JP4661473B2 - Method for producing waterless planographic printing plate precursor laminate - Google Patents

Description

  The present invention relates to a waterless lithographic printing plate precursor laminate comprising a waterless lithographic printing plate precursor and a slip sheet in contact with a silicone rubber layer.

  Conventionally, various printing plates have been proposed for performing lithographic printing (hereinafter referred to as waterless printing) using silicone rubber or fluororesin as an ink repellent layer without using dampening water. In such waterless printing, the image area and the non-image area are basically in the same plane, the image area is an ink receiving layer, and the non-image area is an ink repellent layer. This means a lithographic printing method in which the ink is applied only to the image area using the difference, and then printed by transferring the ink to a printing medium such as paper, and can be printed without using dampening water. Is a feature.

  Above all, the so-called direct drawing type plate making, which does not use the plate making film directly from the manuscript, is so simple that does not require skill, quickness to obtain the printing plate in a short time, various systems Therefore, taking advantage of features such as rationality that can be selected according to quality and cost, the company has begun to enter not only the light printing industry but also general offset printing and flexographic printing. Particularly recently, various types of direct-drawing lithographic printing plates have been developed due to rapid advances in output systems such as prepress systems, imagesetters, and laser printers.

  These direct-drawing lithographic printing plates are classified according to the plate making method: 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, an ink repellent layer or an ink deposit layer by inkjet The method of forming is mentioned. Among them, the method using laser light is superior to other methods in terms of resolution and plate making speed, and there are many types.

  This printing plate using laser light is further divided into two types: a photon mode by photoreaction and a heat mode in which photothermal conversion is performed to cause a thermal reaction. In particular, the heat mode method has the advantage that it can be handled in a bright room, and has been attracting much attention recently due to the rapid progress of semiconductor lasers as a light source, and is said to become the mainstream in the future.

  As a lithographic printing plate in the heat mode, a direct-drawing waterless lithographic plate that can be printed without using a fountain solution, a direct-drawing waterless lithographic plate that performs printing using a fountain solution, and the like have been developed. The direct-drawing waterless lithographic plate has the advantages that high-quality printed materials can be obtained and that the printing start-up is quick, and that there is no alkaline waste solution generated when developing a lithographic plate with water. .

  As the direct drawing type waterless lithographic printing plate, for example, a direct drawing type waterless lithographic printing plate precursor using a laser beam as a light source and a plate making method thereof have been proposed (for example, see Patent Documents 1 and 2). Furthermore, a direct-drawing waterless lithographic printing plate containing a metal chelate compound and an active hydrogen group-containing compound in the heat-sensitive layer has been proposed (see, for example, Patent Documents 3 to 4). This printing plate has very good performances such as practically sufficient sensitivity, excellent image reproducibility, high ink repellency, and stable developability.

These direct-drawing waterless lithographic printing plate precursors have recently been widely used for plate making by a fully automatic plate making system for the purpose of high efficiency and labor saving. When making a direct-drawing waterless lithographic printing plate precursor, the printing plate passes through an automatic plate feeder, protective film remover, laser irradiation device, automatic processor, and water washer that peels the interleaf and sends the plate to the next process. However, there are many problems such as many processes, place, time and cost. As a method of simplifying the process, it is conceivable to use a direct-drawing waterless lithographic printing plate precursor having no protective film. However, in the master plate having a structure in which the protective film is removed from the conventionally known direct-drawing waterless lithographic printing plate precursor, a blocking phenomenon occurs between the silicone rubber layer and the slip sheet, and it is difficult to peel off the slip sheet in the automatic plate feeder. A problem occurred.
JP-A-6-199064 (page 5-6) JP-A-9-244228 (page 2-6) JP 11-334237 A (pages 3-6) Japanese Patent Laid-Open No. 11-348442 (page 3-10)

  An object of the present invention is to solve the problems of the prior art and to obtain a waterless lithographic printing plate precursor laminate with good interleaf separation in an automatic plate feeder.

The present inventors have made various studies in order to solve such problems of the prior art. As a result, they have found that these problems can be solved by the following method.
( 1 ) A waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate and a slip sheet in contact with the silicone rubber layer are laminated, and the silicone rubber layer and the slip sheet are substantially A method for producing a non-adhered waterless lithographic printing plate precursor laminate comprising: a step of providing at least a heat-sensitive layer on a substrate; a step of providing a silicone rubber layer; a step of curing a silicone rubber layer; comprising the step of providing a paper, the step of providing a silicone rubber layer, at least a hydroxyl group-containing silicone, SiH group-containing compound, addition reaction promoting catalyst, ethylenically unsaturated bond-containing silane coupling agent and a silicone rubber layer comprises a condensation reaction promoting catalyst method for producing a waterless planographic printing plate precursor laminate you comprising the step of applying the composition solution.
( 2 ) A waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate and a slip sheet in contact with the silicone rubber layer are laminated, and the silicone rubber layer and the slip sheet are substantially A method for producing a non-adhered waterless lithographic printing plate precursor laminate comprising: a step of providing at least a heat-sensitive layer on a substrate; a step of providing a silicone rubber layer; a step of curing a silicone rubber layer; The step of providing a silicone rubber layer, including the step of providing a paper, is applied with a silicone rubber layer composition liquid containing at least a vinyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, a silane coupling agent, and a condensation reaction promoting catalyst. method for producing a waterless planographic printing plate precursor laminate you comprising the step of.
( 3 ) The silicone rubber layer composition liquid is composed of at least two liquids: (c) a liquid containing at least a SiH group-containing compound and a condensation reaction promoting catalyst, and (d) a liquid containing at least an addition reaction promoting catalyst. ( 1 ) or ( 2 ), The method for producing a waterless lithographic printing plate precursor laminate as described in ( 1 ) or ( 2 ), wherein
(4) (c) a liquid comprising at least SiH group-containing compound and a condensation reaction promoting catalyst, characterized in that it comprises a silane coupling agent or an ethylenically unsaturated bond-containing silane coupling agent (3) without water according A method for producing a lithographic printing plate precursor laminate.
(5) A method for producing a waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, the step of providing at least a heat-sensitive layer on the substrate, the step of providing a silicone rubber layer, the silicone rubber layer The step of providing a silicone rubber layer comprising at least a hydroxyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, an ethylenically unsaturated bond-containing silane coupling agent, and a condensation reaction promoting catalyst. Applying a composition liquid, wherein the silicone rubber layer composition liquid comprises (c) at least a liquid containing at least a SiH group-containing compound and a condensation reaction promoting catalyst, and (d) at least a liquid containing at least an addition reaction promoting catalyst. It consists of two liquids, and these liquids are mixed at an arbitrary ratio immediately before coating, Method for producing a printing plate precursor.
(6) A method for producing a waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, the step of providing at least a heat-sensitive layer on the substrate, the step of providing a silicone rubber layer, a silicone rubber layer And a step of providing a silicone rubber layer is applied with a silicone rubber layer composition liquid containing at least a vinyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, a silane coupling agent, and a condensation reaction promoting catalyst. The silicone rubber layer composition liquid comprises at least two liquids: (c) a liquid containing at least a SiH group-containing compound and a condensation reaction promoting catalyst; and (d) a liquid containing at least an addition reaction promoting catalyst, A method for producing a waterless lithographic printing plate precursor, wherein these liquids are mixed at an arbitrary ratio immediately before coating.
(7) (c) The liquid containing at least a SiH group-containing compound and a condensation reaction promoting catalyst contains a silane coupling agent or an ethylenically unsaturated bond-containing silane coupling agent (5) or (6) The manufacturing method of the waterless planographic printing plate precursor as described.

  According to the present invention, since no protective film is provided on the silicone rubber layer, the protective film peeling step at the time of making the plate can be omitted, and the silicone rubber layer and the interleaf are not substantially adhered to each other. A waterless lithographic printing plate precursor laminate having good interleaving paper peelability in the apparatus is obtained. Furthermore, when a silicone rubber layer composition liquid containing a silane coupling agent or an ethylenically unsaturated bond-containing silane coupling agent and a condensation reaction promoting catalyst is used, adhesion between the silicone rubber layer and the heat-sensitive layer is excellent. Therefore, a waterless lithographic printing plate precursor laminate having good image reproducibility, scratch resistance and printing durability can be obtained.

  The waterless lithographic printing plate precursor laminate of the present invention is formed by laminating a waterless lithographic printing plate precursor and a slip sheet in contact with the silicone rubber layer, and the silicone rubber layer and the slip sheet are not substantially bonded. It is characterized by.

  Various mechanisms have been proposed as a plate surface-slip paper peeling mechanism in an automatic plate feeder. Among them, a general method is to lift the back side of the printing plate precursor of the printing plate precursor laminate set so that the image forming surface faces downward with a suction cup, and peel off the slip sheet from the plate surface mainly by gravity (self-weight of the slip sheet). . In the present invention, “the silicone rubber layer and the slip sheet are not substantially bonded” means that the slip sheet is peeled well from the silicone rubber layer in the plate surface-slip sheet peeling mechanism in such an automatic plate feeder. It refers to a state where it can

  In order to obtain such a waterless lithographic printing plate precursor laminate having excellent interleaving properties, when the interleaving paper is laminated on the silicone rubber layer, the curing reaction of the silicone rubber layer is completed or nearly complete. It is effective to be.

  Examples of a method for obtaining a cured silicone rubber layer include: i) a method in which a silicone rubber layer composition liquid having high curing reactivity is used, and a curing reaction is completed or nearly completed by a heating step and a drying step. And ii) a method in which a protective film is once provided on the heated and dried silicone rubber layer, and after the silicone rubber layer is cured, the protective film is peeled off.

  Examples of the protective film used here include plastic films such as polyester, polyethylene, polypropylene, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, and polyvinylidene chloride.

  In addition, as a method of promoting the curing of the silicone rubber layer of ii), it is possible to leave it at room temperature and humidity for a certain period of time. Moreover, you may perform a heating and humidification for hardening acceleration.

Below the sheet silicone rubbers layer composition liquid <1> can be mentioned those shown in ~ <3>, in the present invention Ru used those shown in <2> to <3>.

  <1> A silicone rubber layer composition liquid comprising at least a hydroxyl group-containing silicone and a silane coupling agent. Examples of the hydroxyl group-containing silicone include compounds having a structure represented by the following general formula (I) and having a hydroxyl group in the molecular terminal and / or main chain.

In the formula, a and b each represent an integer of 1 or more. R ^{1 to} R ¹⁰ are each a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 50 carbon atoms. And at least one group selected from the group consisting of: which may be the same or different, but has at least two hydroxyl groups in the molecule.

  As for the position of the hydroxyl group in the molecule, it is preferable to contain two or more hydroxyl groups at the molecular end, and among them, a compound containing a total of two hydroxyl groups, one each at both molecular ends is preferred.

In the general formula (I), R ^{1 to} R ¹⁰ are preferably 50% or more of the total, more preferably 80% or more of methyl groups from the viewpoint of ink repellency of the printing plate. In addition, the weight average molecular weight is preferably 10,000 to 600,000 from the viewpoints of handleability, ink repellency and scratch resistance of the obtained printing plate.

  Examples of the silane coupling agent include dealcohol-type, deacetic acid-type, deoxime-type, deamid-type, dehydroxylamine-type, and deacetone-type silane coupling agents. Among these, it is preferable to use a deacetic acid-type or deoxime-type silane coupling agent from the viewpoints of adhesive strength with the heat-sensitive layer and curing speed.

  Specific compounds include tetramethoxysilane, tetraethoxysilane, tetraallyloxysilane, tetrapropoxysilane, tetraacetoxysilane, tetrakis (methylethylketooxyimino) silane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane , Methyltris (methylethylketooxyimino) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriacetoxysilane, ethyltris (methylethylketooxyimino) silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriphenoxysilane, vinyltriacetoxy Silane, vinyltris (methylethylketooxyimino) silane, allyltrimethoxysilane, allyltriethoxysilane, Riltriacetoxysilane, allyltris (methylethylketooxyimino) silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, phenyltris (methylethylketooxyimino) silane, (3-acryloyloxypropyl) trimethoxysilane, ( 3-acryloyloxypropyl) triethoxysilane, (3-acryloyloxypropyl) triacetoxysilane, (3-acryloyloxypropyl) tris (methylethylketooxyimino) silane, (3-methacryloyloxypropyl) trimethoxysilane , (3-methacryloyloxypropyl) triethoxysilane, (3-methacryloyloxypropyl) triacetoxysilane, (3-methacryloyloxypropyl) tris (meth) Ethyl ketoximino) silane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) triacetoxysilane, (3-glycidoxypropyl) ) Tris (methylethylketooxyimino) silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriacetoxysilane, 3-aminopropyltris (methylethylketooxyimino) silane, dimethyldimethoxysilane, dimethyl Diethoxysilane, dimethyldiacetoxysilane, dimethylbis (methylethylketooxyimino) silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiacetoxysilane, diethylbis (methylether) Tilketooxyimino) silane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldiacetoxysilane, divinylbis (methylethylketooxyimino) silane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldiacetoxysilane, diallylbis (methylethylketooxyimino) silane , Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiacetoxysilane, diphenylbis (methylethylketooxyimino) silane, vinyltrisisopropenoxysilane, vinylmethylbis (methylethylketooxyimino) silane, diisopropenoxydimethylsilane, triisopro Examples include, but are not limited to, penoxymethylsilane.

  In addition to the above components, a condensation reaction promoting catalyst is preferably contained. As the condensation reaction accelerating catalyst, it is preferable to use one or a combination of two or more of metal fatty acid salts, organic metal fatty acid salts, metal alcoholates, metal chelates, and nitrogen-containing compounds. Specific examples of each are as follows.

  (Metal Fatty Acid Salt) Metal fatty acid salts such as tin, lead, zinc, iron, cobalt, calcium, manganese, titanium, aluminum, zirconium and the like can be mentioned. Specific examples include zinc octylate and iron octylate.

  (Organic metal fatty acid salt) Fatty acid salts of compounds in which organic substances are added to metals such as tin, lead, zinc, iron, cobalt, calcium, manganese, titanium, aluminum, and zirconium. Specific examples include dibutyltin diacetate, dibutyltin dioctate, and dibutyltin dilaurate.

  (Metal alcoholates) Examples of metal alcoholates include tin, lead, zinc, iron, cobalt, calcium, manganese, titanium, aluminum, and zirconium. Specific examples include titanium tetrapropoxide and titanium tetrabutoxide. In the present invention, a metal siloxide such as tetrakis (trimethylsiloxy) titanium is also included in the metal alcoholate.

  (Metal chelates) Metal diketone compounds such as tin, lead, zinc, iron, cobalt, calcium, manganese, titanium, aluminum, zirconium, cheto complexes or chelate / alcolate bodies with keto ester compounds or diester compounds Can be mentioned. Specific examples include iron trisacetylacetonate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, aluminum trisdiethylmalonate, titanium tetraacetylacetonate, titanium diacetylacetonate dipropoxide, and the like.

  (Nitrogen-containing compounds) Triethylamine, tributylamine, N, N-dimethyldecylamine, N, N-dimethyloctadecylamine, N, N-diethyloctadecylamine, pyridine, methylethylketoxime and the like can be mentioned.

  Although the example of content of each component which comprises a silicone rubber layer composition liquid is shown below, it is not limited to this. For example, the content of the silane coupling agent is preferably in the range of 1 to 15% by weight and the content of the condensation reaction promoting catalyst is in the range of 0.001 to 1% by weight with respect to the total solid content of the silicone layer composition liquid. Is preferred.

  <2> A silicone rubber layer composition liquid comprising at least a hydroxyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, and an ethylenically unsaturated bond-containing silane coupling agent. Examples of the hydroxyl group-containing silicone include the compounds described in <1>.

  Examples of the SiH group-containing compound include compounds having a structure represented by the following general formula (II) and having a SiH group in the molecular terminal and / or main chain.

In the formula, c and d represent an integer of 1 or more, and R ^{11 to} R ²⁰ are each hydrogen, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 50 carbon atoms. And at least one group selected from the group consisting of: may be the same or different, but has at least two SiH groups in the molecule.

In terms of storage stability and ink repellency of the printing plate, it is preferable that R ^{11 to} R ²⁰ in the above formula are 50% or more of methyl groups. Moreover, it is preferable to have 3 or more SiH groups in the molecule. By having three or more SiH groups in the molecule, a three-dimensional crosslinked structure is formed, and a good cured film can be obtained.

  As the addition reaction promoting catalyst, a transition metal compound is preferable, and a platinum compound is particularly preferable. Specific examples include platinum alone, platinum chloride, chloroplatinic acid, olefin coordination platinum, alcohol-modified platinum complexes, and methylvinylpolysiloxane complexes of platinum.

  As an ethylenically unsaturated bond containing silane coupling agent, the compound which contains an ethylenically unsaturated bond in the molecule | numerator among the silane coupling agents as described in <1> is mentioned. Specific compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriphenoxysilane, vinyltriacetoxysilane, vinyltris (methylethylketooxyimino) silane, allyltrimethoxysilane, allyltriethoxysilane, allyltriacetoxysilane, Allyltris (methylethylketooxyimino) silane, (3-acryloyloxypropyl) trimethoxysilane, (3-acryloyloxypropyl) triethoxysilane, (3-acryloyloxypropyl) triacetoxysilane, (3-acryloyloxy Propyl) tris (methylethylketooxyimino) silane, (3-methacryloyloxypropyl) trimethoxysilane, (3-methacryloyloxypropyl) triethoxysilane, (3- Tacryloyloxypropyl) triacetoxysilane, (3-methacryloyloxypropyl) tris (methylethylketooxyimino) silane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldiacetoxysilane, divinylbis (methylethylketooxyimino) silane, diallyldimethoxysilane , Diallyldiethoxysilane, diallyldiacetoxysilane, diallylbis (methylethylketooxyimino) silane, vinyltrisisopropenoxysilane, vinylmethylbis (methylethylketooxyimino) silane, and the like, but are not limited thereto.

Also, it contains condensation reaction accelerating catalyst in addition to the above components. As the condensation reaction promoting catalyst, the compound described in <1> can be used.

  Moreover, you may contain an addition reaction retarder from the viewpoint of the pot life of a silicone rubber layer composition liquid other than the said component. Examples of the addition reaction retarder include nitrogen-containing compounds, phosphorus-containing compounds, and unsaturated alcohols, and nitrogen-containing compounds and unsaturated alcohols are preferably used.

  Although the example of content of each component which comprises a silicone rubber layer composition liquid is shown below, it is not limited to this. For example, the content of the silane coupling agent is preferably in the range of 1 to 15% by weight with respect to the total solid content of the silicone layer composition liquid, and the content of the condensation reaction promoting catalyst is 0.001 to 1% by weight. The content of the addition reaction promoting catalyst is preferably in the range of 0.001 to 1% by weight of the transition metal. Moreover, when using an addition reaction retarder, the range of 0.01 to 5 weight% in total solid content is preferable.

  The content of the hydroxyl group-containing silicone and SiH group-containing compound is the amount obtained by subtracting the content of the silane coupling agent, condensation reaction promoting catalyst, addition reaction promoting catalyst, and addition reaction retarding agent from 100% by weight of the total solid content. It becomes. As an index of the content of the SiH group-containing compound, the ratio of the number of SiH groups to the number of functional groups capable of reacting with SiH groups is preferably in the range of 1: 1 to 1: 2, particularly preferably about 1 to 1.5. The functional group capable of reacting with the SiH group herein includes a hydroxyl group-containing silicone, a silane coupling agent, a condensation reaction promoting catalyst, an addition reaction promoting catalyst, an ethylenically unsaturated bond contained in the addition reaction retarding agent, and an acetylenic group. A saturated bond, a hydroxyl group and the like are indicated.

  <3> A silicone rubber layer composition liquid comprising at least a vinyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, and a silane coupling agent. Examples of the vinyl group-containing silicone include compounds having a structure represented by the following general formula (III) and having a vinyl group in the molecular terminal and / or main chain.

In the formula, e and f each represent an integer of 1 or more. R ^{21 to} R ³⁰ are each composed of a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 50 carbon atoms. And at least one group selected from the group, which may be the same or different from each other, but has at least two vinyl groups in the molecule.

  As for the position of the vinyl group in the molecule, it is preferable to contain two or more vinyl groups at the molecular end, and among them, a compound containing a total of two vinyl groups, one at each of both molecular ends, is preferred.

In the general formula (III), R ^{21 to} R ³⁰ are preferably 50% or more of the total, more preferably 80% or more of methyl groups, from the viewpoint of ink repellency of the printing plate. In addition, the weight average molecular weight is preferably 10,000 to 600,000 from the viewpoints of handleability, ink repellency and scratch resistance of the obtained printing plate.

  As the SiH group-containing compound and the addition reaction promoting catalyst, the compounds described in <2> can be used. As the silane coupling agent, the compound described in <1> can be used.

Also, it contains condensation reaction accelerating catalyst in addition to the above components. As the condensation reaction promoting catalyst, the compound described in <1> can be used.

  Moreover, you may contain an addition reaction retarder from the viewpoint of the pot life of a silicone rubber layer composition liquid other than the said component. As the addition reaction retarder, the compound described in <2> can be used.

  Although the example of content of each component which comprises a silicone rubber layer composition liquid is shown below, it is not limited to this. For example, the content of the silane coupling agent is preferably in the range of 1 to 15% by weight with respect to the total solid content of the silicone layer composition liquid, and the content of the condensation reaction promoting catalyst is 0.001 to 1% by weight. The content of the addition reaction promoting catalyst is preferably in the range of 0.001 to 1% by weight of the transition metal. Moreover, when using an addition reaction retarder, the range of 0.01 to 5 weight% in total solid content is preferable.

  The content of vinyl group-containing silicone and SiH group-containing compound is the amount obtained by subtracting the content of silane coupling agent, condensation reaction promoting catalyst, addition reaction promoting catalyst, and addition reaction retarding agent from 100% by weight of the total solid content. It becomes. As an index of the content of the SiH group-containing compound, for example, the ratio of the number of SiH groups to the number of functional groups capable of reacting with SiH groups is preferably in the range of 1: 1 to 1: 2, especially about 1: 1.5. preferable. The functional group capable of reacting with the SiH group herein includes a vinyl group-containing silicone, a silane coupling agent, a condensation reaction promoting catalyst, an addition reaction promoting catalyst, an ethylenically unsaturated bond contained in the addition reaction retarding agent, and an acetylenic property. An unsaturated bond, a hydroxyl group, etc. are pointed out.

  In addition to these components, the silicone rubber layer composition liquid described in <1> to <3> is filled with known fillers such as silica and silicone fine particles in order to improve rubber strength and scratch resistance. An agent may be contained.

  The above-mentioned silicone rubber layer composition liquid can also be diluted with a solvent and used as a solution. Hereinafter, the silicone rubber layer composition liquid includes a solution diluted with a solvent. As a diluting solvent, a solvent that can dissolve or disperse each component satisfactorily is used. Specifically, aliphatic, alicyclic, and aromatic hydrocarbon solvents, ethers, ketones, and esters are used. Are used singly or in combination of two or more. Of these, hydrocarbon solvents are preferably used from the viewpoint of coatability.

  Since the silicone rubber layer composition liquid used in the present invention or each component constituting them is strongly affected by moisture, it is possible to prevent as much as possible the entry of moisture into each component and silicone rubber layer composition liquid. preferable. As a method for preventing moisture from being mixed, a closed container or a container capable of supplying a dry gas can be used, and each constituent component and the silicone rubber layer composition liquid can be handled in the dry gas. Moreover, dehydrating with a dehydrating agent such as bubbling with a dry gas or molecular sieves may be performed.

  In the silicone rubber layer composition liquid according to <2> or <3> using an addition reaction between an ethylenically unsaturated bond and a SiH group, the liquid preparation method and the timing from the liquid preparation to application should be devised. In this case, a silicone rubber layer having good interleaving peelability can be obtained even if interleaving paper is provided immediately after application, heating and drying of the silicone rubber layer composition liquid. In addition, in a system including at least a vinyl group or hydroxyl group-containing silicone, a SiH group-containing compound, and an (ethylenically unsaturated double bond-containing) silane coupling agent, only using an addition reaction promoting catalyst as proposed so far However, the silicone rubber layer can be cured in a shorter time by using both the addition reaction promoting catalyst and the condensation reaction promoting catalyst. As the addition reaction promoting catalyst, a transition metal compound is used, and among them, a platinum compound is generally preferably used from the viewpoint of catalytic activity. On the other hand, as the condensation reaction promoting catalyst, an organic tin compound or a fatty acid salt thereof or an amino group-containing compound is used, and among them, an organic tin compound or a fatty acid salt thereof is generally preferably used from the viewpoint of catalytic activity. At first glance, it seems easy to imagine using both of these catalysts together, but organotin compounds and amino group-containing compounds have extremely strong coordination power to platinum, which can significantly reduce the catalytic activity of platinum. It is widely known, and for this reason, the combined use of an addition reaction promoting catalyst and a condensation reaction promoting catalyst has been avoided. However, in a system including at least a vinyl group or hydroxyl group-containing silicone, SiH group-containing compound, silane coupling agent, and addition reaction promotion catalyst, a small amount of condensation reaction promotion catalyst that should be a poison for the addition reaction promotion catalyst was added. In this case, it was found that the curing of the silicone rubber layer was promoted specifically. It was also found that the adhesion of the silicone rubber layer to the heat sensitive layer was improved by adding a small amount of the condensation reaction catalyst. For this reason, the condensation reaction promoting catalyst also promotes the condensation reaction between the silane coupling agent, which is a constituent component of the silicone rubber layer, and an active hydrogen-containing functional group such as a hydroxyl group or a carboxyl group present on the surface of the heat sensitive layer, This is thought to be because a strong adhesive force due to chemical bonding was developed at the interface between the silicone rubber layer and the heat sensitive layer.

  The liquid preparation method of the silicone rubber layer composition liquid and the timing from the liquid preparation to application are also important. This is because when the silicone rubber layer composition liquid immediately after the liquid preparation is used, good curability and heat-sensitive layer adhesive strength can be obtained, but the curability and adhesive strength of the liquid are extremely reduced with the passage of time. Because there is. The main cause of such deactivation over time is considered to be that the addition reaction promoting catalyst is deactivated due to the influence of other components. From this, i) addition reaction promoting catalyst and ii) two components of other components, or iii) a component that does not deactivate the addition reaction promoting catalyst including the addition reaction promoting catalyst, and iv) the addition reaction promoting catalyst. By separately preparing two liquids of components that deactivate the liquid and mixing these two liquids immediately before coating, a silicone rubber layer that cures well in a short time can be stably obtained. A vinyl group-containing silicone is mentioned as a component which does not deactivate an addition reaction promotion catalyst among structural components. Moreover, the silane coupling agent and the condensation reaction promoting catalyst include those that deactivate the addition reaction promoting catalyst and those that do not deactivate. The addition reaction retarder tends to deactivate the addition reaction promoting catalyst. In addition, since the addition reaction of the SiH group-containing compound is started by contact with the addition reaction promoting catalyst, it is preferable to avoid premixing with the addition reaction promoting catalyst.

The allowable time from mixing the two liquids to coating is difficult to define because it varies depending on the silicone rubber layer composition liquid type, liquid storage temperature, and the like. For example, the silicone rubber layer composition solution of Comparative Example 13 and the heating conditions described later are used. When the silicone rubber layer composition solution aged at 35 ° C. for 4 days or longer was used, the interleaving paper peelability was slightly poor, whereas the liquid aging was within 2 days at 35 ° C. Then, a waterless lithographic printing plate precursor having no problem in practical use and having no significant influence on the interleaving property and other characteristics was obtained. In this example, the allowable time from the two-component mixing to the application is within two days, but from the viewpoint of stabilizing the performance, the time from the two-component mixing to the application is preferably as short as possible.

  In order to use the above-described technology for long-time mass production, for example, the above-mentioned liquids stored in two containers that exist independently of each other are sent in an arbitrary amount to a liquid-feeding pipe connected to a coating apparatus. Then, the two liquids are mixed with a mixing device provided immediately before the coating device, and the mixed silicone rubber layer composition liquid is coated with the coating device. By using such a method, since the silicone rubber layer composition liquid is always mixed immediately before application, a silicone rubber layer that cures well in a short time can be stably obtained. As a mixing device for mixing the two liquids described above, it is preferable to use a spiral type or stator type static mixer.

  As a coating method of the silicone rubber layer composition liquid, slit die coater, direct gravure coater, offset gravure coater, reverse roll coater, natural roll coater, air knife coater, roll blade coater, varibar roll blade coater, two stream coater, Examples of the coating method include a rod coater, a wire bar coater, a dip coater, a curtain coater, and a spin coater. Among these, a slit die coater, a gravure coater, and a roll coater are preferable in terms of coating accuracy, productivity, and cost, and a slit die coater is most preferable.

  When applying the silicone rubber layer composition liquid, it is preferable from the viewpoint of adhesiveness to remove as much water as possible attached to the surface of the heat sensitive layer. Specifically, it can be achieved by applying the silicone rubber layer composition liquid in a space where moisture is removed by filling or continuously supplying a dry gas.

  The applied silicone rubber layer composition liquid is dried and cured under heating. For heating, a general heating device such as a hot air dryer or an infrared dryer can be used. The silicone rubber layer composition liquid is preferably heated immediately after coating from the viewpoint of curability and heat-sensitive layer adhesion.

The thickness of the silicone rubber layer is preferably 0.5 to 20 g / m ² , more preferably 1 to 4 g / m ² . When the film thickness is 0.5 g / m ² or more, the ink repellency, scratch resistance, and printing durability of the printing plate are sufficient, and when it is 20 g / m ² or less, development is not disadvantageous from an economic standpoint. The ink mileage is less likely to deteriorate.

  As the heat-sensitive layer used in the present invention, any type of heat-sensitive layer previously proposed as a heat-sensitive layer for waterless lithographic printing plates can be used. Hereinafter, although a specific example is given and demonstrated, it is not limited to these.

(Heat-sensitive layer-1) Heat-sensitive layer for negative-type waterless CTP lithographic printing plate precursor Examples include a heat-sensitive layer described in JP-A-2004-199016. The component is at least i) an active hydrogen-containing compound, ii) a cross-linking agent, and iii) a heat-sensitive layer containing a photothermal conversion substance, in which a cross-linking structure is formed by the cross-linking agent in a raw plate state, and a near-infrared laser This is a type of heat-sensitive layer in which the adhesive force between the heat-sensitive layer and the silicone rubber layer is reduced by the heat generated by the irradiation. Subsequent development processing removes the silicone rubber layer in the portion irradiated with the laser beam. Although the mechanism is not yet elucidated, it is considered that the structure in which a cross-linked structure was formed at the time of plate preparation was desorbed by the action of heat generated by laser irradiation. As a result, the solvent resistance at the interface between the silicone rubber layer and the heat-sensitive layer changes, and the silicone rubber layer in the laser irradiation part is specifically removed by development processing.

The i) an active hydrogen-containing _{compounds, -OH, -SH, -NH 2,} -NH -, - CO-NH 2, -CO-NH -, - OCO-NH -, - NH-CO-NH -, - _{CO-OH, -CS-OH,} -CO-SH, -CS-SH, -SO 3 H, -PO 3 H 2, -SO 2 -NH 2, -SO 2 -NH -, - CO-CH 2 - It is a polymer having a structural unit having active hydrogen such as CO- in the molecule, and is preferably a polymer having a film forming ability. Examples of the polymer having such a structural unit in the molecule include homopolymers or copolymers of monomers containing carboxyl groups such as acrylic acid and methacrylic acid, and hydroxyl groups such as hydroxyethyl methacrylate and 2-hydroxypropyl acrylate. Homopolymer or copolymer of acrylic acid or methacrylic acid ester containing N-alkylacrylamide, homopolymer or copolymer of acrylamide, reaction product of amines with glycidyl acrylate, glycidyl methacrylate or allyl glycidyl Homopolymers or copolymers of ethylenically unsaturated monomers containing active hydrogen such as homopolymers or copolymers of p-hydroxystyrene, vinyl alcohol homopolymers or copolymers (as copolymerization monomer components) Is active hydrogen Other ethylenically unsaturated monomers may be used, and ethylenically unsaturated monomers containing no active hydrogen may be used.), Polyurethane resins, polyurea resins, polyamide resins (nylon resins), epoxy resins, polyalkylenes Examples thereof include condensates having a structural unit having an active hydrogen in the main chain, such as imines, phenol novolac resins, cresol novolac resins, resol resins, and cellulose derivatives. Among these, a polymer having a hydroxyl group or a carboxyl group is preferable, and a polymer having a phenolic hydroxyl group such as poly (p-hydroxystyrene), novolac resin, or resole resin is more preferable. These active hydrogen-containing compounds may be used alone or in combination of two or more.

  It is also preferable to use a polymer having other film forming ability together with a polymer having active hydrogen in the molecule. Examples of other film-forming polymers include acrylic acid esters such as polymethyl methacrylate and polybutyl methacrylate, homopolymers and copolymers of methacrylic acid esters, styrene monomers such as polystyrene and α-methylstyrene. Homopolymers or copolymers, various synthetic rubbers such as isoprene and styrene-butadiene, homopolymers of vinyl esters such as polyvinyl acetate and copolymers such as vinyl acetate-vinyl chloride, condensation of polyester, polycarbonate, etc. And various types of polymers.

  ii) Examples of the crosslinking agent include known polyfunctional compounds capable of forming a crosslinked structure with the active hydrogen-containing compound, and include isocyanates, epoxy compounds, acrylate compounds, aldehyde compounds, mercapto compounds, alkoxysilyl compounds, Examples include amine compounds, carboxylic acids, vinyl compounds, diazonium salts, azide compounds, and hydrazine.

  Moreover, an organic complex compound is also preferably used. An organic complex compound is an organic complex salt in which an organic ligand is coordinated to a metal, an organic-inorganic complex salt in which an organic ligand or an inorganic ligand is liganded to a metal, and a metal and an organic molecule shared through oxygen Including bonded metal alkoxides. Among these, a metal chelate compound in which a ligand has two or more donor atoms and forms a ring containing a metal atom is preferable from the standpoint of stability of itself and stability of a heat-sensitive layer solution. Used.

  The main metals forming the organic complex compound include Cu (I), Ag (I), Hg (I), Hg (II), Li, Na, K, Be (II), B (III), Zn ( II), Cd (II), Al (III), Co (II), Ni (II), Cu (II), Ag (II), Au (III), Pd (II), Pt (II), Ca ( II), Sr (II), Ba (II), Ti (IV), V (III), V (IV), Cr (III), Mn (II), Mn (III), Fe (II), Fe ( III), Co (III), Pd (IV), Pt (IV), Sc (III), Y (III), Si (IV), Sn (II), Sn (IV), Pb (IV), Ru ( III), Rh (III), Os (III), Ir (III), Rb, Cs, Mg, Ni (IV), Ra, Zr (IV), Hf (IV), Mo (IV), W (IV) , Ge, In, lanthanide, actinide and the like. Among these, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, In, Sn, Zr, and Hf are preferable, and Al, Ti, Fe, and Zr are more preferable.

Moreover, as a ligand, the compound which has the following coordination groups which has O (oxygen atom), N (nitrogen atom), S (sulfur atom) etc. as a donor atom is mentioned. Specific examples of the coordinating group include those having an oxygen atom as a donor atom, -OH (alcohol, enol and phenol), -COOH (carboxylic acid),> C = O (aldehyde, ketone, quinone),- O- (ether), - COOR (ester, R: represents an aliphatic or aromatic hydrocarbon), - N = O (nitroso compounds), - NO ₂ (nitro compound),> NO (N-oxide) , —SO ₃ H (sulfonic acid), —PO ₃ H ₂ (phosphorous acid), and the like with nitrogen atoms as donor atoms include —NH ₂ (primary amine, amide, hydrazine),> NH (2 grade amine, hydrazine),> N- (3 amine), - N = N- (azo compounds, heterocyclic compounds), = N-OH (oxime), - NO ₂ (nitro compound), - N = O ( Nitroso compounds),> C N— (Schiff base, heterocyclic compound),> C═NH (aldehyde, ketone imine, enamines), —NCS (isothiocyanato), etc. having a sulfur atom as a donor atom include —SH (thiol), — S- (thioether),> C = S (thioketone, thioamide), = S- (heterocyclic compound), -C (= O) -SH or -C (= S) -OH and -C (= S)- SH (thiocarboxylic acid), -SCN (thiocyanato), etc. are mentioned.

  Further, some of the specific examples of the ligand include the following.

  (A) As aliphatic carboxylic acids, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, citraconic acid, itacone Acid, tricarballylic acid, propane-1,1,2,3-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, glycolic acid, thioglycolic acid, lactic acid, β-hydroxypropionic acid, apple Acid, tartaric acid, citric acid, isocitric acid, alloisocitric acid, gluconic acid, pyruvic acid, oxalic acid, diglycolic acid, thiodiglycolic acid, mercaptosuccinic acid, dimercaptosuccinic acid and the like.

  (B) As aromatic carboxylic acid, aldehyde and related compounds, benzoic acid, phthalic acid, mandelic acid, salicylaldehyde, salicylic acid, 5-sulfosalicylic acid, α-carboxy-O-anisic acid, O- (carboxymethylthio) benzoic acid , Tropolone, methyl tropolone, tyrone, chromotropic acid and so on.

  (C) As amines and derivatives thereof, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, Nn-propylethylenediamine, N-isopropylethylenediamine, N- (2-hydroxyethyl) ethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, N, N′-di-n-propylethylenediamine, N, N′-di (2-hydroxyethyl) ethylenediamine, N, N, N ′, N ′ -Tetramethylethylenediamine, diaminopropane, diaminobutane, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, diaminocyclohexane, diaminocycloheptane, triethylenediamine, triaminoprop 1,3-diamino-2-aminomethylpropane, diethylenetriamine, 3,3′-diaminodipropylamine, triethylenetetramine, 2,2 ′, 2 ″ -triaminotriethylamine, ethanolamine, 2-methoxyethylamine, diethanolamine , Triethanolamine, 2-mercaptoethylamine, 2-aminoethylmethyl sulfide, di (2-aminoethyl) ether, 2-amino-2′-hydroxydiethyl sulfide, bis (2-aminoethyl) sulfide, pyridine, aminomethyl Pyridine, pyridine-2-carboxylic acid, pyridinedicarboxylic acid, nicotinic acid hydrazide, isonicotinic acid hydrazide, pyridoxamine, piperidine, piperidine dicarboxylic acid, imidazole, histamine, 3-methylhistamine .

  (D) As aminopolycarboxylic acid, iminodiacetic acid, iminodipropionic acid, N-methyliminodiacetic acid, N- (3,3-dimethylbutyl) iminodiacetic acid, phenyliminodiacetic acid, hydroxyethyliminodiacetic acid, mercaptoethyliminodia Acetic acid, hydroxyethyliminodipropionic acid, hydroxypropyliminodiacetic acid, 2-hydroxycyclohexyliminodiacetic acid, methoxyethyliminodiacetic acid, methylthioethyliminodiacetic acid, 2-hydroxybenzyliminodiacetic acid, N- (carboxyphenyl) iminodi Acetic acid, N- (carbamoylmethyl) iminodiacetic acid, cyanomethyliminodiacetic acid, aminoethyliminodiacetic acid, phosphonomethyliminodiacetic acid, sulfoethyliminodiacetic acid, sulfophenyliminodiacetic acid, nitrilotriacetic acid, carboxyl Ethyliminodiacetic acid, carboxymethyliminodipropionic acid, nitrilotripropionic acid, N, N'-ethylenediaminediacetic acid, ethylenediamine-N, N'-dipropionic acid, N, N'-di (hydroxyethyl) ethylenediaminediacetic acid, N- n-butylethylenediaminetriacetic acid, N-cyclohexylethylenediaminetriacetic acid, N′-hydroxyethyl-N, N, N′-triacetic acid, benzylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, ethylenediamine-N, N′-diacetic acid, N , N'-dipropionic acid, ethylenediaminetetrapropionic acid, 1,2-propylenediaminetetraacetic acid, trimethylenediaminetetraacetic acid, cyclohexane-1,2-diaminetetraacetic acid, 1,3,5-triaminocyclohexanehex Acetate, ethyl ether diaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol ether diaminetetraacetic acid, etc. trimethylene tetraamine hexaacetic acid.

  (E) Examples of β-diketone and oxine include acetylacetone (2,4-pentadione), 3,5-heptanedione, trifluoroacetylacetone, hexafluoroacetylacetone, methyl acetoacetate, ethyl acetoacetate, propylacetoacetate, aceto Butyl acetate, dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, benzoylacetone, benzoyltrifluoroacetone, dibenzoylmethane, furoylacetone, trifluorofuroylacetone, benzoylfuroylmethane, tenoylacetone, trifluoro Ruthenoylacetone, furoylthenoylmethane, oxine (also known as 8-hydroxyquinoline), methyloxine, oxine-5-sulfonic acid, quinolinecarboxylic acid, 8-hydroxycinoline, Roxynaphthyridine, hydroxyquinoxaline, hydroxyquinazoline, 2,2′-bipyridine, 2- (2′-chenyl) pyridine, 1,10-phenanthroline, methyl-1,10-phenanthroline, dimethyl-1,10-phenanthroline, dimethylglycine Oxime, dimethyldithiocarbamic acid, nitrosonaphthol, hydroxyflavone, 1- (2-pyridylazo) -2-naphthol, eriochrome black A and B, eriochrome blue black B and R, phthalein complexone and the like.

  (F) Others, glycine, sarcosine, alanine, α-aminobutyric acid, valine, leucine, phenylalanine, tyrosine, serine, threonine, cysteine, methionine, aspartic acid, asparagine, glutamic acid, 1,2-diaminopropionic acid, ornithine, lysine Amino acids such as arginine, proline, histidine, tryptophan, N, N-bis (2-hydroxyethyl) glycine, glycylglycine, albumin, casein, myosin A, peptides, proteins and the like. Pyrimidines such as purine, adenine, hypoxanthine, inosine, xanthosine, guanosine, adenosine-5'-phosphate, adenosine-5'-diphosphate, adenosine-5'-triphosphate, purine bases, nucleosides, nucleotides and the like. Antibiotics such as penicillin G, tetracycline, oxytetracyclone, chlorotetracyclone.

  Among the organic complex compounds formed from the metal and ligand as described above, the compounds preferably used include Al, Ti, Fe, Mn, Co, Ni, Cu, Zn, Ge, In, Sn, Zr, Examples include complexes with metal diketones such as Hf, ketoesters, diesters, amines, alcohols, and carboxylic acids, and also acetylacetone, ethyl acetoacetate, and malonic acid of Al, Fe (III), Ti, and Zr. A particularly preferred compound is diethyl complex.

  Specific examples of such compounds include the following compounds, but are not limited thereto. Aluminum tris acetylacetonate, aluminum tris (ethyl acetoacetate), aluminum tris (propyl acetoacetate), aluminum tris (butyl acetoacetate), aluminum tris (hexyl acetoacetate), aluminum tris (nonyl acetoacetate), aluminum tris (hexa) Fluoropentadionate), aluminum tris (2,2,6,6-tetramethyl-3,5-heptanedionate), aluminum bisethylacetoacetate monoacetylacetonate, aluminum diacetylacetonate ethylacetoacetate, aluminum monoacetyl Acetonate bispropyl acetoacetate, aluminum monoacetylacetonate bisbutyl acetoacetate, aluminum Um monoacetylacetonate bishexyl acetoacetate, aluminum monoethyl acetoacetate bispropyl acetoacetonate, aluminum monoethyl acetoacetate bisbutyl acetoacetonate, aluminum monoethyl acetoacetate bishexyl acetoacetonate, aluminum monoethyl acetoacetate bisnonyl Acetoacetonate, aluminum dibutoxide monoacetoacetate, aluminum dipropoxide monoacetoacetate, aluminum diisopropoxide ethylacetoacetate, aluminum-s-butoxidebis (ethylacetoacetate), aluminum di-s-butoxide ethylacetoacetate, Aluminum-9-octadecenyl acetoacetate diisopropoxide, etc.Titanium allyl acetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium bis (triethanolamine) di-n-butoxide, titanium diisopropoxide bis (2,4-pentadionate), Titanium di-n-butoxide bis (2,4-pentanedionate), Titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), Titanium diisopropoxide bis ( Ethyl acetoacetate), titanium di-n-butoxide bis (ethyl acetoacetate), titanium ethyl acetoacetate tri-n-butoxide, titanium methacryloxyethyl acetoacetate triisopropoxide, titanium oxy Bis (2,4-pentanedionate), titanium tetra (2-ethyl-3-hydroxyhexyl oxide), dihydroxy bis (lactate) titanium, etc. (ethylene glycolate) titanium bis (dioctyl phosphate). Zirconium di-n-butoxide bis (2,4-pentanedionate), zirconium tetrakis (hexafluoropentanedionate), zirconium tetrakis (trifluoropentanedionate), zirconium methacryloxyethyl acetoacetate tri-n-propoxide, zirconium tetrakis (2,4-pentanedionate), zirconium tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate), triglycolate zirconate, trilactate zirconate, iron (III) acetylacetonate , Dibenzoylmethane iron (II), tropolone iron, tristropolono iron (III), hinokitiol iron, tris hinokitioro iron (III), acetoacetate iron (III), iron (III) benzoylacetonate, iron (III) Phenylpropane dionate, iron (III) tetramethylheptanedionate, iron (III) trifluoro pentanedionate like.

  iii) The photothermal conversion substance is not particularly limited as long as it absorbs laser light. For example, black pigments such as carbon black, aniline black and cyanine black, phthalocyanine, naphthalocyanine-based green pigments, carbon graphite , Iron powder, diamine-based metal complex, dithiol-based metal complex, phenolthiol-based metal complex, mercaptophenol-based metal complex, crystal water-containing inorganic compound, copper sulfate, chromium sulfide, silicate compound, titanium oxide, vanadium oxide, oxidation It is preferable to add additives such as metal oxides such as manganese, iron oxide, cobalt oxide and tungsten oxide, hydroxides and sulfates of these metals, and metal powders of bismuth, iron, magnesium and aluminum.

  Among these, carbon black is preferable from the viewpoint of photothermal conversion, economic efficiency, and handleability.

  In addition to the above substances, dyes that absorb infrared rays or near infrared rays are also preferably used as photothermal conversion materials.

  As these dyes, all dyes having a maximum absorption wavelength in the range of 400 nm to 1200 nm can be used. Preferred dyes include cyanine series, phthalocyanine series, phthalocyanine metal complex series, naphthalocyanine series for electronics and recording dyes. , Naphthalocyanine metal complex, dithiol metal complex, naphthoquinone, anthraquinone, indophenol, indoaniline, pyrylium, thiopyrylium, squarylium, croconium, diphenylmethane, triphenylmethane, triphenylmethanephthal , Triallylmethane, phenothiazine, phenoxazine, fluoran, thiofluorane, xanthene, indolylphthalide, spiropyran, azaphthalide, chromenopyrazole Leucooramine, rhodamine lactam, quinazoline, diazaxanthene, bislactone, fluorenone, monoazo, ketoneimine, disazo, polymethine, oxazine, nigrosine, bisazo, bisazostilbene, bis Azooxadiazole, bisazofluorenone, bisazohydroxyperinone, azochrome complex, trisazotriphenylamine, thioindigo, perylene, nitroso, 1: 2 type metal complex, intermolecular CT , Quinoline, quinophthalone, fulgide acid dyes, basic dyes, dyes, oil-soluble dyes, triphenylmethane leuco dyes, cationic dyes, azo disperse dyes, benzothiopyran spiropyran, 3,9-dibromoant Antron, Indanthron, Feno Rufutarein, sulfo phthalein, ethyl violet, methyl orange, fluorescein, methyl viologen, methylene blue, and the like gym loss betaine.

  Among these, cyanine dyes, azurenium dyes, squarylium dyes, croconium dyes, azo disperse dyes, bisazostilbenes, which are dyes for electronics and recording and have a maximum absorption wavelength in the range of 700 nm to 900 nm. Dyes, naphthoquinone dyes, anthraquinone dyes, perylene dyes, phthalocyanine dyes, naphthalocyanine metal complex dyes, polymethine dyes, dithiol nickel complex dyes, indoaniline metal complex dyes, intermolecular CT dyes, benzothiopyrans Spiropyran, nigrosine dye and the like are preferably used.

Further, among these dyes, those having a large molar absorbance coefficient are preferably used. Specifically, ε = 1 × 10 ⁴ or more is preferable, and more preferably 1 × 10 ⁵ or more. If ε is 1 × 10 ⁴ or more, an effect of improving sensitivity can be exhibited.

  These photothermal conversion materials are preferably used alone or in combination of two or more. By using two or more kinds of photothermal conversion substances having different absorption wavelengths in combination, it is possible to cope with two or more kinds of lasers having different emission wavelengths.

  In addition to the above components, any compound or the like can be contained for the purpose of improving other properties. For example, a reaction promoting catalyst can be contained for the purpose of promoting the crosslinking reaction, other dyes or dye precursors can be contained for the purpose of improving the plate inspection property, and for the purpose of improving the coatability. A surfactant or the like can also be contained.

  Moreover, it is preferable to dilute with the solvent which can melt | dissolve or disperse | distribute the said structural component favorably, and to use for coating as a diluted solution.

  Furthermore, in addition to the above-mentioned solvent, by applying and heating as a dilute solution containing a small amount of a high boiling point solvent that cannot dissolve or hardly dissolve the heat-sensitive layer constituent components, fine pores are formed in the heat-sensitive layer. May be formed. By forming such minute holes, the sensitivity as a plate material is dramatically improved.

As the high boiling point solvent that cannot dissolve the heat-sensitive layer constituents or is difficult to dissolve, an organic solvent having a solubility parameter of 8.3 (cal · cm ⁻³ ) ^1/2 or less is preferable. The solubility parameter refers to an amount δ defined by δ = (ΔH / V) ^1/2 where ΔH is the heat of molar evaporation of the liquid and V is the molar volume. Solubility parameter 8.3 (cal · cm ⁻³ ) ^1/2 or less of organic solvents include linear, branched, and cyclic saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, halogenated Examples include hydrocarbons and ethers. Specifically, hexane, heptane, octane, nonane, decane, dodecane, isooctane, cyclopentane, cyclohexane, methylcyclohexane, “Isopar C”, “Isopar E”, “Isopar G”, “Isopar H”, “Isopar K” "Saturated aliphatic hydrocarbons such as Exxon Chemical Co., Ltd.", unsaturated aliphatic hydrocarbons such as hexene, heptene, octene, nonene and decene, halogenated hydrocarbons such as trifluorotrichloroethane, diisopropyl ether, diisobutyl ether Although ethers, such as these, are mentioned, It is not limited to these. Aliphatic hydrocarbons are preferred from the viewpoint of economy and safety.

The thickness of the heat sensitive layer is preferably in the range of 0.5 to 3 g / m ² .

(Heat-sensitive layer-2) Heat-sensitive layer for positive-type waterless CTP lithographic printing plate precursor Examples of the heat-sensitive layer include those described in JP-A-11-157236 and JP-A-11-240271. The component is at least i) an active hydrogen-containing compound, ii) a heat-activated cross-linking agent, and iii) a heat-sensitive layer containing a photothermal conversion substance, and heat-activated cross-linking agent by heat generated by irradiation with a near-infrared laser. This is a type of heat-sensitive layer in which a crosslinked structure is formed. Subsequent development processing leaves a portion of the silicone rubber layer that has been irradiated with laser light, and removes the portion of the silicone rubber layer that has not been irradiated.

  i) As the active hydrogen-containing compound, a compound similar to the active hydrogen-containing compound described in the thermal layer-1 can be used.

  ii) Examples of the heat-activated crosslinking agent include polyfunctional compounds that can be activated by heat and form a crosslinked structure with an active hydrogen-containing compound. Specific examples include blocked isocyanates, metals Examples include chelate compounds, epoxy compounds, polyamines, resole resins, alkylated urea resins, and alkylated melamine resins.

  iii) As the photothermal conversion substance, the same compounds as the photothermal conversion substance described in the thermosensitive layer-1 can be used.

  In addition to the above components, any compound or the like can be contained for the purpose of improving other properties. For example, it may contain a crosslinking agent other than the above-mentioned heat-activated crosslinking agent capable of forming a crosslinked structure at a low temperature for the purpose of improving chemical resistance, and may contain a reaction promoting catalyst for the purpose of promoting the crosslinking reaction. In addition, other dyes and dye precursors can be contained for the purpose of improving plate inspection properties, and surfactants and the like can be contained for the purpose of improving coating properties.

  Moreover, it is preferable to dilute with the solvent which can melt | dissolve or disperse | distribute the said structural component favorably, and to use for coating as a diluted solution.

The thickness of the heat sensitive layer is preferably in the range of 0.5 to 3 g / m ² .

(Heat-sensitive layer-3) Heat-sensitive layer for negative-type waterless CTP lithographic printing plate precursor Examples include the heat-sensitive layer described in JP-A-9-23943. The constituent components are a heat-sensitive layer containing at least i) a self-oxidizing binder, ii) a photothermal conversion substance, and a heat-sensitive layer of a type in which the heat-sensitive layer is destroyed by heat generated by irradiation with a near-infrared laser. Finally, by removing this portion by development, the silicone rubber layer on the surface is peeled off at the same time to form an image portion.

  i) Nitrocellulose can be preferably used as the self-oxidizing binder.

  ii) As the photothermal conversion substance, the same photothermal conversion substance as that described in thermosensitive layer-1 can be used.

  In addition to the above components, any compound or the like can be contained for the purpose of improving other properties. For example, a flexible resin or rubber can be contained for the purpose of improving printing durability, an adhesive can be contained for the purpose of improving the adhesion to the silicone rubber layer or the substrate, and chemical resistance can be improved. For the purpose, a crosslinking agent may be contained.

  Moreover, it is preferable to dilute with the solvent which can melt | dissolve or disperse | distribute the said structural component favorably, and to use for coating as a diluted solution.

The thickness of the heat sensitive layer is preferably in the range of 3 g / m ² or less.

(Heat-sensitive layer-4) Heat-sensitive layer for negative-type waterless CTP lithographic printing plate precursor Examples of the metal thin film described in JP-A-7-314934 and JP-A-9-086065 can be given. This is a type of heat sensitive layer in which the metal thin film is destroyed by heat generated by irradiation with a near infrared laser. Finally, by removing this portion by development, the silicone rubber layer on the surface is peeled off at the same time to form an image portion.

  For the formation of thin films, metals such as aluminum, titanium, tellurium, chromium, bismuth, zinc, lead, tin, antimony, gallium, magnesium, polonium, selenium, thallium, alloys thereof, oxides, carbides thereof, Nitride, boride, fluoride, etc. can be used. Among these, from the viewpoint of sensitivity, it is preferable to use a metal having a melting point of 930 (K) or less, such as bismuth, zinc, tellurium, tin, antimony, gallium, magnesium, polonium, selenium, and thallium.

  The thickness of the heat sensitive layer is preferably 100 nm or less, and more preferably in the range of 10 to 25 nm.

  As the application method and heating method of each of the above-mentioned heat-sensitive layer composition solutions, the same methods as the application and heating of the silicone rubber layer composition solution can be used.

  Moreover, the metal thin film as described in the thermosensitive layer-4 can be obtained by general methods, such as a vacuum evaporation method and sputtering method.

  As the substrate used in the present invention, known dimensionally stable paper, metal, film and the like conventionally used as a substrate of a printing plate can be used. Specifically, paper, paper laminated with plastic (polyethylene, polypropylene, polystyrene, etc.), aluminum (including aluminum alloy), zinc, copper and other metal plates, cellulose acetate, polyethylene terephthalate, polyethylene, polyester, polyamide, Examples thereof include a plastic film such as polyimide, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and a paper or plastic film on which a metal as described above is laminated or vapor-deposited. The plastic film can be either transparent or opaque. Among these, the use of an opaque film is preferable from the viewpoint of plate inspection.

  Of these substrates, an aluminum plate is particularly preferred because it is extremely dimensionally stable and inexpensive. A polyethylene terephthalate film is particularly preferable as a flexible substrate for light printing.

  For the purpose of improving adhesion between the substrate and the heat-sensitive layer, preventing light halation, improving plate inspection, improving heat insulation, and improving printing durability, a primer layer is preferably provided on the substrate.

  Examples of the resin used for the primer layer include epoxy resins, phenol resins, acrylic resins, alkyd resins, polyester resins, polyamide resins, urea resins, melamine resins, polyvinyl butyral resins, polyurethane resins, rubbers, casein, and gelatin. Can do. These resins can be used alone or in admixture of two or more. Moreover, you may use what hardened | cured the composition similar to these resin. In these, it is preferable to use a polyurethane resin, a polyester resin, an acrylic resin, an epoxy resin, a urea resin etc. independently or in mixture of 2 or more types.

  For the purpose of improving the solvent resistance of the primer layer, it is preferable to contain a crosslinking agent. As the cross-linking agent, a cross-linking agent or an organic complex compound used in the heat-sensitive layer can be used.

  It is preferable to contain various pigments and dyes for the purpose of preventing light halation and improving plate inspection. Among them, it is preferable to use a white or yellow pigment, and it is preferable to use a titanium oxide pigment from the viewpoint of hiding performance and coloring performance.

  Moreover, you may contain arbitrary compounds, such as surfactant, a leveling agent, a pigment dispersant, a hollow particle, fine particles other than a pigment other than the said component.

  Moreover, it is preferable to dilute with the solvent which can melt | dissolve or disperse | distribute the said structural component favorably, and to use for coating as a diluted solution.

The thickness of the primer layer is preferably 0.5 to 50 g / m ² from the viewpoint of the effect of preventing morphological defects on the substrate surface and blocking adverse chemical effects and economical efficiency, and more preferably 1 to 10 g / m ² . .

  As a method for applying the primer layer composition solution and a heating method, the same methods as those for applying the silicone rubber layer composition solution and heating can be used.

Slip sheet used in the present invention preferably has a basis weight 30 to 120 g / ^{m 2,} more preferably from 30~90g / ^{m 2.} If the weight is 30 g / m ² or more, the mechanical strength is sufficient, and if it is 120 g / m ² or less, not only is it economically advantageous, but the water-less lithographic printing plate precursor and paper laminate become thin, Workability becomes advantageous. For example, information recording base paper 40 g / m ² (manufactured by Nagoya Pulp Co., Ltd.), metal interleaving paper 30 g / m ² (manufactured by Nagoya Pulp Co., Ltd.), unbleached kraft paper 50 g / m ² (manufactured by Chuetsu Pulp Co., Ltd.) ), NIP paper 52 g / m ² (manufactured by Chuetsu Pulp Co., Ltd.), pure white roll paper 45 g / m ² (Oji Paper Co., Ltd.), Kurpac 73 g / m ² (Oji Paper Co., Ltd.), and the like. It is not limited to these.

  As the light source used in the laser exposure step, one having an emission wavelength region in the range of 300 nm to 1500 nm is used. Among these, a semiconductor laser or YAG laser having an emission wavelength region near the near infrared region is preferably used. It is done. Specifically, from the viewpoint of handling of the plate material in a bright room, laser beams having wavelengths of 780 nm, 830 nm, and 1064 nm are preferably used for plate making.

  The original plate after laser irradiation is developed by a friction treatment in the presence or absence of a developer. The rubbing treatment can be performed by rubbing the plate surface with a nonwoven fabric, absorbent cotton, cloth, sponge, brush or the like, or by wiping the plate surface with a nonwoven fabric, absorbent cotton, cloth, sponge, etc. impregnated with a developer. Alternatively, the plate surface can be pretreated with a developer and then rubbed with a rotating brush while showering tap water or the like, or high-pressure water, hot water, or steam can be sprayed onto the plate surface.

  Prior to development, a pretreatment in which a plate is immersed in a pretreatment solution for a certain time may be performed. As the pretreatment liquid, for example, water or water added with a polar solvent such as alcohol, ketone, ester or carboxylic acid, polar solvent such as aliphatic hydrocarbons, aromatic hydrocarbons, etc. A solvent added or a polar solvent is used. Furthermore, it is preferable to use a glycol compound or a glycol ether compound as a main component, and it is more preferable for an amine compound to coexist.

  Examples of the developer used in the development treatment include water and water added with a surfactant, water added with a polar solvent such as alcohol, ketone, ester, carboxylic acid, and aliphatic carbonization. A solvent in which at least one polar solvent is added to at least one solvent such as hydrogen and aromatic hydrocarbons, or a polar solvent is used. In addition, a known surfactant can be freely added to the developer composition. As the surfactant, those having a pH of 5 to 8 when made into an aqueous solution are preferable from the viewpoints of safety, cost for disposal, and the like. The content of the surfactant is preferably 10% by weight or less of the developer. Such a developer has high safety and is preferable from the viewpoint of economics such as cost for disposal.

  In addition, for the purpose of improving the visibility of the image area and the measurement accuracy of the halftone dots, dyes such as crystal violet, Victoria pure blue, and Astrazone red are added to these developers to develop ink reception at the same time as the development. The layer can also be dyed. It can also be dyed with a solution to which the above dye is added after development.

  In the case where the developed printing plates are stacked and stored, it is preferable to sandwich a slip sheet between the plates for the purpose of protecting the printing plate.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples, isoparaffinic hydrocarbon “Isopar” E used was dehydrated by bubbling dry nitrogen gas. Further, α, ω-dihydroxypolydimethylsiloxane and α, ω-divinylpolydimethylsiloxane were diluted to 30% by weight with the above-mentioned dehydrated “Isopar” E, and further dehydrated by bubbling with dry nitrogen gas. Using. In addition, each silicone rubber layer constituent component is weighed in a glove box that drains the moisture in the box, and the silicone rubber layer composition liquid is prepared by mixing each constituent component in a container filled with dry nitrogen gas. Prepared.

<Interleaving paper peelability evaluation method>
The interleaving paper peel test was performed under the following conditions.
Automatic plate feeder: “Multi cassette unit” (manufactured by Creo)
Plate setter: “Lotem” 800II Quantum (manufactured by Creo)
Plate material: Example, comparative sample production sample (size) 560 × 670 mm
(Interleaf) “Kurupack” <73 g / m ² > (Oji Paper Co., Ltd.)
(Number of layers) 50 (Evaluation)
Good: ○ (the number of slip sheets that did not peel off was 0 out of 50)
Slightly poor: Δ (the number of slip sheets that did not peel was 1 to 2 out of 50)
Defect: x (the number of interleaving sheets not peeled is 3 or more out of 50).

( Comparative Example 1)
The following primer layer composition liquid is applied onto a 0.24 mm thick degreased aluminum substrate (Mitsubishi Aluminum Co., Ltd.) and dried at 200 ° C. for 1 minute to provide a primer layer having a thickness of 8 g / m ^2. It was.
<Primer layer composition liquid>
(A) Epoxy resin: “Epicoat” 1010 (manufactured by Japan Epoxy Resin Co., Ltd.): 18 parts by weight (b) Polyurethane: “Samprene” LQ-T1331D (manufactured by Sanyo Chemical Industries, Ltd., concentration 20%, N, N -Dimethylformamide / 2-ethoxyethanol solution): 285 parts by weight (polyurethane: 57 parts by weight)
(C) Aluminum tris (ethyl acetoacetate): “Aluminum chelate” ALCH-TR (manufactured by Kawaken Fine Chemical Co., Ltd.): 4 parts by weight (d) Vinyl polymer: “Dispalon” LC951 (manufactured by Enomoto Kasei Co., Ltd.) ): 0.1 part by weight (e) Titanium oxide: N, N-dimethylformamide dispersion (Titanium oxide 50 wt%) of “Taipeku” CR-50 (manufactured by Ishihara Sangyo Co., Ltd.): 42 parts by weight (f) N , N-dimethylformamide: 48 parts by weight (g) Methyl ethyl ketone: 270 parts by weight.

Next, the following heat-sensitive layer composition liquid-1 was applied onto the primer layer and heated at 130 ° C. for 90 seconds to provide a heat-sensitive layer having a thickness of 1.5 g / m ² .
<Thermosensitive layer composition liquid-1>
(A) Infrared absorbing dye: YKR-2900 (manufactured by Yamamoto Kasei Co., Ltd.): 10 parts by weight (b) Titanium di-n-butoxide bis (2,4-pentandionate): “Narsem” titanium (Nippon Chemical Industry Co., Ltd.) )): 22 parts by weight (c) Phenol novolak resin: “Sumilite Resin” PR54652 (manufactured by Sumitomo Durez): 60 parts by weight (d) Polyurethane: “Samprene” LQT1331D (manufactured by Sanyo Chemical Co., Ltd.): 10 parts by weight (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane = 1/3/1 mol ratio addition reaction product: 15 parts by weight (f) tetrahydrofuran: 800 parts by weight (g) dimethyl Formamide: 100 parts by weight.

Next, the following silicone rubber layer composition liquid-1 prepared immediately before coating was applied on the heat-sensitive layer, heated at 130 ° C. for 90 seconds, and provided with a silicone rubber layer having a thickness of 2.0 g / m ^2. A waterless CTP lithographic printing plate precursor was obtained.
<Silicone rubber layer composition liquid-1>
(A) α, ω-dihydroxypolydimethylsiloxane: DMS-S42 (weight average molecular weight 77,000, manufactured by GELEST Inc.): 100 parts by weight (b) vinyltris (methylethylketooxyimino) silane: 5 parts by weight (c) dibutyl Tin diacetate: 0.03 parts by weight (d) “Isopar” E (Esso Chemical Co., Ltd.): 1035 parts by weight.

On the silicone rubber layer immediately after heating, a 6 μm polypropylene film: “Trephan” (manufactured by Toray Industries, Inc.) was laminated and left for 4 days. After standing, the polypropylene film was peeled off, and a slip sheet: “Kurupack” <73 g / m ² > (manufactured by Oji Paper Co., Ltd.) was provided on the silicone rubber layer. When the obtained waterless lithographic printing plate precursor laminate was set in an automatic plate feeder and the interleaf release property was evaluated, the interleaf release failure did not occur and was good.

The printing plate precursor after separation of the interleaf is mounted on a plate making machine: GX-3600 (manufactured by Toray Industries, Inc.), and a halftone dot of 175 lines / inch-1 to 99% is irradiated using a semiconductor laser (wavelength 830 nm). Exposure was performed at 150 mJ / cm ² . Subsequently, automatic processor: TWL-860KII (manufactured by Toray Industries, Inc., pretreatment liquid: NP-1 (manufactured by Toray Industries, Inc.), developer: water, post-treatment liquid: NA-1 (manufactured by Toray Industries, Inc.) ), The exposed plate was developed with a pretreatment solution immersion time of 45 seconds to obtain a direct-drawing waterless lithographic printing plate, and the obtained waterless lithographic printing plate was observed with an optical microscope. No peeling of the rubber layer or thickening of the halftone dots was observed, and the halftone dots of 1 to 99% were reproduced well.

(Comparative Example 2 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 1 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaf paper was firmly adhered to the silicone rubber layer, and the interleaving paper peelability was poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

( Comparative Example 3 )
Sample preparation and performance evaluation were performed in the same manner as in Comparative Example 1, except that the silicone rubber layer composition liquid-1 was prepared, and then the liquid that was allowed to stand at 35 ° C. for 4 days was used as the silicone rubber layer composition liquid. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 4 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 3 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper was firmly adhered to the silicone rubber layer, and the interleaving paper peelability was poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

( Comparative Example 5 )
A negative waterless CTP lithographic printing plate precursor laminate was produced and its performance was evaluated in the same manner as in Comparative Example 1 except that the following silicone rubber layer composition liquid-2 was used as the silicone rubber layer composition liquid. .
<Silicone rubber layer composition liquid-2>
(A) α, ω-dihydroxypolydimethylsiloxane: DMS-S42 (weight average molecular weight 77,000, manufactured by GELEST Inc.): 100 parts by weight (b) Trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer at both ends : HMS-501 (manufactured by GELEST Inc.): 3 parts by weight (c) Pyridine: 3 parts by weight (d) Platinum catalyst: SRX-212 (manufactured by Toray Dow Corning Silicone Co., Ltd.): 7 parts by weight (e) “ Isopar "E (Esso Chemical Co., Ltd.): 1035 parts by weight.

  In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, the silicone rubber layer on the entire surface of the developed plate was peeled off, and the adhesion between the silicone rubber layer and the heat sensitive layer was poor.

( Comparative Example 6 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 5 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, the silicone rubber layer on the entire surface of the plate after development was peeled off, and the adhesion between the silicone rubber layer and the heat sensitive layer was poor.

( Comparative Example 7 )
Sample preparation and performance evaluation were performed in the same manner as in Comparative Example 5 except that the silicone rubber layer composition liquid-2 was prepared, and then the liquid that was allowed to stand at 35 ° C. for 4 days was used as the silicone rubber layer composition liquid. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, the silicone rubber layer on the entire surface of the plate after development was peeled off, and the adhesion between the silicone rubber layer and the heat sensitive layer was poor.

(Comparative Example 8 )
Sample preparation and performance evaluation were performed in the same manner as in Comparative Example 7 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, the silicone rubber layer on the entire surface of the plate after development was peeled off, and the adhesion between the silicone rubber layer and the heat sensitive layer was poor.

( Comparative Example 9 )
A negative waterless CTP lithographic printing plate precursor laminate was produced and evaluated for performance in the same manner as in Comparative Example 1 except that the following silicone rubber layer composition liquid-3 was used as the silicone rubber layer composition liquid. .
<Silicone rubber layer composition liquid-3>
(A) α, ω-dihydroxypolydimethylsiloxane: DMS-S42 (weight average molecular weight 77,000, manufactured by GELEST Inc.): 100 parts by weight (b) Trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer at both ends : HMS-501 (manufactured by GELEST Inc.): 4 parts by weight (c) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (d) Platinum catalyst: SRX-212 (manufactured by Toray Dow Corning Silicone Co., Ltd.): 7 Part by weight (e) “Isopar” E (Esso Chemical Co., Ltd.): 1035 parts by weight.

  In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 10 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 9 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

( Comparative Example 11 )
Sample preparation and performance evaluation were performed in the same manner as in Comparative Example 9 except that the silicone rubber layer composition liquid-3 was prepared as the silicone rubber layer composition liquid and then the liquid was allowed to stand at 35 ° C. for 4 days. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, a slight dot thickening due to peeling of the silicone rubber layer was observed, and the halftone dot reproducibility was 1 to 96%.

(Comparative Example 12 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 11 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper was firmly adhered to the silicone rubber layer, and the interleaving paper peelability was poor. In the halftone dot reproducibility test, a slight dot thickening due to peeling of the silicone rubber layer was observed, and the halftone dot reproducibility was 1 to 96%.

(Example 1 )
A negative waterless CTP lithographic printing plate was prepared and its performance was evaluated in the same manner as in Comparative Example 1 except that the following silicone rubber layer composition liquid-4 was used as the silicone rubber layer composition liquid.
<Silicone rubber layer composition liquid-4>
(A) α, ω-dihydroxypolydimethylsiloxane: DMS-S42 (weight average molecular weight 77,000, manufactured by GELEST Inc.): 100 parts by weight (b) Trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer at both ends Compound: HMS-501 (manufactured by GELEST Inc.): 4 parts by weight (c) Vinyl tris (methylethylketooxyimino) silane: 3 parts by weight (d) Dibutyltin diacetate: 0.03 parts by weight (e) Platinum catalyst: SRX- 212 (Toray Dow Corning Silicone Co., Ltd.): 7 parts by weight (f) “Isopar” E (Esso Chemical Co., Ltd.): 1035 parts by weight.

  In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 2 )
A sample was prepared and performance was evaluated in the same manner as in Example 1 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 3 )
Sample preparation and performance evaluation were performed in the same manner as in Example 1 except that the silicone rubber layer composition solution-4 was prepared and then the solution was allowed to stand at 35 ° C. for 4 days. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 13 )
A sample was prepared and performance was evaluated in the same manner as in Example 3 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

( Comparative Example 14 )
A negative waterless CTP lithographic printing plate precursor laminate was produced and its performance was evaluated in the same manner as in Comparative Example 1 except that the following silicone rubber layer composition liquid-5 was used as the silicone rubber layer composition liquid. .
<Silicone rubber layer composition liquid-5>
(A) α, ω-divinylpolydimethylsiloxane: DMS-V52 (weight average molecular weight 110,000, manufactured by GELEST Inc.): 100 parts by weight (b) Trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer at both ends Combined: HMS-501 (manufactured by GELEST Inc.): 3 parts by weight (c) Pyridine: 3 parts by weight (d) Platinum catalyst: SRX-212 (manufactured by Toray Dow Corning Silicone): 7 parts by weight (e ) “Isopar” E (Esso Chemical Co., Ltd.): 1035 parts by weight.

  In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, the silicone rubber layer on the entire surface of the plate after development was peeled off, and the adhesion between the silicone rubber layer and the heat sensitive layer was poor.

( Comparative Example 15 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 14 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, the silicone rubber layer on the entire surface of the plate after development was peeled off, and the adhesion between the silicone rubber layer and the heat sensitive layer was poor.

( Comparative Example 16 )
Sample preparation and performance evaluation were performed in the same manner as in Comparative Example 14 except that the silicone rubber layer composition liquid-5 was prepared, and then the liquid that was allowed to stand at 35 ° C. for 4 days was used as the silicone rubber layer composition liquid. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, the silicone rubber layer on the entire surface of the plate after development was peeled off, and the adhesion between the silicone rubber layer and the heat sensitive layer was poor.

(Comparative Example 17 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 16 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, the silicone rubber layer on the entire surface of the plate after development was peeled off, and the adhesion between the silicone rubber layer and the heat sensitive layer was poor.

( Comparative Example 18 )
A negative waterless CTP printing plate precursor laminate was produced and its performance was evaluated in the same manner as in Comparative Example 1 except that the following silicone rubber layer composition liquid-6 was used as the silicone rubber layer composition liquid.
<Silicone rubber layer composition liquid-6>
(A) α, ω-divinylpolydimethylsiloxane: DMS-V52 (weight average molecular weight 110,000, manufactured by GELEST Inc.): 100 parts by weight (b) Trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer at both ends Combined: HMS-501 (manufactured by GELEST Inc.): 4 parts by weight (c) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (d) Platinum catalyst: SRX-212 (manufactured by Toray Dow Corning Silicone) : 7 parts by weight (e) “Isopar” E (Esso Chemical Co., Ltd.): 1035 parts by weight.

  In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 19 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 18 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

( Comparative Example 20 )
Sample preparation and performance evaluation were performed in the same manner as in Comparative Example 18 , except that the silicone rubber layer composition liquid-6 was prepared and then the liquid left at 35 ° C. for 4 days was used as the silicone rubber layer composition liquid. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, some halftone dots due to peeling of the silicone rubber layer were observed, and the halftone dot reproducibility was 1 to 96%.

(Comparative Example 21 )
Sample preparation and performance evaluation were performed in the same manner as in Comparative Example 20 , except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper was firmly adhered to the silicone rubber layer, and the interleaving paper peelability was poor. In the halftone dot reproducibility test, a slight dot thickening due to peeling of the silicone rubber layer was observed, and the halftone dot reproducibility was 1 to 96%.

(Example 4 )
A negative waterless CTP lithographic printing plate precursor laminate was prepared and performance was evaluated in the same manner as in Comparative Example 1 except that the following silicone rubber layer composition solution-7 was used as the silicone rubber layer composition solution. .
<Silicone rubber layer composition liquid-7>
(A) α, ω-divinylpolydimethylsiloxane: DMS-V52 (weight average molecular weight 110,000, manufactured by GELEST Inc.): 100 parts by weight (b) Trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer at both ends Compound: HMS-501 (manufactured by GELEST Inc.): 4 parts by weight (c) Vinyl tris (methylethylketooxyimino) silane: 3 parts by weight (d) Dibutyltin diacetate: 0.03 parts by weight (e) Platinum catalyst: SRX- 212 (Toray Dow Corning Silicone Co., Ltd.): 7 parts by weight (f) “Isopar” E (Esso Chemical Co., Ltd.): 1035 parts by weight.

  In the interleaving paper peelability test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 5 )
A sample was prepared and performance was evaluated in the same manner as in Example 4 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 6 )
Sample preparation and performance evaluation were performed in the same manner as in Example 4 except that the silicone rubber layer composition liquid-7 was prepared, and then the liquid that was allowed to stand at 35 ° C. for 4 days was used as the silicone rubber layer composition liquid. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 22 )
Sample preparation and performance evaluation were performed in the same manner as in Example 6 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 7 )
No negative water was applied in the same manner as in Example 4 except that the following heat-sensitive layer composition liquid-2 was applied and heated at 80 ° C. for 60 seconds to provide a heat-sensitive layer having a thickness of 1.5 g / m ² . A CTP planographic printing plate precursor laminate was obtained.
<Thermosensitive layer composition liquid-2>
(A) Photothermal conversion substance (near infrared absorbing dye): “PROJET” 825LDI (manufactured by Avecia): 10 parts by weight (b) Organic complex compound: titanium di-n-butoxide bis (2,4-pentanedionate): “Narsem” titanium (manufactured by Nippon Chemical Industry Co., Ltd., titanium concentration of about 8.8%, n-butanol solution): 22 parts by weight (c) Polymer having active hydrogen: phenol novolac resin: “Sumilite resin” PR54652 ( Sumitomo Durez Co., Ltd.): 60 parts by weight (d) Acetone: 654 parts by weight (e) Ethanol: 40 parts by weight (f) “Isopar” H (Esso Chemical Co., Ltd.): (SP value 8.2 ( cal · cm ⁻³ ) ^1/2 , boiling point 178-188 ° C.): 14 parts by weight.

In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. The printing plate precursor after separation of the interleaf is mounted on a plate making machine: GX-3600 (manufactured by Toray Industries, Inc.), and a halftone dot of 175 lines / inch-1 to 99% is irradiated using a semiconductor laser (wavelength 830 nm). Exposure was performed at 150 mJ / cm ² . Subsequently, the exposed plate is developed with an automatic developing machine: TWL-860KII (manufactured by Toray Industries, Inc., pretreatment liquid, developer, posttreatment liquid: all water) with a pretreatment liquid immersion time of 45 seconds. , Got a printing plate. When the obtained waterless lithographic printing plate was observed with an optical microscope, no peeling of the silicone rubber layer or thickening of the halftone dots was observed, and the halftone dots of 1 to 99% were reproduced well.

(Example 8 )
A sample was prepared and performance was evaluated in the same manner as in Example 7 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 9 )
Sample preparation and performance evaluation were performed in the same manner as in Example 7 , except that the silicone rubber layer composition liquid-7 was prepared and then the liquid was allowed to stand at 35 ° C. for 4 days. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 23 )
Sample preparation and performance evaluation were performed in the same manner as in Example 9 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 10 )
The heat sensitive layer composition liquid-3 below was applied, except having a heat-sensitive layer having a thickness of 2.5 g / m ² by heating for 60 seconds at 80 ° C. without positive water in the same manner as in Example 4 A CTP planographic printing plate precursor laminate was obtained.
<Thermosensitive layer composition liquid-3>
(A) “KAYASORB” IR-820B (infrared absorbing dye, manufactured by Nippon Kayaku Co., Ltd.): 10 parts by weight (b) Organic complex compound: titanium di-n-butoxide bis (2,4-pentanedionate): “Narsem "Titanium (Nippon Chemical Industry Co., Ltd., titanium concentration of about 8.8%, n-butanol solution): 15 parts by weight (c) pentaoxypropylenediamine / glycidyl methacrylate / methyl glycidyl ether = 1/3/1 mol ratio addition Reaction product: 15 parts by weight (d) m-xylylenediamine / glycidyl methacrylate / methyl glycidyl ether = 1/2/2 mol ratio addition reaction product: 15 parts by weight (e) m-xylylenediamine / glycidyl methacrylate / 3-glycol Sidoxypropyltrimethoxysilane = 1/3/1 mol ratio addition reaction product: 3 parts by weight (f) Cole "EX-411 (pentaerythritol polyglycidyl ether, manufactured by Nagase Kasei Kogyo Co., Ltd.) 5 parts by weight (g)" Samprene "LQ-T1331 (polyurethane resin, manufactured by Sanyo Chemical Industries, Ltd., glass transition temperature Tg: -37 ° C): 30 parts by weight (h) Maleic acid: 0.5 parts by weight (i) Tetrahydrofuran: 200 parts by weight (j) Dimethylformamide: 50 parts by weight.

In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. The printing plate precursor after separation of the interleaf paper is mounted on a plate making machine: GX-3600 (manufactured by Toray Industries, Inc.), and a halftone dot of 175 lines / inch-1 to 99% is irradiated using a semiconductor laser (wavelength 830 nm). Exposure was performed with an energy of 250 mJ / cm ² . Subsequently, automatic processor: TWL-860KII (manufactured by Toray Industries, Inc., pretreatment liquid: PP-F (manufactured by Toray Industries, Inc.), developer: water, post-treatment liquid: PA-F (manufactured by Toray Industries, Inc.) The exposed plate was developed with a pretreatment solution immersion time of 45 seconds to obtain a printing plate, and the obtained waterless lithographic printing plate was observed with an optical microscope. No dot thickening was observed, and a dot of 1 to 99% was reproduced well.

(Example 11 )
A sample was prepared and performance was evaluated in the same manner as in Example 10 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 12 )
Preparation of a sample and performance evaluation were performed in the same manner as in Example 10 except that a silicone rubber layer composition solution-7 was prepared as a silicone rubber layer composition solution, and then the solution was allowed to stand at 35 ° C. for 4 days. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 24 )
A sample was prepared and performance was evaluated in the same manner as in Example 12 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 13 )
No negative water was applied in the same manner as in Example 4 except that the following heat-sensitive layer composition liquid-4 was applied and heated at 140 ° C. for 60 seconds to provide a heat-sensitive layer having a thickness of 1.5 g / m ² . A CTP planographic printing plate precursor laminate was obtained.
<Thermosensitive layer composition liquid-4>
(A) Nitrocellulose (average polymerization degree 85, nitrogen content 11.0%, “Bergerac NC” manufactured by SNP Japan Co., Ltd.) 30 parts by weight (b) Carbon black (manufactured by Mitsubishi Chemical Corporation) 24 parts by weight (c) polyurethane resin 30 parts by weight “Milactolan” P22S (manufactured by Nippon Miractolan Co., Ltd.)
(D) 20 parts by weight of “KP color 8704 clear” (manufactured by Kansai Paint Co., Ltd., epoxy / urea resin)
(E) Hydroxyethyl acrylate 15 parts by weight (f) Methyl ethyl ketone 700 parts by weight

In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. The printing plate precursor after separation of the interleaf paper is mounted on a plate making machine: GX-3600 (manufactured by Toray Industries, Inc.), and a halftone dot of 175 lines / inch-1 to 99% is irradiated using a semiconductor laser (wavelength 830 nm). Exposure was performed with an energy of 500 mJ / cm ² . Subsequently, the exposed plate is developed with an automatic developing machine: TWL-860KII (manufactured by Toray Industries, Inc., pretreatment liquid, developer, posttreatment liquid: all water) with a pretreatment liquid immersion time of 45 seconds. , Got a printing plate. When the obtained waterless lithographic printing plate was observed with an optical microscope, no peeling of the silicone rubber layer or thickening of the halftone dots was observed, and the halftone dots of 1 to 99% were reproduced well.

(Example 14 )
A sample was prepared and performance was evaluated in the same manner as in Example 13 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 15 )
Sample preparation and performance evaluation were performed in the same manner as in Example 13 except that the silicone rubber layer composition liquid-7 was prepared, and then the liquid that was allowed to stand at 35 ° C. for 4 days was used as the silicone rubber layer composition liquid. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 25 )
Samples were prepared and performance was evaluated in the same manner as in Example 15 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 16 )
As a heat-sensitive layer, a negative waterless CTP lithographic printing plate precursor laminate was obtained in the same manner as in Example 4 except that a 25 nm zinc thin film was provided by vacuum deposition.

In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. The printing plate precursor after separation of the interleaf paper is mounted on a plate making machine: GX-3600 (manufactured by Toray Industries, Inc.), and a halftone dot of 175 lines / inch-1 to 99% is irradiated using a semiconductor laser (wavelength 830 nm). Exposure was performed with an energy of 500 mJ / cm ² . Subsequently, the exposed plate is developed with an automatic developing machine: TWL-860KII (manufactured by Toray Industries, Inc., pretreatment liquid, developer, posttreatment liquid: all water) with a pretreatment liquid immersion time of 45 seconds. , Got a printing plate. When the obtained waterless lithographic printing plate was observed with an optical microscope, no peeling of the silicone rubber layer or thickening of the halftone dots was observed, and the halftone dots of 1 to 99% were reproduced well.

(Example 17 )
A sample was prepared and performance was evaluated in the same manner as in Example 16 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 18 )
Sample preparation and performance evaluation were performed in the same manner as in Example 16 except that the silicone rubber layer composition liquid-7 was prepared, and then the liquid that was allowed to stand at 35 ° C. for 4 days was used as the silicone rubber layer composition liquid. . In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 26 )
A sample was prepared and its performance was evaluated in the same manner as in Example 18 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peelability test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was somewhat poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

  The above results are summarized in Table 1.

( Comparative Example 27 )
As the silicone rubber layer composition liquid, the following silicone rubber layer composition precursor liquid-A and silicone rubber layer composition precursor liquid-B are prepared, and the A and B liquids are mixed at the following weight ratio using an in-line mixer immediately before coating. A negative waterless CTP lithographic printing plate precursor laminate was produced and its performance was evaluated in the same manner as in Comparative Example 1 except for the above.
<Silicone rubber layer composition precursor solution-A>
(A) α, ω-dihydroxypolydimethylsiloxane: DMS-S42 (weight average molecular weight 77,000, manufactured by GELEST Inc.): 100 parts by weight (b) Trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer at both ends Combined: HMS-501 (manufactured by GELEST Inc.): 4 parts by weight (c) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (d) “Isopar” E (manufactured by Esso Chemical Co., Ltd.): 972 parts by weight <silicone Rubber Layer Composition Precursor-B>
(E) Platinum catalyst: SRX-212 (Toray Dow Corning Silicone Co., Ltd.): 7 parts by weight (f) “Isopar” E (Esso Chemical Co., Ltd.): 63 parts by weight.

  In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 28 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 27 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was slightly poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not observed, and a halftone dot of 1 to 99% was reproduced well.

( Comparative Example 29 )
As the silicone rubber layer composition liquid, after preparing the silicone rubber layer composition precursor liquid-A and the silicone rubber layer composition precursor liquid-B, both liquids which were allowed to stand at 35 ° C. for 4 days were used as in Comparative Example 27. Sample preparation and performance evaluation were performed by the method described above. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 30 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 29 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was slightly poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not observed, and a halftone dot of 1 to 99% was reproduced well.

(Example 19 )
As the silicone rubber layer composition liquid, the following silicone rubber layer composition precursor liquid-C and silicone rubber layer composition precursor liquid-D are prepared, and the C and D liquids are mixed at the following weight ratio using an in-line mixer immediately before coating. A negative waterless CTP lithographic printing plate precursor laminate was produced and its performance was evaluated in the same manner as in Comparative Example 1 except for the above.
<Silicone Rubber Layer Composition Precursor-C>
(A) α, ω-dihydroxypolydimethylsiloxane: DMS-S42 (weight average molecular weight 77,000, manufactured by GELEST Inc.): 100 parts by weight (b) Trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer at both ends Combined: HMS-501 (manufactured by GELEST Inc.): 4 parts by weight (c) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (d) Dibutyltin diacetate: 0.03 parts by weight (e) “Isopar” E ( Esso Chemical Co., Ltd.): 972 parts by weight <Silicone rubber layer composition precursor solution-D>
(F) Platinum catalyst: SRX-212 (Toray Dow Corning Silicone Co., Ltd.): 7 parts by weight (g) “Isopar” E (Esso Chemical Co., Ltd.): 63 parts by weight.

  In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 20 )
A sample was prepared and performance was evaluated in the same manner as in Example 19 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 21 )
Similarly as the silicone rubber layer composition liquid, a silicone rubber layer composition precursor solution -C, after preparation of the silicone rubber layer composition precursor solution -D, as in Example 19 except for using both liquid was allowed to stand at 35 ° C. 4 days Sample preparation and performance evaluation were performed by the method described above. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 22 )
A sample was prepared and performance was evaluated in the same manner as in Example 21 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

( Comparative Example 31 )
As the silicone rubber layer composition liquid, the following silicone rubber layer composition precursor liquid-E and silicone rubber layer composition precursor liquid-F are prepared, and the E and F liquids are mixed at the following weight ratio using an in-line mixer immediately before coating. A negative waterless CTP lithographic printing plate precursor laminate was produced and its performance was evaluated in the same manner as in Comparative Example 1 except for the above.
<Silicone Rubber Layer Composition Precursor-E>
(A) α, ω-divinylpolydimethylsiloxane: DMS-V52 (weight average molecular weight 110,000, manufactured by GELEST Inc.): 100 parts by weight (b) Copolymer of trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) at both ends Combined: HMS-501 (manufactured by GELEST Inc.): 4 parts by weight (c) vinyltris (methylethylketooxyimino) silane: 3 parts by weight (d) “Isopar” E (manufactured by Esso Chemical Co., Ltd.): 972 parts by weight <silicone Rubber Layer Composition Precursor-F>
(E) Platinum catalyst: SRX-212 (Toray Dow Corning Silicone Co., Ltd.): 7 parts by weight (f) “Isopar” E (Esso Chemical Co., Ltd.): 63 parts by weight.
In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 32 )
A sample was prepared and performance was evaluated in the same manner as in Comparative Example 31 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was slightly poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not observed, and a halftone dot of 1 to 99% was reproduced well.

( Comparative Example 33 )
As the silicone rubber layer composition liquid, the same procedure as in Comparative Example 31 was conducted , except that both liquids that were allowed to stand at 35 ° C. for 4 days after preparation of silicone rubber layer composition precursor liquid-E and silicone rubber layer composition precursor liquid-F were used. Sample preparation and performance evaluation were performed by the method described above. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Comparative Example 34 )
A sample was prepared and its performance was evaluated in the same manner as in Comparative Example 33 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper was adhered to the silicone rubber layer, and the interleaving paper peelability was slightly poor. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not observed, and a halftone dot of 1 to 99% was reproduced well.

(Example 23 )
As the silicone rubber layer composition liquid, the following silicone rubber layer composition precursor liquid-G and silicone rubber layer composition precursor liquid-H are prepared, and the G and H liquids are mixed at the following weight ratio using an in-line mixer immediately before coating. A negative waterless CTP lithographic printing plate precursor laminate was produced and its performance was evaluated in the same manner as in Comparative Example 1 except for the above.
<Silicone Rubber Layer Composition Precursor-G>
(A) α, ω-divinylpolydimethylsiloxane: DMS-V52 (weight average molecular weight 110,000, manufactured by GELEST Inc.): 100 parts by weight (b) Copolymer of trimethylsilyl (methylhydrogensiloxane) (dimethylsiloxane) at both ends Compound: HMS-501 (manufactured by GELEST Inc.): 4 parts by weight (c) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (d) Dibutyltin diacetate: 0.03 parts by weight (f) “Isopar” E ( Esso Chemical Co., Ltd.): 972 parts by weight <Silicone rubber layer composition precursor solution-H>
(E) Platinum catalyst: SRX-212 (Toray Dow Corning Silicone Co., Ltd.): 7 parts by weight (f) “Isopar” E (Esso Chemical Co., Ltd.): 63 parts by weight.

  In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 24 )
Sample preparation and performance evaluation were performed in the same manner as in Example 23 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 25 )
Similarly as the silicone rubber layer composition liquid, a silicone rubber layer composition precursor solution -G, after preparation of the silicone rubber layer composition precursor solution -H, except for using both liquid and left for 4 days at 35 ° C. Example 23 Sample preparation and performance evaluation were performed by the method described above. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

(Example 26 )
A sample was prepared and performance was evaluated in the same manner as in Example 25 except that a slip sheet was immediately provided on the silicone rubber layer immediately after heating. In the interleaving paper peel test, the interleaving paper peeling failure did not occur and was good. In the halftone dot reproducibility test, peeling of the silicone rubber layer and thickening of the halftone dots were not recognized, and a halftone dot of 1 to 99% was reproduced well.

  The above results are summarized in Table 2.

Claims (7)

A waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate and a slip sheet in contact with the silicone rubber layer are laminated, and the silicone rubber layer and the slip sheet are substantially adhered to each other. A method for producing a waterless lithographic printing plate precursor laminate comprising a step of providing at least a heat-sensitive layer on a substrate, a step of providing a silicone rubber layer, a step of curing the silicone rubber layer, and providing a slip sheet on the silicone rubber layer And a step of providing a silicone rubber layer comprising at least a hydroxyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, an ethylenically unsaturated bond-containing silane coupling agent, and a condensation reaction promoting catalyst. A process for producing a waterless planographic printing plate precursor laminate, comprising the step of applying A waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate and a slip sheet in contact with the silicone rubber layer are laminated, and the silicone rubber layer and the slip sheet are substantially adhered to each other. A method for producing a waterless lithographic printing plate precursor laminate comprising a step of providing at least a heat-sensitive layer on a substrate, a step of providing a silicone rubber layer, a step of curing the silicone rubber layer, and providing a slip sheet on the silicone rubber layer A step of providing a silicone rubber layer, the step of applying a silicone rubber layer composition liquid comprising at least a vinyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, a silane coupling agent, and a condensation reaction promoting catalyst. A method for producing a waterless lithographic printing plate precursor laminate, comprising: The silicone rubber layer composition liquid comprises at least two liquids: (c) a liquid containing at least a SiH group-containing compound and a condensation reaction promoting catalyst, and (d) a liquid containing at least an addition reaction promoting catalyst. The method for producing a waterless lithographic printing plate precursor laminate according to claim 1 or 2, wherein the waterless lithographic printing plate precursor laminate is mixed in any proportion. 4. The waterless lithographic printing plate according to claim 3, wherein the liquid containing at least a SiH group-containing compound and a condensation reaction promoting catalyst contains a silane coupling agent or an ethylenically unsaturated bond-containing silane coupling agent. A method for producing an original laminate. A method for producing a waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, the step of providing at least a heat-sensitive layer on the substrate, the step of providing a silicone rubber layer, and curing the silicone rubber layer And a step of providing a silicone rubber layer comprising at least a hydroxyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, an ethylenically unsaturated bond-containing silane coupling agent, and a condensation reaction promoting catalyst. The silicone rubber layer composition liquid comprises at least two liquids: (c) a liquid containing at least a SiH group-containing compound and a condensation reaction promoting catalyst; and (d) a liquid containing at least an addition reaction promoting catalyst. Waterless lithographic printing, characterized in that these liquids are mixed at an arbitrary ratio immediately before application Manufacturing method of the original. A method for producing a waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, the step of providing at least a heat-sensitive layer on the substrate, the step of providing a silicone rubber layer, and curing the silicone rubber layer A step of providing a silicone rubber layer, the step of applying a silicone rubber layer composition liquid comprising at least a vinyl group-containing silicone, a SiH group-containing compound, an addition reaction promoting catalyst, a silane coupling agent, and a condensation reaction promoting catalyst. The silicone rubber layer composition liquid is composed of at least two liquids: (c) a liquid containing at least a SiH group-containing compound and a condensation reaction promoting catalyst, and (d) a liquid containing at least an addition reaction promoting catalyst. A method for producing a waterless lithographic printing plate precursor, characterized in that is mixed at an arbitrary ratio immediately before coating. (C) The waterless lithographic plate according to claim 5 or 6, wherein the liquid containing at least the SiH group-containing compound and the condensation reaction promoting catalyst contains a silane coupling agent or an ethylenically unsaturated bond-containing silane coupling agent. A method for producing a printing plate precursor.