JPH0986065A - Direct drawing type waterless planographic printing base plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently absorb laser beam and to enhance sensitivity, in a direct drawing type waterless planographic printing base plate obtained by successively laminating a thermal layer and a silicone rubber layer to a substrate, by forming the thermal layer from a metal membrane having a specific m.p. SOLUTION: A planographic printing base plate made printable without using soaking water is obtained by successively laminating a thermal layer and a silicone rubber layer on a substrate and the thermal layer is formed from a membrane of a metal with an m.p. of 930K or less. Metal has an m.p. of 2000K or less and is composed of at least one kind selected from a group consisting of titanium, aluminum, nickel, iron, chromium, tellurium, tin, antimony, gallium, magensium, polynium, selenium, thallium, zinc and bismuth or an alloy composed of a combination of two kinds selected from a group consisting of tellurium, tin, antimony, gallium, bismuth and zinc. The thickness of the thermal layer is set to 1000Å or less and the optiical density thereof is set to 0.6-2.3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterless planographic printing plate precursor which can be printed without using dampening water, and more particularly to a direct drawing type waterless planographic printing plate precursor which can be directly made by laser light. Things.

[0002]

2. Description of the Related Art Direct plate making, in which an offset printing plate is produced directly from an original without using a plate making film, is simple, does not require skill, is quick in obtaining a printing plate in a short time, Utilizing features such as rationality that can be selected according to quality and cost from the system,
In addition to the light printing industry, it has begun to enter the general offset printing and gravure printing fields.

In recent years, new types of various lithographic printing materials have been developed in recent years due to rapid advances in output systems such as prepress systems, imagesetters, and laser printers.

[0004] These lithographic printing plates can be classified according to plate making methods: a method of irradiating a laser beam, a method of writing with a thermal head, a method of partially applying a voltage with a pin electrode,
A method of forming an ink repellent layer or an ink deposited layer by ink jetting, and the like can be given.

[0005] Above all, the method using laser light is superior to other methods in resolution and plate making speed.
There are many types.

[0006] The lithographic printing plate using the laser light is further classified into two types, a photon mode by a photoreaction and a heat mode by which photothermal conversion is performed to cause a thermal reaction.

As the photon mode type, (1) a high sensitivity PS plate using a photopolymer (2) an electrophotographic lithographic plate using an organic photoconductor or zinc oxide (3) a silver salt lithographic plate (4) a silver salt composite System lithography (5) Direct drawing master, etc., and the heat mode type includes (6) Thermal destruction system lithography.

[0008]

[Problems to be Solved by the Invention] However, (1)
The method uses an argon ion laser as the laser light source, which makes the equipment large, and the printing plate uses high-sensitivity photopolymer. There is a drawback that the property is easily reduced.

The electrophotographic lithographic method (2) has an advantage that it can be handled in a bright room, but since the dark decay becomes large within 2 to 5 minutes after charging of the photosensitive layer, the exposure and development process is performed in a short time after charging. Therefore, it is difficult to output a large format with high resolution.

In the silver salt method (3), printing plates corresponding to lasers of various wavelengths have been developed. However, there is a problem that silver waste liquid comes out, and since the sensitivity is high, care must be taken when handling. There is also a problem that requires.

(4) The silver-salt composite lithographic plate is provided with a high-sensitivity silver halide emulsion layer on a photosensitive layer, exposing the upper silver halide emulsion layer with an argon ion laser, developing the resultant, and further using the mask as a mask for further ultraviolet irradiation. Exposure and development. However, since this printing plate has two exposure and development steps, there is a problem that the processing of the printing plate becomes complicated.

The direct drawing master (5) does not directly write on a printing plate with a laser, but transfers a toner image formed by a laser printer onto a printing plate as an ink-coated portion. However, the resolution of the printing plate is inferior to other methods.

For the above photon mode type,
The thermal destruction method of (6) has an advantage that it can be handled in a bright room, and its usefulness has recently been reviewed due to the rapid progress of the semiconductor laser that serves as a light source.

For example, Japanese Patent Laid-Open No. 6-199064, US
P5339737, USP5353705, EP0
580393, JP-A-6-55723, EP057.
No. 3091 and US Pat. No. 5,378,580 describe a direct drawing type waterless planographic printing plate precursor using a laser beam as a light source.

The heat-sensitive layer of the printing plate precursor of this thermal destruction method is
Carbon black is used as the laser light absorbing compound, and nitrocellulose is used as the thermal decomposition compound. This carbon black is converted into thermal energy by absorbing the laser beam, and the heat destroys the heat-sensitive layer.

Finally, by removing this portion by development, the silicone rubber layer on the surface is peeled off at the same time to form an ink inking portion.

However, this printing plate has a problem that the sensitivity of the printing plate is low because the absorptance of laser light is not sufficient.

The cause of this is that the primary particle diameter of the carbon black used is not appropriate.

That is, the primary particle diameters of the carbon blacks used in the above patents are all 30 μm or more,
It cannot be said that the light of the semiconductor laser used (wavelength near 800 nm) is absorbed efficiently.

This is one measure of the absorption efficiency of laser light, and when the optical density of the printing plate is the above particle size,
This is because it does not reach the maximum.

That is, the optical density becomes maximum when the particle diameter is around 20 μm, and when it exceeds 30 μm, the blackness is lowered. This is because the reflection of light on the surface increases.

Further, even if the particle diameter is smaller than 15 μm, the optical density is lowered.

This is because the smaller the particles, the more easily the carbon black itself becomes transparent and the lower the dispersibility of the particles.

In addition, since the carbon black of the above-mentioned patent has a high oiling amount, that is, has a high structure structure, the particles agglomerate with each other and the viscosity of the heat-sensitive layer solution becomes high, which makes the handling inconvenient. However, there is a problem that the coating film does not become uniform.

Further, in particular, JP-A-6-55723, EP
In 0573991 and US Pat. No. 5,378,580, since an Nd-YAG laser is used as a light source, there is another problem that the exposure apparatus becomes quite large.

Further, US Pat. No. 5,379,698 describes a direct drawing type waterless planographic printing plate using a metal thin film as a heat sensitive layer.

Since this printing plate material has a very thin heat-sensitive layer, a very sharp image can be obtained and it is advantageous in terms of the resolution of the printing plate, but there is a problem that the sensitivity of the printing plate is poor.

This is because the metals used are titanium, aluminum, iron, nickel and chromium, and when these metals are used as a vapor deposition film, the reflection of laser light on the surface is large and the melting point of the metal is It was due to the high price.

Further, in order to solve this problem, an antireflection layer must be provided on the metal thin film, which further increases the number of coating steps and results in cost increase.

In order to remedy the drawbacks of the prior art, the present invention has conducted extensive studies on a material that efficiently absorbs laser light and easily evaporates or melts due to its heat. We have found a metal material that has a good absorptivity and that allows easy pattern formation.

Therefore, according to the present invention, it becomes possible to efficiently absorb the laser beam by only one heat-sensitive layer and to perform exposure with lower energy than the conventional one.

Therefore, the object of the present invention is to improve the sensitivity,
To provide a direct drawing type waterless planographic printing plate.

[0033]

To achieve the above object, the present invention comprises the following constitution.

1. A direct drawing type waterless planographic printing plate precursor in which a heat sensitive layer and a silicone rubber layer are sequentially laminated on a substrate, wherein the heat sensitive layer is a metal thin film having a melting point of 930 (K) or less. Waterless planographic printing plate original.

2. 1. The direct drawing waterless lithographic printing plate precursor as described in 1 above, wherein the metal is at least one selected from the group consisting of tellurium, tin, antimony, gallium, magnesium, polonium, selenium, thallium, zinc and bismuth.

3. In the above 1, the metal is a combination of any two kinds selected from the group consisting of tellurium, tin, antimony, gallium, bismuth and zinc,
Direct drawing type waterless planographic printing plate precursor characterized by being an alloy.

4. In the above 1, the metal is a combination of any three kinds selected from the group consisting of tellurium, tin, antimony, gallium, bismuth and zinc,
Direct drawing type waterless planographic printing plate precursor characterized by being an alloy.

5. In the above 1, the thickness of the heat sensitive layer is 1
A direct drawing type waterless planographic printing plate precursor characterized by having a thickness of 000 angstroms or less.

6. 1. The direct drawing type waterless planographic printing plate precursor as described in 1 above, wherein the heat sensitive layer has an optical density of 0.6 to 2.3.

7. 1. A direct drawing type waterless planographic printing plate precursor as described in 1 above, wherein a silane coupling agent layer is provided between the heat sensitive layer and the silicone rubber layer.

8. A waterless planographic printing plate obtained by selectively exposing and developing the direct drawing type waterless planographic printing plate precursor described in any one of 1 to 7 above.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Here, the direct drawing type means that an image is formed directly from a recording head on a printing plate without using a negative or positive film at the time of exposure.

Further, the optical density here means the Ratten filter No. Macbeth Densitometer RD with 106
-Numerical value when measured at 514.

Next, the direct drawing type waterless planographic printing plate used in the present invention will be explained.

It is important that the heat-sensitive layer used in the present invention efficiently absorbs a laser beam and a part or all of it is evaporated or melted instantaneously by the heat.

First, in order to absorb the laser light efficiently, the wavelength of the semiconductor laser used as the light source (800
The absorption rate for (near nm) becomes important.

Then, the optical density of the heat-sensitive layer is measured as an index of the absorptance for the light near 800 nm. That is, the higher the optical density, the more efficiently the laser light can be absorbed.

The optical density is preferably 0.6 to 2.3, more preferably 0.8 to 1.8. If the optical density is less than 0.6, the sensitivity of the printing plate is likely to be lowered because the laser light is not efficiently absorbed, and the film thickness is increased even if it is more than 2.3 to form an image. Extra energy is required and the sensitivity is reduced.

From the viewpoint of the sensitivity of the printing plate, the melting point of the metal is very important. That is, if the melting point is too high, the metal does not melt or evaporate even when irradiated with laser light. Specifically, any metal can be used as long as it has a melting point of 930 (K) or less.

Specific examples of such a metal include tellurium, tin, antimony, gallium, magnesium, polonium, selenium, thallium, zinc and bismuth.

These metals are preferable in the case of forming a vapor deposition film because a pattern is easily formed by laser light.

However, if the melting point is too low, on the other hand, the shape retention of the printing plate tends to deteriorate, so that the particularly preferable melting point range is 500 (K) to 930 (K).

Specific examples of such a metal include tellurium, tin, antimony, magnesium, polonium, thallium, zinc and bismuth.

The use of two or three types of alloys of these metals makes it easier to lower the melting point and improves the sensitivity as a printing plate, and is particularly preferable.

When an alloy is used, various materials can be produced by combining metals, and therefore the above-mentioned melting point 9
Combinations of all the metals of 30 (K) or less can be used, but among these, from the viewpoint of ease of handling, two or three of the metals of tellurium, tin, antimony, gallium, bismuth, and zinc are used. Is preferred.

Specific combinations include tellurium / tin, tellurium / antimony, tellurium / gallium, tellurium / bismuth, tellurium / zinc, and tin / tin.
Antimony, tin / gallium, tin / bismuth, tin /
Zinc is preferred, and more preferably tellurium / tin, tellurium / antimony, tellurium / zinc, tin / antimony, tin / zinc.

These alloys have good shape retention,
Since the melting point is 930 (K) or less, the sensitivity becomes high, which is particularly preferable.

The three alloys include tellurium / tin / antimony, tellurium / tin / gallium, tellurium / tin / bismuth, tellurium / tin / zinc, tellurium / zinc / antimony, tellurium / zinc / gallium, tellurium / zinc / bismuth. , Tin / zinc / antimony, more preferably tellurium / tin / antimony, tellurium / tin / zinc,
Tin / zinc / antimony.

These alloys also have good shape retention,
Since the melting point is 930 (K) or less, the sensitivity becomes high, which is particularly preferable.

At this time, the film thickness of the thin film also greatly affects the sensitivity of the plate material.

That is, if the film thickness is too thick, extra energy is required to evaporate and melt the thin film, so that the sensitivity of the plate material decreases.

Therefore, the film thickness is preferably 1000 angstroms or less, more preferably 200 angstroms or less.

As a method of forming such a thin film, it is preferable to carry out either of vacuum vapor deposition and sputtering.

The vacuum vapor deposition is generally carried out by heating and evaporating metal and carbon in a decompression container of 10 ⁻⁴ to 10 ⁻⁷ mmHg to form a thin film on the surface of the substrate.

Sputtering is 10 ^-1 to 10 ^-3 mmHg
Direct current or alternating current voltage is applied to the pair of electrodes in the decompression container to cause glow discharge, and a thin film is formed on the substrate by utilizing the sputtering phenomenon of the cathode.

It is also important to provide a silane coupling agent layer on the heat-sensitive layer in order to improve the adhesion between the heat-sensitive layer and the silicone rubber layer.

As a result, the printing durability and solvent resistance of the printing plate are greatly improved.

As the silane coupling agent, vinyl silane, (meth) acryloyl silane, epoxy silane,
All known aminosilanes such as aminosilane, mercaptosilane and chlorosilane can be used, but of these, (meth) acryloylsilane, epoxysilane, aminosilane and mercaptosilane are preferably used.

Specifically, the (meth) acryloylsilane is 3- (meth) acryloylpropyltrimethoxysilane, 3- (meth) acryloylpropyltriethoxysilane, and the epoxysilane is 3-glycidoxy. Propyltrimethoxysilane, 2- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, and as the aminosilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2
It is-(aminoethyl) -3-aminopropylmethyldimethoxysilane and 3-aminopropyltriethoxysilane, and examples of the mercaptosilane include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

These silane coupling agents are dissolved in a suitable solvent and applied as a dilute solution on the heat-sensitive layer.
Perform heat cure.

The film thickness of the silane coupling agent layer is sufficient as long as a monomolecular film of the silane coupling agent is formed, and specifically, it is preferably 1000 angstroms or less, more preferably. It is 500 angstroms or less.

When the film thickness is thicker than 1000 angstroms, the adhesiveness with the silicone rubber layer is likely to be lowered, and the printing durability and solvent resistance of the printing plate are reduced.

As a substrate for forming the above heat sensitive layer, a dimensionally stable plate is used. Such dimensionally stable plate-like objects include those conventionally used as substrates for printing plates, and they can be suitably used. Such substrates include paper and plastic (eg polyethylene, polypropylene, polystyrene, etc.)
Laminated paper, for example, a metal plate such as aluminum (including aluminum alloy), zinc, copper, etc.,
For example, plastic films such as cellulose, carboxymethyl cellulose, cellulose acetate, polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, and the like, and the metals described above. Include laminated or vapor deposited paper or plastic film. Among these substrates, the aluminum plate is particularly preferable because it is extremely stable in dimension and inexpensive. Further, a polyethylene terephthalate film used as a substrate for light printing is also preferably used.

The waterless planographic printing plate used in the present invention may be provided with a primer layer in order to strengthen the adhesion between the substrate and the heat sensitive layer. The primer layer of the direct drawing type waterless planographic printing plate precursor used in the invention is required to satisfy the following conditions. That is, the substrate and the heat-sensitive layer are well adhered, stable over time, and the solvent resistance of the developer to the solvent is good. As a material satisfying such a condition, in addition to a material containing an epoxy resin as shown in Japanese Patent Publication No. 61-54219, a polyurethane resin,
Phenol resin, acrylic resin, alkyd resin, polyester resin, polyamide resin, melamine resin, urea resin, benzoguanamine resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, polyvinyl butyral resin,
Ethylene-vinyl acetate copolymer, polycarbonate resin, polyacrylonitrile-butadiene copolymer, polyether resin, polyether sulfone resin, milk casein, gelatin and the like can be used. These resins may be used alone or in combination of two or more.

Of these, polyurethane resins, polyester resins, acrylic resins, epoxy resins, urea resins and the like are preferably used alone or in admixture of two or more.

As the anchor agent constituting the primer layer, a known adhesive such as a silane coupling agent can be used, and organic titanate is also effective.

It is also optional to add a surfactant for the purpose of improving the coatability.

In the exposed area of the printing plate, the primer layer is exposed and becomes an image area. Therefore, it is preferable to add an additive such as a dye to the primer layer to improve the plate inspection property.

The composition for forming the above-mentioned primer layer is prepared as a composition solution by dissolving it in a suitable organic solvent such as DMF, methyl ethyl ketone, methyl isobutyl ketone, dioxane, toluene, xylene and THF. A primer layer is formed by uniformly applying the composition solution on a substrate and heating it at a required temperature for a required time.

The thickness of the primer layer is 0.5 as a coating layer.
５０50 g / m ² , preferably 1-10 g
/ M ² . When the thickness is less than 0.5 g / m ² , the effect of blocking morphological defects and chemical adverse effects on the surface of the substrate is reduced, and when it is more than 50 g / m ^2, it is disadvantageous from the economical point of view, so the above range is preferable.

As the uppermost silicone rubber layer, all conventional silicone rubber compositions for waterless lithographic printing plates can be used.

Such a silicone rubber layer is obtained by sparsely cross-linking a linear organopolysiloxane (preferably dimethylpolysiloxane), and a typical silicone rubber layer is represented by the following formula (I). It has a repeating unit as shown in.

[0083]

Embedded image (Here, n is an integer of 2 or more. R has 1 to 10 carbon atoms.)
Alkyl, aryl, or cyanoalkyl group. Preferably, 40% or less of the whole R is vinyl, phenyl, vinyl halide, or halogenated phenyl, and 60% or more of R is a methyl group. Further, it has at least one or more hydroxyl group in the molecular chain at the chain end or in the form of a side chain. In the case of the silicone rubber layer applied to the printing plate of the present invention, a silicone rubber (R
TV, LTV type silicone rubber). As such a silicone rubber, R of an organopolysiloxane chain is used.
Although a part of H may be substituted with H, it is usually crosslinked by condensation of the terminal groups represented by the following formulas (II), (III) and (IV). In some cases, an excess of a crosslinking agent may be present.

[0084]

Embedded image

Embedded image

Embedded image (Where R is the same as R described above; R1, R2
Is a monovalent lower alkyl group, and Ac is an acetyl group. ) Silicone rubber which performs such condensation type crosslinking includes:
A metal carboxylate such as tin, zinc, lead, calcium, or manganese, for example, dibutyltin laurate, tin (II) octoate, naphthenate, or a catalyst such as chloroplatinic acid is added.

In addition to these compositions, it is also effective to add the above-mentioned known silane coupling agent for the purpose of improving the adhesiveness to the heat-sensitive layer.

When the silane coupling agent is added to the silicone rubber layer, it is not necessary to provide the silane coupling agent layer.

In addition to the above, it is optional to add a hydroxyl group-containing organopolysiloxane or a hydrolyzable functional group-containing silane (or siloxane), which is a composition of the condensation type silicone rubber layer, and to improve the rubber strength. For this purpose, it is optional to add a known filler such as silica.

Further, in the present invention, in addition to the above condensation type silicone rubber, addition type silicone rubber can be used.

As the addition type silicone rubber, it is preferable to use, as shown below, a hydrogen polysiloxane having a Si--H bond and a vinyl polysiloxane having a CHCH bond which are crosslinked and cured by a platinum catalyst. .

(1) 100 parts by weight of organopolysiloxane having at least two alkenyl groups (preferably vinyl groups) directly bonded to a silicon atom in one molecule (2) at least 2 groups of the formula (V) in one molecule Organohydrogenpolysiloxane having 0.1 to 1000 parts by weight (3) Addition catalyst 0.00001 to 10 parts by weight The alkenyl group of the component (1) may be at the end of the molecular chain or at the middle thereof. As organic groups other than
It is a substituted or unsubstituted alkyl group or aryl group.
The component (1) may have a small amount of hydroxyl groups. The component (2) reacts with the component (1) to form a silicone rubber layer,
It plays a role of imparting adhesiveness to the photosensitive layer. The hydrogen group of the component (2) may be at the terminal of the molecular chain or at the middle, and the organic group other than hydrogen is selected from those similar to the component (1). The organic groups of the components (1) and (2) preferably have a methyl group content of 60% or more of the total number of the groups from the viewpoint of improving the ink repellency. Component (1) and component (2)
The molecular structure of may be linear, cyclic, or branched, and it is preferable that at least one of them has a molecular weight of more than 1000 from the viewpoint of rubber physical properties, and further, the molecular weight of component (2) may exceed 1,000. preferable. Examples of the component (1) include α, ω-divinylpolydimethylsiloxane and a (methylvinylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and the component (2) has a hydrogen group at both ends. Polydimethylsiloxane, α, ω-
Examples thereof include dimethyl polymethyl hydrogen siloxane, (methyl hydrogen siloxane) (dimethyl siloxane) copolymer having methyl groups at both ends, and cyclic polymethyl hydrogen siloxane. The addition catalyst of the component (3) is arbitrarily selected from known catalysts, and is particularly preferably a platinum compound, such as platinum alone, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. In order to control the curing rate of these compositions, organopolysiloxanes containing vinyl groups such as tetracyclo (methylvinyl) siloxane, alcohols containing carbon-carbon triple bonds, etc.
It is also possible to add crosslinking inhibitors such as toluene, acetone, methyl ethyl ketone, methanol, ethanol and propylene glycol monomethyl ether. These compositions have the characteristic that, when the three components are mixed, an addition reaction occurs and curing starts, but the curing rate increases rapidly as the reaction temperature increases. Therefore, for the purpose of prolonging the pot life of the composition until it becomes rubber, and shortening the curing time on the photosensitive layer, the curing conditions of the composition are temperature conditions in which the characteristics of the substrate and the photosensitive layer do not change, Further, it is preferable to keep the temperature at a high temperature until it is completely cured, from the viewpoint of stability of the adhesive force with the photosensitive layer.

The thickness of these silicone rubber layers is 0.5.
To 50 g / m ² , more preferably 0.5 to 50 g / m ^2.
It is 10 g / m ² . When the film thickness is less than 0.5 g / m ² , the ink repellency of the printing plate tends to decrease, and
If it is larger than g / m ² , it is disadvantageous from an economic point of view.

For the purpose of protecting the silicone rubber layer on the surface of the waterless lithographic printing plate precursor constructed as described above, a thin protective film having a plane or a concavo-convex surface is laminated on the surface of the silicone rubber layer. It is also possible to form a polymer coating film which can be dissolved in the developing solvent described in JP-A-5-323588.

In particular, when a protective film is laminated, laser exposure is performed on the protective film, and then the protective film is peeled off to form a pattern on the printing plate. It is also possible to create.

Next, the method for producing a waterless planographic printing plate according to the present invention will be described. An ordinary coater such as a reverse roll coater, an air knife coater, and a Mayer bar coater or a spin coater such as a whaler was applied on the substrate, and the primer layer composition was applied if necessary and cured at 100 to 300 ° C. for several minutes. After that, a heat-sensitive layer is formed by vapor deposition or sputtering, a silicone rubber composition is applied, and heat-treated at a temperature of 50 to 150 ° C. for several minutes to cure the rubber to form a layer.

Then, a protective film is laminated or a protective layer is formed, if necessary.

The direct drawing type waterless planographic printing plate precursor thus obtained is imagewise exposed with a laser beam after peeling off the protective film or on the protective film.

A laser beam is usually used for the exposure, and the light source at this time has an oscillation wavelength of 300 nm to 1500.
such as Ar ion laser, Kr ion laser, He-Ne laser, He-Cd laser, ruby laser, glass laser, semiconductor laser, YAG laser, titanium sapphire laser, dye laser, nitrogen laser, metal vapor laser in the range of nm. Various lasers can be used. Among them, the semiconductor laser is preferable because it is miniaturized due to the recent technical progress and is economically advantageous over other laser light sources.

The direct drawing type waterless planographic printing plate exposed by the above-mentioned method is subjected to peeling development or usual solvent development treatment, if necessary.

The developing solution used in the present invention includes, for example, water, one obtained by adding the following polar solvent to water, and aliphatic hydrocarbons (hexane, heptane, “Isopar E,
G, H "(trade names of isoparaffinic hydrocarbons manufactured by ESSO), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), and halogenated hydrocarbons (trichlene, etc.). A mixture obtained by adding at least one of the following polar solvents to a mixed solvent is preferably used.

Alcohols (methanol, ethanol,
Propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol,
2,3-butylene glycol, hexylene glycol,
2-ethyl-1,3-hexanediol, etc.) Ethers (ethylene glycol monoethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2
-Ethylhexyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dioxane, tetrahydrofuran, etc. Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone) , Diacetone alcohol, etc. Esters (ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.) Acid (2-ethylbutyric acid, Prong acid, caprylic acid, 2-ethylhexanoic acid, capric acid, oleic acid,
In addition, a known surfactant can be freely added to the above-mentioned developer composition. In addition, further alkaline agent,
For example, sodium carbonate, monoethanolamine, diethanolamine, diglycolamine, monoglycolamine, triethanolamine, sodium silicate, potassium silicate, potassium hydroxide, sodium borate and the like can be added.

Further, well-known basic dyes such as crystal violet, Victor Pure Blue, Astrazone Red, acid dyes and oil-soluble dyes may be added to these developers to dye the image area at the same time as development. You can

When developing, these developing solutions may be impregnated in a non-woven fabric, absorbent cotton, cloth, sponge or the like, and the plate surface may be wiped off to develop.

For development, Japanese Patent Laid-Open No. 63-163357.
It is possible to suitably develop by pretreatment of the plate surface with the above-mentioned developing solution using an automatic developing machine as described in 1) and then rubbing the plate surface with a rotating brush while showering with tap water or the like.

Development can also be performed by spraying hot water or steam onto the plate surface instead of the above developing solution.

[0105]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Examples 1 to 7 On a degreased aluminum plate having a thickness of 0.24 mm, a primer solution having the following composition was applied and dried at 230 ° C. for 2 minutes to provide a 4 g / m ² primer layer. .

(A) Cancoat 90T-25-3094 (Epoxy phenol resin manufactured by Kansai Paint Co., Ltd.) 15 parts by weight (b) Victoria Pure Blue BOH naphthalene sulfonic acid 0.1 part by weight (c) 85 parts by weight of dimethylformamide Next, the following metal was formed on this primer layer by vacuum deposition to provide a heat-sensitive layer.

(A) Metal (Table 1) Subsequently, the following silane coupling agent solution was applied on the heat-sensitive layer and dried at 120 ° C. for 2 minutes to form an adhesive layer.

(A) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane 1 part by weight (b) Ethanol 1000 parts by weight Further, a silicone rubber solution having the following composition was formed on the adhesive layer. Apply, dry for 2 minutes at 120 ℃, thickness 2g
/ M ² of silicone rubber layer was provided.

(A) Polydimethylsiloxane (molecular weight about 25,000, terminal hydroxyl group) 100 parts by weight (b) Ethyltriacetoxysilane 12 parts by weight (c) Dibutyltin diacetate 0.1 parts by weight (d) "Isopar" G "(manufactured by Exxon Chemical Co., Ltd.) 1200 parts by weight The laminated plate obtained as described above is laminated with a polyester film" Lumirror "(manufactured by Toray Co., Ltd.) having a thickness of 8 μm using a calendar roller, A direct drawing type waterless planographic printing plate precursor was obtained.

After that, the "lumirror" of the printing plate precursor was peeled off, and the semiconductor laser (SL) mounted on the XY table was peeled off.
D-304XT, output 1 W, wavelength 809 nm, manufactured by Sony Corporation), beam diameter 20 μm, exposure time 1
Pulse exposure was performed at 0 μs. At this time, the laser output is L
The laser power on the printing plate was measured while being arbitrarily changed by a D pulse modulation driving device.

Subsequently, rubbing with a cotton pad impregnated with a developing solution having the following composition was carried out to develop.

(A) 80 parts by weight of water (b) 20 parts by weight of diethylene glycol mono-2-ethylhexyl ether The image reproducibility of this printing plate was evaluated with a magnifying power of 50 times to determine the minimum laser power for forming dots. Then, the sensitivity of the printing plate was measured from the result.

The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine), and was manufactured by Dainippon Ink and Chemicals, Inc. "Dry Ocolor" ink, indigo,
Printing was carried out on high-quality paper using red and yellow inks, and the number of sheets showing damage on the plate surface was evaluated as printing durability.

Comparative Examples 1 to 3 Printing plates were prepared and evaluated in the same manner as in Example 1, except that the silane coupling agent layer was not provided on the heat-sensitive layer.

As shown in Table 1, it can be seen that when the melting point of the metal deviates from the specified range, the sensitivity of the printing plate decreases, and when there is no silane coupling agent layer, the printing durability decreases.

[0117]

[Table 1]

[0118]

The direct drawing type waterless planographic printing plate of the present invention has improved sensitivity and printing durability as compared with the conventional direct drawing type waterless planographic printing plate.

Claims (8)

[Claims] 1. A direct drawing type waterless lithographic printing plate precursor in which a heat sensitive layer and a silicone rubber layer are sequentially laminated on a substrate, wherein the heat sensitive layer is a metal thin film having a melting point of 930 (K) or less. Direct drawing type waterless planographic printing plate precursor. 2. The metal according to claim 1, wherein the metal is tellurium, tin,
A direct-drawing waterless planographic printing plate precursor characterized by being at least one selected from the group consisting of antimony, gallium, magnesium, polonium, selenium, thallium, zinc and bismuth. 3. The metal according to claim 1, wherein the metal is a combination of any two kinds selected from the group consisting of tellurium, tin, antimony, gallium, bismuth and zinc.
Direct drawing type waterless planographic printing plate precursor characterized by being an alloy. 4. The metal according to claim 1, wherein the metal is a combination of any three selected from the group consisting of tellurium, tin, antimony, gallium, bismuth and zinc.
Direct drawing type waterless planographic printing plate precursor characterized by being an alloy. 5. The heat sensitive layer according to claim 1, wherein the film thickness is 10
A direct drawing type waterless planographic printing plate precursor characterized by having a thickness of 00 angstroms or less. 6. The direct drawing type waterless planographic printing plate precursor as claimed in claim 1, wherein the heat-sensitive layer has an optical density of 0.6 to 2.3. 7. A direct drawing type waterless planographic printing plate precursor according to claim 1, wherein a silane coupling agent layer is provided between the heat sensitive layer and the silicone rubber layer. 8. A direct drawing type waterless planographic printing plate precursor according to claim 1, which is selectively exposed and developed.
Waterless planographic printing plate.