyl acetate was spin-coated and cured at 100°C for 1 hour. Thereafter, in the same manner as in Example 1, the resin on the non-image areas was removed using an adhesive tape to produce a lithographic printing plate.

When this printing plate was subjected to the same printing test as in Example 1, it showed a printing durability of 20,000 sheets or more.

Example 10 Primer on polished aluminum plate
After applying and drying a 1% IPA solution of KBP41, a cured film (thickness: 10 μm) of dimethylpolysiloxane KS705F was formed thereon. On the cured film, a screen printing plate prepared in advance was printed using a screen ink consisting of 20 parts of screen oil containing ethyl cellulose and pine oil as main components and 80 parts of glass frit, and after drying, it was printed in the same manner as in Example 1. Corona treatment was carried out.

Thereafter, the same treatment as in Example 1 was carried out to prepare a lithographic printing plate using adhesive tape. When this printing plate was used to print on a KOR printing machine without supplying dampening water, a printing life of over 20,000 sheets was observed.

Example 11 Example 10 except that flame treatment was performed in the same manner as Example 2 instead of corona treatment.
When a lithographic printing plate was manufactured in the same manner as in Example 10, it had a printing life of over 20,000 sheets.

Example 12 A 1% IPA solution containing an equal amount of γ-glycidoxypropyltrimethoxysilane and n-butyl orthotitanate was spin-coated on a degreased and cleaned aluminum plate, and after drying, organopolysiloxane (KS774 ), 10 parts of curing agent PL-3, and 290 parts of toluene were applied to the solution and heated at 100℃ for 20 minutes.
Allow to dry and harden. The film thickness was 10μ.

50 parts of FPER100 manufactured by Fuji Pharmaceutical Co., Ltd., 5% photosensitive organopolysiloxane produced in Example 9
7 parts of MEK solution and 136 parts of MEK were mixed and coated on the organopolysiloxane cured film layer by Whaler, and after drying, the positive master plate was developed with trichlene after contact exposure. This material was subjected to corona treatment in the same manner as in Example 1.

On the other hand, 12 parts of Takerak A-310 and 1 part of Takenate A-3 were placed on the surface-untreated 15 μOPP film.
A solution obtained by diluting 120 parts of ethyl acetate and 120 parts of ethyl acetate was further diluted 8 times with ethyl acetate, and this solution was immediately laminated onto the organopolysiloxane surface. When the OPP film is peeled off after curing at 100℃ for 1 hour, the protective layer and the resin on the protective layer are
It was peeled off together with the OPP film, and a lithographic printing plate was obtained.

When this lithographic printing plate was used for direct printing on a letterpress rotary press, it showed a printing durability of 10,000 sheets or more.

Example 13 In Example 12, a lithographic printing plate was produced in the same manner as in Example 2 except that flame treatment was performed in place of the corona treatment, and it exhibited a printing durability of 20,000 sheets or more.

Example 14 A 10:1 mixture of Adkoat 76PI and hardener ADFJ was applied onto a 100μ thick polyester film, and 14μ aluminum foil was laminated thereon, and the film was dried and cured at 60°C for one week to form a laminated layer of aluminum foil and polyester. I got the film. After polishing and cleaning the aluminum surface of this laminated film, a hardened film of organopolysiloxane (KS774) was formed on the aluminum foil in the same manner as in Example 3.

Next, add 1 part of surfactant (FC431) to 100 parts of photosensitive resin liquid (AZ111S) and dilute with a 4:1 mixed solvent of MEK and silicone oil (KF96L) to obtain a film thickness of 3μ after drying. I rolled coated it like this. After a predetermined negative original plate was brought into close contact and exposed to light and the image was developed using a developer, corona treatment was performed in the same manner as in Example 1 at an output of 700W.

Next, Cymel manufactured by American Cyanamid Company
370, 1.2 parts of para-toluenesulfonic acid, and 100 parts of toluene were mixed, and this mixed solution was further diluted 16 times and roll coated on the organopolysiloxane cured film. After curing, the resin on the non-image areas was removed using adhesive tape in the same manner as in Example 1.

When the lithographic printing plate thus obtained was subjected to the same printing test as in Example 1, it showed a printing durability of 10,000 sheets or more.

[Brief explanation of the drawing]

1 to 5 are partially enlarged cross-sectional views showing successive steps of the manufacturing process of the lithographic printing plate of the present invention. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Organopolysiloxane cured film layer, 3... Protective layer, 4... Ink-friendly resin layer, 2'... Corona or flame treated surface.

Claims (1)

[Claims] 1. After providing an organopolysiloxane cured film layer on one surface of a substrate and forming a protective layer in a pattern on this cured film layer, the non-protective layer portion of the cured film layer is subjected to corona treatment. Alternatively, a non-image area made of an organopolysiloxane cured film layer is formed on the substrate by flame treatment, then forming an ink-philic resin layer on the entire surface, and then removing the protective layer together with the resin layer on the protective layer. and an image area made of an ink-philic resin layer. 2. The method for producing a lithographic printing plate according to claim 1, wherein the ink-philic resin is an ink-philic thermosetting resin.