JPS6155671B2 - - 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 producing 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 In other words, first of all, water and fat repel each other,
The non-image area is made hydrophilic by chemical or mechanical treatment, and the image area is made lipophilic by transfer of a fatty resin or photographic printing, and then water is transferred to the printing plate. After that, water is applied only to the hydrophilic non-image areas, and then ink is further transferred to this plate surface. 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 is then transferred to a substrate to obtain the desired printed material.

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 is not 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, high energy is used to thermally destroy the silicone, causing 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 selectively chemically treating with activated chemical species in a plasma state, the oil-repellent cured organopolysiloxane film changes to lipophilicity, and this change, unlike corona discharge or fire treatment, makes the cured film layer more oleophilic. It extends not only to the surface but also to the interior, and by interposing an appropriate protective layer, chemical treatment can be selectively prevented, and activation of a plasma state between the substrate and the organopolysiloxane cured film layer. The present invention was achieved by discovering that the degree of plasma treatment can be accurately determined by providing a layer of material that changes color depending on the chemical species used, that the treatment can be performed in a short time with low energy, and that it has high resolution. It is.

That is, in the present invention, a cured film layer of organopolysiloxane is provided on one surface of a substrate via a material layer that changes color due to activated chemical species in a plasma state, and then a protective layer is formed in a pattern on the cured film layer. The cured film layer of organopolysiloxane is deposited on the substrate by chemically treating the non-protective layer portion of the cured film layer with activated chemical species in a plasma state, and then removing the protective layer. The gist of this invention is a method for producing a printing plate for lithographic printing, which is characterized by forming a non-image area consisting of the chemically treated organopolysiloxane layer and an image area consisting of the chemically treated organopolysiloxane layer.

The method for producing a printing plate for lithographic printing of the present invention applies chemical treatment using plasma, and therefore has 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) Since chemical treatment using plasma utilizes a reaction between the gas phase and the solid phase, almost no physical force is applied to the protective layer, and the adhesiveness with 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 from one generator to multiple chambers, and at the same time Multiple printing plates can be made in an hour, and the equipment is relatively inexpensive.

(5) The printing plate for lithographic printing of the present invention has no difference in height between the image area and the non-image area, so compared to the conventional plano intaglio plate obtained by removing the silicone layer.
The transfer of ink to the plate blanket is improved, resulting in improved print quality.

(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. , an ink-repellent layer 3 (non-image area) consisting of an organopolysiloxane cured film layer, and an ink-receptive layer 3' (image area) consisting of an organopolysiloxane cured film layer chemically treated by plasma.
and has.

Next, a method for producing a printing plate for lithographic printing according to the present invention will be explained. As shown in FIG. After forming the organopolysiloxane cured film layer 3 to a thickness of 2 to 50 μm, a protective layer 4 is formed in a pattern on the organopolysiloxane cured film layer 3 as shown in FIG. establish. Next, when chemically treated with plasma, the organopolysiloxane cured film layer in the area where the protective layer 4 is not provided is modified and made lipophilic, as shown in FIG. ' is formed. After that, protective layer 4
When removed, the printing plate of the present invention described above is obtained as 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, an organopolysiloxane cured film layer 3 is placed on the substrate via the material layer 2 that changes color with the plasma.
The organopolysiloxane used to provide the material (the material layer 2 that changes color with plasma will be described later) has excellent strength and abrasion resistance, and has good printing durability.
It is desirable to have strong ink repellency, and various thermosetting organopolysiloxanes containing polydimethylsiloxane as a main component are preferably used. There are two types of thermosetting organopolysiloxanes: one-component type and two-component type.
This is due to a catalytic crosslinking reaction between siloxanes having reactive groups such as OH, ≡Si-OR, ≡Si-H, ≡Si-CH= _CH2 , and can be used in dehydration condensation, dealcoholization condensation, dehydrogenation condensation, and addition polymerization. A crosslinking reaction occurs. 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 can be applied 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 them.

The specific type of organopolysiloxane used to form the ink-repellent organopolysiloxane cured film layer 3 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; An organic compound whose chain ends are blocked with hydroxyl groups.
A highly polymerized diorganopolysiloxane in which 90 mol% or more is methyl groups, methylhydrodiene polysiloxane or ethyl polysilicate as a crosslinking agent, and an organic acid gold layer salt as a condensation catalyst; (2) a highly polymerized diorganopolysiloxane containing methyl groups; Polymerized diorganopolysiloxane (90 mol% or more of organic groups other than vinyl groups are methyl groups), methylhydrodiene polysiloxane as a crosslinking agent, and a platinum-based catalyst as an addition reaction catalyst, (3) molecule A highly polymerized diorganopolysiloxane in which both chain ends are capped with hydroxyl groups and 90 mol% or more of the organic groups are methyl groups, and as a crosslinking agent, three or more acetoxy groups, amino groups, oxime groups or Examples include those made of silane or low polymerization degree siloxane compounds having a hydrolyzable group such as a propenoxy group.
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, 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-
Silanes such as (3-trimethoxysilylpropyl)ethylenediamine, 3-aminopropyltriethoxysilane alone or mixtures thereof, as well as their partial hydrolysates or partially co-hydrolysates, are used, and these can be applied by spin coating, rod coating, etc. It is applied by conventional methods such as coating, brushing, and spraying.

Next, the protective layer 4 formed on the organopolysiloxane cured film layer 3 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 3. 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, many materials can be used because chemical treatment using plasma is usually performed within tens of seconds to several minutes. Become. Examples of such materials include Photoresist AZ manufactured by Shippray Co., Ltd. and 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 polyethylene, polypropylene, etc. film, 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 having substituted atoms or groups (JP-A No. 51-120804, No. 51 −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-
No. 21779, No. 48-23880, No. 48-47997, No. 48
-48000, 48-83722, 51-34291, 48-83722, 51-34291,
No. 51-52001, No. 52-105003, No. 52-105004
No. 52-113805, No. 52-113801, etc.)
A mixture of an organopolysiloxane having a mercapto group-containing siloxane unit and an organopolysiloxane having a vinyl group-containing siloxane unit (see JP-A-53-17405, etc.), an organopolysiloxane having a vinyl group-containing siloxane unit and an organohydrogen Mixtures with empolysiloxane (see JP-A-53-15907, etc.), organopolysiloxanes having siloxane units containing amide groups (see JP-A-52-139200, JP-A-52-139504, etc.);
Examples include 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 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 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 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 fire treatment only work on the surface, and this effect is usually lost just by rubbing 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 surrounding atmosphere for forming plasma active chemical species may generally be air, but it may also be an inert gas such as Ar, Ne, He, etc., or an active gas such as O ₂ , N ₂ , HN ₃ , CO ₂ , or fluorinated hydrocarbon gas. can be used.

The plasma treatment time varies depending on the conditions, but for example, under the conditions of 3 x 0.01 Torr and 300W, the organopolysiloxane cured film layer is effectively modified in 30 seconds or more, but under the same conditions for 20 minutes or more. This is not preferable because the etching effect causes deterioration of the protective layer.

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 material 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, Sn, Ni, Cu,
Ge, Al and other metal powders, metal sulfides, double salts, complex salt powders, etc. (inorganic pigments are preferred)
10 to 70% by weight in the protective layer alone or in combination
It is desirable to mix it to some degree.

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. Fortunately, the organopolysiloxane cured film layer has good gas permeability, and during plasma treatment, the active gas can penetrate into the layer and the entire layer can be treated, so the present invention was developed to determine the effect of this treatment. Therefore, it becomes effective to provide a material layer 2 that changes color due to plasma. In other words, if the undercoat layer (anchor layer or silane coupling agent layer) of the organopolysiloxane cured film layer 3 contains a plasma discoloration substance, it will act on the discoloration substance in the undercoat layer when plasma treatment is completed. It can cause color development, decolorization, and other discoloration. This method is extremely effective in determining the end point of plasma processing.

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 is decolored, allowing the treated area and the degree of treatment to 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, methylene blue, etc., and it is desirable that the dye be contained in the undercoat layer in an amount of about 0.01 to 5% by weight;

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. As examples of this type, lactone-cyclized leuco dyes (methylene blue, etc.) and dyes that have been reduced and made colorless (vat dyes) are generally easy to use.

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.

The lithographic printing plate of the present invention produced as described above has a structure as shown in FIG. When ink is supplied from an ink roller to a printing plate for lithographic printing, the adhesion between the ink and the non-image area, that is, the organopolysiloxane cured film layer, is reduced between the ink and the roller, or the ink is Because the ink is lower than the cohesive force between particles, etc., the ink is not transferred to the non-image area 3, and the ink adheres only to the image area 3' whose surface has been plasma-treated. Therefore, this provides the advantage that dampening water, which is conventionally required, is completely unnecessary.

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

Example 1 One surface of an aluminum substrate was coated with a coating solution containing 0.01% by weight of crystal violet lactone in 3-aminopropyltriethoxysilane as a primer, and after drying, this treated surface was coated. After forming a cured film layer of polydimethylsiloxane (KS774, manufactured by Shin-Etsu Chemical Co., Ltd.) to a thickness of 5 μm, 100 parts by weight of polycinnamic acid photosensitive resin (TPR, manufactured by Tokyo Ohka Co., Ltd.) and a surfactant (manufactured by 3M Co., Ltd., FC431) 0.4 parts by weight of the mixed solution was applied to a thickness of 4 μm, dried, and then exposed and exposed according to the TPR processing method.
A patterned protective layer was formed by development. This material is placed in a plasma reaction chamber under the atmosphere.
When plasma treatment was performed for 5 minutes under the conditions of 300W and 0.3 Torr, only the sufficiently treated areas developed a blue color, indicating that the treatment time was short (about 1 minute) or that the plasma treatment was uneven due to uneven development of the protective layer. Some parts did not develop color. With this method,
It has been found that plasma treatment can penetrate not only the surface but also the organopolysiloxane cured film layer, and it has also been found to be an indicator of the end point of plasma treatment.

After the plasma treatment, the resist layer was peeled off using ethyl cellosolve to produce a printing plate for lithographic printing.
The printing durability was 30,000 to 50,000 sheets.

[Brief explanation of the drawing]

FIGS. 1 to 4 are partially enlarged cross-sectional views of successive steps showing the manufacturing process of a printing plate for lithographic printing according to the present invention. 1...Substrate, 2...Plasma discoloration material layer, 3...
. . . Non-image area consisting of an organopolysiloxane cured film layer, 3' . . . Image area consisting of an organopolysiloxane cured film layer whose surface has been chemically treated with plasma, 4 . . . Protective layer.

Claims (1)

[Claims] 1. A cured film layer of organopolysiloxane is provided on one side of the substrate via a material layer that changes color due to the action of activated chemical species in a plasma state, and then a protective layer is provided in a pattern on the cured film layer. , chemically treating the non-protective layer portions of the cured film layer with activated chemical species in a plasma state, and then removing said protective layer to form a non-image line of the cured film layer of organopolysiloxane on the substrate. 1. A method for producing a printing plate for lithographic printing, the method comprising: forming an image area comprising the chemically treated organopolysiloxane layer;