JPS6155668B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a printing plate for lithographic printing that does not require dampening water and a method for manufacturing the same, and more specifically,
This invention relates to a printing plate for lithographic printing that has extremely excellent properties in terms of resolution, printing durability, etc., and a method for manufacturing the same.

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 causes stains, and also The transfer to the printing material also causes a change in the dimensions of the printing material, so there is a major drawback that the printed image becomes unclear, especially in multicolor printing. In addition, in this lithographic 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 balance, which has the disadvantage of causing variations in the color tone of the 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. It has not yet reached the point where it shows the characteristics it 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 then exposed to light. 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. There is a serious drawback that it does not become sharp,
This also has the disadvantage of a complicated operation, since its manufacture involves the steps of successively depositing two or three layers on a substrate, exposing and developing.

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 ink repellent layer of dimethylpolysiloxane and generate low molecular weight dimethylpolysiloxane, and the plate making apparatus 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 and the sharpness of the image to be lost, 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 selective chemical treatment with activated chemical species in a plasma state, cured films of organopolysiloxane can be bonded to ink-philic and wear-resistant materials such as thermosetting resins such as acrylic polyol resins. Become a product with excellent adhesive properties,
Furthermore, we have discovered that chemical treatment can be selectively prevented by interposing a suitable protective layer, that chemical treatment can be performed in a short time with low energy, and that high resolution can be achieved, leading to the present invention.

That is, the present invention has a non-image area made of an organopolysiloxane cured film layer on one side of the substrate,
A printing plate for lithographic printing having an image area formed of a layer of an ink-friendly and abrasion-resistant substance formed on a cured organopolysiloxane film layer whose surface is chemically treated with activated chemical species in a plasma state; and The gist is the manufacturing method.

The lithographic printing plate of the present invention and its manufacturing method apply chemical treatment using plasma, and therefore have the following excellent characteristics.

(1) Since the organopolysiloxane itself does not require pattern forming ability, it can be freely selected from organopolysiloxanes with excellent solvent resistance, abrasion resistance, adhesion to substrates, etc.

(2) Chemical treatment using plasma utilizes a reaction between the gas phase and the solid phase, so almost no physical force is applied to the protective layer, and its adhesion to the organopolysiloxane cured film layer is comparatively low. It's good to have a small target. The resolution depends only on the resolution of the protective layer itself and is not affected by patterning, so high resolution can be obtained.

(3) The organopolysiloxane cured film layer has high gas permeability, and active chemical species can easily penetrate into the layer. For this reason, not only the surface but also the inside is chemically treated.

(4) Since activated chemical species in a plasma state can be guided from the plasma generation chamber to other chambers, activated chemical species can be supplied to multiple chambers from one generator, and the activated chemical species can be supplied to multiple chambers at the same time. Multiple printing plates can be produced in a short period of time, and the equipment is relatively inexpensive.

(5) The layer of ink-friendly and abrasion-resistant material formed on the chemically treated portion of the cured organopolysiloxane film is firmly adhered to the base, and has excellent printing durability and durability. In addition, this layer (image area) is slightly protruding, resulting in a flat relief type, and therefore exhibits better printability.
Shows printing durability of 10,000 sheets.

(6) Negative and positive plates can be easily produced by selecting the protective layer.

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 printing plate for lithographic printing of the present invention. layer 2 (non-printing part),
A layer 4 of an ink-philic and wear-resistant material is formed on the plasma-treated organopolysiloxane cured film layer 2'. Ink is deposited on this layer 4 (not shown).

Next, a method for producing a printing plate for lithographic printing according to the present invention will be explained. As shown in FIG.
After providing the film with a thickness of 2 to 50 μm,
As shown in FIG. 2, a protective layer 3 is provided in a pattern on the organopolysiloxane cured film layer 2. As shown in FIG. Next, by applying plasma treatment,
As shown in FIG. 3, the organopolysiloxane cured film layer in the area where the protective layer 3 is not covered is chemically treated with activated chemical species in a plasma state.

Next, the method of the present invention goes through the steps shown in FIG. 4a or 4b to produce the lithographic printing plate shown in FIG. 5, but when going through the step shown in FIG. 4a, As shown in the figure, the protective layer 3 is first removed, and then a layer 4 of an ink-philic and wear-resistant material is formed on the plasma treated layer 2'. On the other hand, the fourth
When going through the process shown in Figure b, after the plasma treatment in Figure 3, a layer of an ink-friendly and wear-resistant material is formed on the entire surface of the protective layer 3 without removing it. Then, the protective layer 3 is removed together with the layer of ink-philic and abrasion-resistant material present thereon to obtain the lithographic printing plate shown in FIG.

The above-mentioned substrates are made of materials that are not affected by oxidation or etching due to chemical treatment using plasma, or photodegradation reactions caused by ultraviolet light generated by plasma. Specific examples include copper plates, aluminum plates, and stainless steel plates. Metal plates such as plates, zinc plates, iron plates, nickel-plated copper plates or iron plates, or chrome-plated iron plates, and the above-mentioned various metal foils placed on other substrate materials such as paper and plastic, as well as paper and plastic alone or Compounds etc. can be used.

Next, as the organopolysiloxane used to form the organopolysiloxane cured film layer 2 on the substrate, it is desirable that the organopolysiloxane has excellent strength and abrasion resistance, has good printing durability, and has strong ink repellency. Various thermosetting organopolysiloxanes as the main component are preferably used. Thermosetting organopolysiloxanes are available in one-component and two-component types, and the two-component type cures with ≡Si.
−OH, ≡Si−OR, ≡Si−H, ≡Si−CH=CH ₂
This is due to a catalytic crosslinking reaction between siloxanes having reactive groups such as, and crosslinking reactions such as dehydration condensation, dealcoholization condensation, dehydrogenation condensation, addition polymerization, etc. occur. One-component curing reacts with moisture in the air to cause a condensation curing reaction, and includes deacetic acid type, deamined type, dealcoholized type, and deoxime type.
These are applied to one surface of the substrate by dissolving them in a suitable solvent such as benzene or toluene, applying them by a spin coating method, dipping method, dripping method, etc., and then heating and drying.

The specific type of organopolysiloxane used to form the ink-repellent organopolysiloxane cured film layer 2 is one that crosslinks and cures at room temperature or by heating after coating to become an ink-repellent silicone rubber elastic body. Highly polymerized organopolysiloxanes (which have excellent ink repellency), in which 90 mol% or more of all organic groups bonded to elementary atoms are methyl groups, are preferred; Highly polymerized diorganopolysiloxane in which 90 mol% or more of organic groups are methyl groups, with both chain ends capped with hydroxyl groups, methylhydrodiene polysiloxane or ethyl polysilicate as a crosslinking agent, and organic acid metal salt as a condensation catalyst. (2) a vinyl group-containing highly polymerized diorganopolysiloxane (at least 90 mol% of organic groups other than vinyl groups are methyl groups), a methylhydrodiene polysiloxane as a crosslinking agent, and an addition reaction catalyst. (3) a highly polymerized diorganopolysiloxane in which 90 mol% or more of the organic groups with both ends of the molecular chain blocked with hydroxyl groups are 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. is exemplified.

If necessary, the compositions exemplified in (1), (2) and (3) above may contain conventional diorganopolysiloxanes such as dimethylpolysiloxane to further improve ink repellency, which have an adverse effect on the properties of the cured coating film. There is no problem in adding a small amount of reinforcing filler such as fine powder of silica, aluminum oxide, titanium oxide, zinc oxide, etc. for the purpose of improving printing durability.

In order to form a uniform film of organopolysiloxane, it is desirable to clean the surface of the substrate in advance by an appropriate method and, if necessary, roughen the surface to improve adhesion with the film. In addition, a primer may be applied to the surface of the substrate in advance to improve adhesion with the coating.
This primer includes vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-(3-trimethoxysilylpropyl)ethylenediamine, 3-glycidoxypropyltrimethoxysilane,
Silanes such as aminopropyltriethoxysilane alone or mixtures thereof, as well as partial hydrolysates or co-hydrolysates thereof, are used;
These are applied by conventional methods such as spin coating, rod coating, brush coating, and spray coating.

Next, the protective layer 3 formed on the organopolysiloxane cured film layer 2 is not significantly affected by various radical reactions, photodecomposition reactions, etc. that occur during chemical treatment using plasma, and is not significantly affected by the organopolysiloxane cured film layer 2. Materials that do not peel off from the surface of the film layer are used, but if the film is thicker than a few microns, chemical treatment using plasma can usually be performed within tens of seconds to several minutes, so many materials can be used. . Examples of such materials include, for example, Photoresist AZ manufactured by Shippray Co., Ltd., Photoresist manufactured by Tokyo Ohka Co., Ltd.
Commercially available photoresists such as OMR and TPR, a variety of 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. In addition, to form a photoresist image, there are two methods: directly applying a photoresist solution onto the organopolysiloxane cured film layer using a conventional coating method, and applying the photoresist solution onto a film of polyethylene, polypropylene, etc., drying it, and then heat-pressing it. A method of transferring onto an organopolysiloxane cured film layer can be applied, and patterning is then performed. In the method of directly coating onto the organopolysiloxane cured film layer, the photoresist solution may be repelled by the cured organopolysiloxane film, so it is necessary to reduce the viscosity of the photoresist solution by adding an appropriate surfactant or the like.

Although the commercially available photoresists mentioned above cannot necessarily be said to have good affinity with the organopolysiloxane cured film layer, the photosensitive silicone liquid in which a photosensitive group is introduced into the organopolysiloxane exhibits good affinity and is the most easily coated. It's easy to do. In this case, the film thickness is 2
Shows sufficient plasma resistance at ~5 μm.

The photosensitive silicone liquid (photocurable organopolysiloxane) needs to have good wettability to the organopolysiloxane cured film layer 2,
For this purpose, organopolysiloxane cured film layer 2
It is preferable that the surface tension is approximately the same as that of the photocurable organopolysiloxane. The surface tension is 18 to 25 dyn/cm, preferably 20 to 23 dyn/cm.

Among the above-mentioned photosensitive silicones, organopolysiloxanes having siloxane units bonded to maleimide groups or maleimide groups containing substituted atoms or groups (JP-A-51-120804, 51−
No. 125277, No. 52-13907, No. 52-105002, No.
52-116304, etc.), organopolysiloxanes having siloxane units bonded to acryloxy groups or acryloxy groups containing substituted atoms or groups (JP-A-48-16991, JP-A-48-19682, JP-A-48-19682)
No. 48-21779, No. 48-23880, No. 48-47997,
No. 48-48000, No. 48-83722, No. 51-34291
No. 51-52001, No. 52-105003, No. 52-
105004, 52-113805, 52-113801, etc.), mixtures of organopolysiloxanes having mercapto group-containing siloxane units and organopolysiloxanes having vinyl group-containing siloxane units (JP-A-53-17405) etc.), mixtures of organopolysiloxanes and organohydrodiene polysiloxanes having vinyl group-containing siloxane units (see JP-A-53-15907, etc.), organopolysiloxanes having siloxane units containing amide groups (see JP-A-15907-15907, etc.), (Refer to JP-A No. 52-139200, No. 52-139504, etc.), a mixture of an organopolysiloxane having an acryloxy group-containing siloxane unit and an organopolysiloxane having a vinyl group-containing siloxane unit (Refer to JP-A No. 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 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 printing suitability. 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 organopolysiloxane cured film layer is an insulator, it is possible to form good electrostatic latent images and toner images. More simply, the film-forming resin liquid may be hand-painted or transferred by an appropriate printing means.

In the present invention, in order to chemically treat the surface of the cured film layer of organopolysiloxane using plasma,
Plasma treatment with inert gases such as Ar, He, Ne or active gases such as oxygen or air is suitable. In chemical treatment using plasma,
(1) Etching, (2) Chemical modification, (3) Crosslinking, (4) Polymerization
Although it is said that a complex combination of types of changes occur, in the plasma treatment using an inert gas or active gas in the present invention, electron microscopic observation and infrared absorption measurements show that surface etching does not occur, but mainly organopolymerization. Chemical modification of the siloxane cured film layer, ie, elimination of alkyl groups and generation of hydroxyl groups and carbonyl groups, occurs. As a result, the active chemical species in the plasma state collide with the surface of the organopolysiloxane cured film, resulting in
It is thought that elimination of alkyl radicals, generation of silicon radicals, three-dimensionalization of the organopolysiloxane due to crosslinking, generation of hydroxyl groups and carbonyl groups due to oxidation of alkyl groups, etc. occur. Furthermore, these reactions proceed not only on the surface of the cured organopolysiloxane film layer but also considerably deep inside the organopolysiloxane cured film layer depending on the processing time. It is presumed that this is because the cured organopolysiloxane film layer generally has high gas permeability, so that the active chemical species reach the inside of the layer.

On the other hand, corona treatment and flame treatment only work on the surface, and this effect is usually lost by simply rubbing it with your hands or cloth. In contrast, in the plasma treatment according to the present invention, the effect is not lost even if the treated film is rubbed to the point of wear.

The low-pressure atmosphere for forming plasma active chemical species may generally be air, but it may also contain inert gases such as Ar, Ne, He, etc., active gases such as O ₂ , N ₂ , NH ₃ , CO ₂ , fluorinated hydrocarbon gases, etc. Gas can be used.

The plasma lipophilization treatment time varies depending on the conditions, but for example, under the conditions of 3 × 10 ^-2 Torr and 300 W, the organopolysiloxane cured film layer is effectively modified in 30 seconds or more, but under the same conditions If the time is longer than 20 minutes, the protective layer will deteriorate due to the etching effect, which is not preferable.

When the plasma protective layer is made thinner to provide higher resolution, plasma resistance generally decreases. This is because the general organic protective layer, like the silicone layer, is attacked by plasma and vaporized and scattered for a while, becoming thinner. Therefore, if a substance having plasma resistance is mixed in the organic protective layer, even a thin protective layer can function satisfactorily and high resolution can be obtained. Organic or inorganic fillers are generally used, with inorganic fillers being particularly preferred. The reason for this is that even if the inorganic filler is attacked by oxygen plasma and undergoes a chemical change, it tends to remain as an oxide. Therefore, if a metal oxide, for example
ZnO, TiO ₂ , Cu ₂ O and others do not undergo chemical changes and are not attacked.

Since the characteristic of plasma attack is that it attacks perpendicular objects at right angles, even a substance simply placed on the organopolysiloxane cured film layer has a protective effect.
For this reason, the filler in the protective layer can therefore be regulated to a suitable amount.

These inorganic substances include SiO ₂ , TiO ₂ , ZnO,
_PbO2 , _Al2O3 , Al(OH) _{3 ,} Fe, Zn, Sn, Ni,
It is desirable that metal powders such as Cu, Ge, Al, or metal sulfides, double salts, complex salt powders, etc. (inorganic pigments are preferred) be mixed alone or in a mixture of about 10 to 70% by weight in the protective layer. .

When the organopolysiloxane cured film layer is sufficiently plasma-treated, it becomes slightly matte and has a whiter surface than the untreated portion. However, visibility is not very good. Therefore, if the organopolysiloxane cured film layer contains a substance that causes color development, decolorization, or other color change by utilizing the chemical reactivity of plasma gas, the plasma treatment effect becomes very obvious. For example, in oxygen or air plasma treatment, if a solvent-soluble basic dye or other oxidative decolorizing dye is present, the plasma-treated area and the degree of treatment can be recognized.

As the dye, ordinary disperse dyes and cationic dyes can be used. For example, Kayaset Blue FR (manufactured by Nippon Kayaku), TS
- Violet 501 (manufactured by Sumitomo Chemical); cationic dyes include crystal violet and methylene blue; it is desirable to contain the dye in an amount of about 0.01 to 5% by weight based on the organopolysiloxane;

On the other hand, if it contains an oxidative color-forming dye or pigment, the plasma treated area will be colored. For example, when a leuco dye is included, the color of the dye is formed only in the treated area. Examples of this type of dye include lactone-cyclized leuco dyes (methylene blue, etc.) and reduction-colorless dyes (PAT dyes).

Since the organopolysiloxane cured film layer has good gas permeability, active gas can penetrate into the layer during plasma treatment, and the entire layer can be treated. Therefore, in order to determine the end point of the treatment, if the subbing layer (anchor layer or silane coupling agent layer) of the organopolysiloxane cured film layer contains the above-mentioned color-changing substance, the subbing layer (anchor layer or silane coupling agent layer) of the organopolysiloxane cured film layer can be submerged once the plasma treatment is completed. It can act on the discoloration substance in the coating layer to cause color development, decolorization, and other discoloration. This method is extremely effective in determining the end point of plasma processing.

Next, in order to remove the protective layer after chemical treatment with plasma, in the case of photoresist, it is not preferable to use strong acids or strong alkalis that can damage the organopolysiloxane cured film layer, such as acetone, ethyl cellosolve, toluene, etc. It is desirable to remove it with a solvent such as for example,
Photoresist AZ manufactured by Shippray is acetone,
It can be removed by dissolving with methyl ethyl ketone (MEK), etc., and with Tokyo Ohka TPR, it can be removed with ethyl cellosolve. A resist layer formed by screen printing can be removed using a solvent such as toluene, and a resist layer formed by electrostatic printing can be removed using a polar solvent such as MEK. Furthermore, since the organopolysiloxane cured film layer generally has weak adhesion to other substances, the residual resist film can be easily removed using a suitable adhesive tape, adhesive sheet, or the like.

Next, in order to give the printing plate of the present invention practical printing durability and durability, a layer of a material that is ink-friendly and has excellent abrasion resistance is applied to the plasma-treated surface of the organopolysiloxane cured film layer. Form.

Fortunately, the plasma-treated part exhibits hydrophilic and lipophilic properties, so other resins with high wear resistance can be bonded to it. For example, if a general thermosetting resin is applied with a roller, it will adhere only to the plasma treated area shown in FIG.

These cured resins are ink-friendly and wear-resistant, and are used in the wear-resistant image area 4 (fifth
(Fig.), the durability is now superior to that of an organopolysiloxane cured film layer. In addition, since the image area 4 protrudes about 0.1 to 5 μm from the surface of the organopolysiloxane cured film layer 2, it becomes a planar relief type, exhibiting better printing suitability, and the printing durability of the organopolysiloxane cured film in the non-image area. It is determined by the durability of the layers, and has a printing life of 200,000 to 300,000 sheets.

In addition to being able to manufacture the printing plate having the configuration shown in FIG. 5 in the manner described above, it can also be manufactured in the following manner. That is, as shown in FIG. 4b, an ink-philic and abrasion-resistant material such as a thermosetting resin such as acrylic polyol resin is applied to the surface having the plasma treated part 2' and the protective layer 3 shown in FIG. The cured resin film on the protective layer 3 is coated to a thickness of ~10 μm, cured, and then removed by the above-described method of removing the protective layer, such as lightly rubbing with a soft cloth impregnated with a solvent such as methyl ethyl ketone. It is easily peeled off together with the protective layer 3, while the cured resin film on the plasma-treated portion 2' remains as it is because it is strongly adhered, and as a result, a printing plate having the structure shown in FIG. 5 is obtained.

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

Example 1 After forming a cured film layer of polydimethylsiloxane (KS774, manufactured by Shin-Etsu Chemical Co., Ltd.) to a thickness of 5 μm on an aluminum substrate, it was coated at the interface with 100 parts by weight of a polycinnamic acid-based photosensitive resin (TPR, manufactured by Tokyo Ohka Chemical Co., Ltd.). Add 0.4 parts by weight of activator (manufactured by 3M, FC431) to 4μ
It was applied to a thickness of m and dried.

The coating performance was very good, and the adhesion to the polydimethylsiloxane cured film layer was also improved.

After exposure and development according to the TPR processing method, this product is placed in a plasma reaction chamber and exposed to the atmosphere.
After plasma treatment for 2 minutes under the conditions of 300W and 0.3 Torr, a silane coupling agent (manufactured by Shin-Etsu Chemical,
KBM603) was made into a 0.5% toluene solution and applied to Whaler, and dried at 100°C.

Next, acrylic polyol resin (manufactured by Soken Chemical Co., Ltd.,
Thermorac U-245B) 15 parts by weight, isocyanate curing agent (Takenate Pharmaceutical Co., Ltd., Takenate A-3) 10
A solution containing 350 parts by weight of ethyl acetate was coated on Whaler and cured at 100°C. When this cured surface was lightly rubbed with a soft cloth soaked in methyl ethyl ketone, the cured resin film on the plasma-treated dimethylpolysiloxane cured film layer was firmly adhered and did not peel off, but the other parts It was easily peeled off along with the resist film, and a cured resin image was obtained on the dimethylpolysiloxane cured film layer. This cured resin protrudes by about 3 μm from the surface of the dimethylpolysiloxane cured film, forming a planar relief plate, with good ink receptivity and printing durability of approximately 3 μm when offset printing is performed.
There were 300,000 letters.

Example 2 In Example 1, immediately after the plasma treatment, the resist film was removed by rubbing lightly with a cloth impregnated with methyl ethyl ketone. Next, urethane thermosetting adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., base material Takerakku A-310 No. 12)
Weight parts and isocyanate curing agent Takenate A-
A mixture of 1 part by weight of No. 3 and 520 parts by weight of ethyl acetate) was applied using a Whaler and heated to 60°C.

At this time, the adhesive on the dimethylpolysiloxane cured film layer that had not been plasma-treated by the protective film aggregated on the dimethylpolysiloxane cured film layer that had been plasma-treated. This material was heated to 100°C to complete curing of the resin and create a strong image. In this case as well, the resin part was of a planar relief type in which the resin part protruded by about 5 μm from the surface of the dimethylpolysiloxane cured film layer, the ink receptivity was good, and the printing life in offset printing was about 200,000 passes.

[Brief explanation of the drawing]

1 to 5 are partially enlarged step-by-step views of successive steps showing the manufacturing process of a printing plate for lithographic printing according to the present invention. DESCRIPTION OF SYMBOLS 1...Substrate, 2...Non-image area consisting of an organopolysiloxane cured film layer, 2'...An image area consisting of an organopolysiloxane cured film layer whose surface has been chemically treated with plasma, 3...Protective layer , 4...
A layer of ink-philic and wear-resistant material.

Claims (1)

[Scope of Claims] 1. On one side of the substrate, a non-image area consisting of an organopolysiloxane cured film layer and an organopolysiloxane cured film layer whose surface has been chemically treated with activated chemical species in a plasma state. 1. A printing plate for lithographic printing, having an image area formed of a layer of an ink-friendly and abrasion-resistant material. 2. After providing an organopolysiloxane cured film layer on one side of the substrate, and then providing a protective layer in a pattern on the cured film layer, the cured film layer is deprotected using activated chemical species in a plasma state. A cured organopolysiloxane film is formed on the substrate by chemically treating the layer portion, then removing the protective layer, and then forming a layer of an ink-philic and wear-resistant material on the plasma-treated surface of the cured film layer. Lithographic printing characterized by forming a non-image area consisting of a layer and an image area consisting of a layer of an ink-philic and abrasion-resistant material formed on a plasma-treated organopolysiloxane cured film layer. Method of manufacturing printing plates. 3. After providing an organopolysiloxane cured film layer on one side of the substrate, and then providing a protective layer in a pattern on the cured film layer, the cured film layer is deprotected using activated chemical species in a plasma state. After chemically treating the layer portion and then forming a layer of ink-philic and wear-resistant material on the entire surface, the protective layer is removed together with the layer of ink-philic and wear-resistant material formed thereon. By this, a non-image area consisting of an organopolysiloxane cured film layer on the substrate and an image area consisting of a layer of an ink-philic and wear-resistant material formed on the plasma-treated organopolysiloxane cured film layer. A method for producing a printing plate for lithographic printing, characterized by forming a lithographic printing plate.