JP2017167537A - Silicone composition for printing plate, and method of manufacturing lithographic printing plate original plate, lithographic printing plate and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic printing plate original plate and a lithographic printing plate having a silicone rubber layer excellent in adhesive force with a lower layer and scratch resistance, and a silicone composition for printing plate used in manufacturing the lithographic printing plate original plate.SOLUTION: There are provided a silicone composition for printing plate containing (A) organopolysiloxane having a silanol group and (B) a compound represented by the following general formula (VII), a method of manufacturing a lithographic printing plate original plate and a lithographic printing plate using the same, and a method of manufacturing a printed matter using the lithographic printing plate. In the general formula (VII), M represents a linear, branched, cyclic bivalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, R represents a linear or branched monovalent alkyl group having 1 to 3 carbon atoms and L represents a monovalent functional group.SELECTED DRAWING: None

Description

  The present invention relates to a silicone composition for a printing plate, a lithographic printing plate precursor using the silicone composition for a printing plate, a method for producing a lithographic printing plate, and a method for producing a printed material using the lithographic printing plate.

  There are various types of printing such as letterpress printing, intaglio printing, stencil (screen) printing, and lithographic printing, and printing is performed taking advantage of the characteristics of each method. In particular, lithographic printing is more advantageous than other printing methods in that printed matter with high definition can be obtained and the total cost including running cost is low.

  In lithographic printing, an ink-receptive image area and an ink repellent non-image area are present on the same plane of the printing plate, and ink is applied only to the image area using the difference in ink adhesion. After that, the printing method is to transfer the ink to a printing medium such as paper. Printing plates for lithographic printing (hereinafter referred to as lithographic printing plates) include non-image areas that are ink repellent by the action of dampening water, and silicone rubber and fluororesin without using dampening water. Are generally used as ink repellent non-image areas.

  Various proposals have been made so far for lithographic printing plates using such a silicone rubber or fluororesin as an ink repellent non-image area.

  For example, a lithographic printing plate precursor using a condensation reaction (wet curing) type silicone rubber layer as the ink repellent layer is exemplified (see, for example, Patent Document 1).

  Moreover, a lithographic printing plate precursor using a condensation reaction type silicone rubber layer as the ink repellent layer and containing silicone oil in the silicone rubber layer is mentioned (for example, see Patent Documents 2 and 3).

  On the other hand, various proposals have been made regarding inks used for lithographic printing using a lithographic printing plate using silicone rubber or fluororesin as an ink repellent non-image area.

  For example, there is UV ink that is instantly cured by irradiation with ultraviolet light (for example, see Patent Document 4).

JP-A-61-230151 (Claims) JP 2001-232959 A (Claims) JP-A-7-36178 (Claims) Japanese Patent No. 5158274 (Claims)

  Although the condensation reaction type silicone rubber layer described in Patent Document 1 includes a tetrafunctional silane coupling agent and has excellent curability, the content of the amino group-containing silane coupling agent is too low or too high. Adhesive strength and scratch resistance were insufficient. Further, since ink repellency liquid was not included, ink repellency was insufficient. Although the condensation reaction type silicone rubber layer described in Patent Document 2 contains a small amount of silicone oil, it has good resilience to conventional oil-based inks. The resilience was insufficient for a small amount of active energy ray-curable ink. In addition, since it does not contain a tetrafunctional silane coupling agent, it cures slowly, and in addition to the excessive content of the amino group-containing silane coupling agent, it is ethoxysilane, so it is poor in reactivity. Adhesiveness with was also insufficient. Although the condensation reaction type silicone rubber layer described in Patent Document 3 also contains a small amount of silicone oil, the resilience to conventional oil-based inks is good, but the resilience to active energy ray-curable inks is insufficient. Met. In addition, since it does not contain a tetrafunctional silane coupling agent, it cures slowly. Further, since it does not contain a silane coupling agent containing an amino group as described in Patent Documents 1 and 2 above, The scratch resistance was also insufficient.

  Therefore, an object of the present invention is to provide a lithographic printing plate precursor and a lithographic printing plate that have a silicone rubber layer that is excellent in adhesion to the lower layer and scratch resistance, in order to solve the problems in the prior art. Another object of the present invention is to provide a printing plate silicone composition for use in the production of such a lithographic printing plate precursor.

In order to solve the above problems, the silicone composition for a printing plate according to the present invention has the following constitution. That is,
(A) an organopolysiloxane having a silanol group;
(B) A silicone composition for a printing plate containing a compound represented by the following general formula (VII).

（一般式（ＶＩＩ）中、Ｍは炭素数１〜６の直鎖状、枝分かれ状、環状の２価の飽和または不飽和炭化水素基を表し、Ｒは炭素数１〜３の直鎖状または枝分かれ状の１価のアルキル基を表す。また、Ｌは１価の官能基を表す。）

(In General Formula (VII), M represents a linear, branched, or cyclic divalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents a linear or branched structure having 1 to 3 carbon atoms. Represents a branched monovalent alkyl group, and L represents a monovalent functional group.)

  The present invention also provides a lithographic printing plate precursor using the silicone composition for a printing plate as described above, a method for producing a lithographic printing plate, and a method for producing a printed material using the lithographic printing plate. Details will be described later.

  According to the present invention, it is possible to provide an optimum silicone composition for a printing plate that is used in the production of a lithographic printing plate precursor and a lithographic printing plate. By using this silicone composition for a printing plate, adhesion to a lower layer can be achieved. A lithographic printing plate precursor and a lithographic printing plate having a silicone rubber layer excellent in strength and scratch resistance are obtained. Moreover, a desired printed matter can be obtained by performing lithographic printing with high ink repulsion using the lithographic printing plate and appropriate ink.

It is a schematic sectional drawing which shows an example of the manufacturing method of the printed matter of this invention.

  The present invention is a printing plate silicone composition comprising (A) an organopolysiloxane having a silanol group and (B) a compound represented by the aforementioned general formula (VII) (hereinafter each referred to as component (A)) , (B) may be omitted).

  (B) By containing the compound represented by general formula (VII), the adhesive force and scratch resistance with respect to a lower layer improve.

  Further, by containing (C) ink repellent liquid (hereinafter, may be abbreviated as (C) component), the ink repulsion property, especially in ink represented by active energy ray curable ink, etc. It is possible to improve the resilience to inks that do not contain or contain a small amount of stain inhibiting components. Further, since (D) a tetrafunctional silane coupling agent (hereinafter, may be abbreviated as (D) component) improves the curability of the silicone rubber layer, production of a lithographic printing plate precursor In the line, it is possible to suppress contamination due to transfer of the silicone component to a conveyance roller or the like due to poor curing of the silicone rubber layer.

  As described above, the lithographic printing plate precursor and the lithographic printing plate having a silicone rubber layer excellent in adhesion to the lower layer and scratch resistance can be obtained from the silicone composition for a printing plate of the present invention.

Hereinafter, the present invention will be described in more detail.
First, the silicone composition for printing plates will be described. The silicone composition for a printing plate of the present invention is a silicone composition for a printing plate containing (A) an organopolysiloxane having a silanol group and (B) a compound represented by the aforementioned general formula (VII).

  (A) As organopolysiloxane which has a silanol group, the compound represented by the following general formula (IV) can be mentioned, It is organopolysiloxane which has a 2 or more silanol group in a molecule | numerator. Among them, a compound having silanol groups at both ends of the molecular main chain is preferable in terms of improving the curability of the silicone rubber layer. Moreover, you may contain 2 or more types of these.

（一般式（ＩＶ）中、Ｔは下記一般式（Ｖ）で示される官能基である。）

(In general formula (IV), T is a functional group represented by the following general formula (V).)

（一般式（ＩＶ）および（Ｖ）中、Ｒ^１は水酸基または脂肪族不飽和結合を含まない一価の有機基のいずれかを示し、Ｒ^２は脂肪族不飽和結合を含まない一価の有機基を示す。脂肪族不飽和結合を含まない一価の有機基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基などのアルキル基；フェニル基、トルイル基、キシリル基、ナフチル基などのアリール基；ベンジル基、フェネチル基などのアラルキル基；クロロメチル基、３−クロロプロピル基、３，３，３−トリフロロプロピル基などのハロゲン化アルキル基などが挙げられる。ａは０〜４，０００、ｂは０〜５、ｃは０〜２，０００、およびｄは０〜４，０００の範囲内の整数を示す。Ｒ^１が脂肪族不飽和結合を含まない一価の有機基である場合、ｂは２以上の整数であり、Ｒ^１およびＲ^２はそれぞれ独立し、同じであっても異なっていてもよい。また、少なくともａ、ｂ、ｃのいずれか１つは１以上の整数であり、ｄは０または１以上の整数である。）

(In the general formulas (IV) and (V), R ¹ represents either a hydroxyl group or a monovalent organic group that does not contain an aliphatic unsaturated bond, and R ² represents a monovalent organic group that does not contain an aliphatic unsaturated bond. Examples of monovalent organic groups not containing an aliphatic unsaturated bond include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; Aryl groups such as a group, xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group A represents 0 to 4,000, b represents 0 to 5, c represents 0 to 2,000, and d represents an integer within the range of 0 to 4,000, and R ¹ represents an aliphatic unsaturated bond. Monovalent organic group not included Some cases, b is an integer of 2 or more, R ¹ and R ² each independently may be different even in the same. Also, at least a, b, one of c is 1 or more (It is an integer, and d is an integer of 0 or 1 or more.)

In the general formulas (IV) and (V), it is preferable from the viewpoint of ink repellency of the lithographic printing plate that R ¹ and R ² are each 50% by mole or more of methyl groups.

  The weight average molecular weight of the organopolysiloxane having (A) silanol group is preferably 30,000 or more in terms of improving printing durability and scratch resistance, and 300 in terms of improving curability and image reproducibility. 1,000 or less is preferable.

  The molecular weight of these (A) organopolysiloxanes having silanol groups can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.

  (A) The content of the organopolysiloxane having a silanol group is preferably 60% by mass or more and more than 70% by mass in the silicone composition for a printing plate in terms of improving the ink resilience of the silicone rubber layer. More preferred. Moreover, 99 mass% or less is preferable at the point which ensures the sclerosis | hardenability of a silicone rubber layer.

  The silicone composition for a printing plate of the present invention contains (B) the compound represented by the general formula (VII) (component (B)) in addition to the component (A).

  (B) As a compound represented by the said general formula (VII), 1 or more types selected from the compound represented by the following general formula (VIII)-(X) are mentioned.

（一般式（ＶＩＩＩ）〜（Ｘ）中、Ｍは炭素数１〜６の直鎖状、枝分かれ状、環状の２価の飽和または不飽和炭化水素基を表し、Ｒは炭素数１〜３の直鎖状または枝分かれ状の１価のアルキル基を表し、Ｘは水素、炭素数１〜６の直鎖状、枝分かれ状、環状の１価の飽和または不飽和炭化水素基のいずれかを表す。また、Ｊは炭素数１〜６の直鎖状、枝分かれ状、環状の１価の飽和または不飽和炭化水素基を表す。）

(In the general formulas (VIII) to (X), M represents a linear, branched or cyclic divalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents 1 to 3 carbon atoms. A linear or branched monovalent alkyl group is represented, and X represents any one of hydrogen, a linear, branched, and cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. J represents a linear, branched, or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms.)

  (B) As a compound represented by the said general formula (VIII)-(X), 1 or more types selected from the compound represented by the following general formula (XI)-(XIII) are mentioned.

（一般式（ＸＩ）〜（ＸＩＩＩ）中、Ｘは水素、炭素数１〜６の直鎖状、枝分かれ状、環状の１価の飽和または不飽和炭化水素基のいずれかを表し、Ｒは炭素数１〜３の直鎖状または枝分かれ状の１価のアルキル基を表す。また、Ｊは炭素数１〜６の直鎖状、枝分かれ状、環状の１価の飽和または不飽和炭化水素基を表す。）

(In General Formulas (XI) to (XIII), X represents hydrogen, a linear, branched, or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents carbon. Represents a linear or branched monovalent alkyl group having 1 to 3 and J represents a linear, branched, or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. Represents.)

  R of the compounds represented by the general formulas (VII) and (VIII) to (XIII) is preferably a methyl group from the viewpoint of improving adhesion to the lower layer and scratch resistance. Specific examples of the compounds represented by the general formulas (VII) and (VIII) to (XIII) in which R is a methyl group include 3-ureidopropyltrimethoxysilane and methyl [3- (trimethoxysilyl) propyl] carbamate. , Ethyl [3- (trimethoxysilyl) propyl] carbamate, tert-butyl [3- (trimethoxysilyl) propyl] carbamate, and the like, but are not limited thereto.

  (B) As content of the compound represented by said general formula (VII), (VIII)-(XIII), 0.20 mass% or more and 0.40 mass in all the components of the said silicone composition for printing plates. % Or less is preferable. By containing 0.20% by mass or more, the adhesive force and scratch resistance to the lower layer are improved, and by containing 0.40% by mass or less, high adhesive force to the lower layer can be maintained. More preferably, it is 0.25 mass% or more and 0.35 mass% or less.

  Other examples of the compound represented by (B) the general formula (VII) include one or more selected from compounds represented by the following general formulas (XIV) to (XVII).

（一般式（ＸＩＶ）〜（ＸＶＩＩ）中、Ｍは炭素数１〜６の直鎖状、枝分かれ状、環状の２価の飽和または不飽和炭化水素基を表し、Ｒは炭素数１〜３の直鎖状または枝分かれ状の１価のアルキル基を表す。また、Ｒ^４は炭素数１〜６の直鎖状、枝分かれ状、環状の１価の飽和または不飽和炭化水素基のいずれかを表し、Ｘは水素、炭素数１〜６の直鎖状、枝分かれ状、環状の１価の飽和または不飽和炭化水素基のいずれかを表す。）

(In the general formulas (XIV) to (XVII), M represents a linear, branched or cyclic divalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents 1 to 3 carbon atoms. Represents a linear or branched monovalent alkyl group, and R ⁴ represents a linear, branched or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. X represents hydrogen, a straight-chain, branched or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms.)

  (B) As a compound represented by the said general formula (XIV)-(XVII), 1 or more types selected from the compound represented by the following general formula (I)-(III) are mentioned.

（一般式（Ｉ）〜（ＩＩＩ）中、Ｘは水素、炭素数１〜６の直鎖状、枝分かれ状、環状の１価の飽和または不飽和炭化水素基のいずれかを表し、Ｒは炭素数１〜３の直鎖状または枝分かれ状の１価アルキル基を表す。）

(In the general formulas (I) to (III), X represents hydrogen, a linear, branched, or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents carbon. Represents a linear or branched monovalent alkyl group of 1 to 3)

  R is preferably a methyl group in the compounds represented by the general formulas (VII), (XIV) to (XVII) and (I) to (III) from the viewpoint of improving the adhesion and scratch resistance with the lower layer. . Specific examples of the compounds represented by the general formulas (VII), (XIV) to (XVII) and (I) to (III) in which R is a methyl group include 3-aminopropyltrimethoxysilane, N-methylamino Propyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (6-aminoethyl) aminopropyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl Examples thereof include, but are not limited to, ethylenediamine, 3- (N-allylamino) propyltrimethoxysilane, aminophenyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, and the like.

  (B) As content of the compound represented by said general formula (VII), (XIV)-(XVII), (I)-(III), it is set to 0. in all the components of the said silicone composition for printing plates. It is preferable that it is 20 mass% or more and 0.40 mass% or less. By containing 0.20% by mass or more, the adhesive force and scratch resistance to the lower layer are improved, and by containing 0.40% by mass or less, high adhesive force to the lower layer can be maintained. More preferably, it is 0.25 mass% or more and 0.35 mass% or less.

  (C) The ink repellent liquid is preferably a silicone compound, and more preferably silicone oil. The silicone oil in the present invention refers to a free organopolysiloxane component that is not involved in crosslinking of the silicone rubber layer. For example, silicone oils such as polydimethylsiloxane terminated with trimethylsilyl group, cyclic polydimethylsiloxane, dimethylsiloxane-methylphenylsiloxane copolymer terminated with trimethylsilyl group, dimethylsiloxane-diphenylsiloxane copolymer terminated with trimethylsilyl group, alkyl-modified silicone oil, fluorine Modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy polyether modified silicone oil, phenol modified silicone oil, carboxy modified silicone oil, mercapto modified silicone oil, amide modified silicone Oil, carbana modified silicone oil, higher fatty acid modified silico Modified silicone oils obtained by introducing part to various organic groups such as methyl groups in the molecule, such as N'oiru the like.

(C) The ink repellent liquid preferably has a mass reduction rate of 0% by mass or more and 0.5% by mass or less after heating at 150 ° C. for 24 hours under an atmosphere of 1 atm. If the mass reduction rate after heating at 150 ° C. for 24 hours in a 1 atm environment is 0% by mass or more and 0.5% by mass or less, it is difficult to volatilize during the production and storage of a lithographic printing plate precursor, and the ink repellent effect It is hard to lose. The mass reduction rate of the ink repellent liquid in the present invention can be calculated by the following measurement and calculation. An arbitrary amount of ink repellent liquid (A [g]) is weighed into a petri dish under an atmosphere of 1 atm. Heating is performed for 24 hours under the condition of ° C., and the mass (B [g]) of the ink repellent liquid after heating is measured. The mass reduction rate of the ink repellent liquid can be calculated by applying each mass before and after heating obtained by the measurement to the following mathematical formula (1).
Weight reduction rate of ink repellent liquid [% by mass] = 100 × (A−B) / A (1)

  The surface tension of the ink repellent liquid at 25 ° C. is preferably 15 mN / m or more and 30 mN / m or less. When the surface tension at 25 ° C. is 15 mN / m or more, the affinity with the other components of the silicone composition for printing plates is higher, and the stability of the silicone composition for printing plates is improved. If the surface tension at 25 ° C. is 30 mN / m or less, the ink is easily peeled off, and the ink resilience can be further improved. In addition, the surface tension in this invention points out the surface tension obtained by the Wilhelmy method (plate method). The surface tension of the ink repellent liquid at 25 ° C. can be measured using a commercially available surface tension meter (for example, “FACE automatic surface tension meter” CBVP-Z type (manufactured by Kyowa Interface Science Co., Ltd.)). . The ink repellent liquid is placed in a petri dish in contact with the heat bath, and is maintained at 25 ° C. by controlling the temperature of the circulating liquid (water, oil, etc.) in the heat bath.

  (C) As a content rate of an ink repellent liquid, it is preferable to contain 10 to 30 mass% in all the components of the silicone composition for printing plates. 10 mass% or more is preferable at the point which improves ink repellency remarkably, and 30 mass% or less is preferable at the point which maintains the film | membrane intensity | strength of an ink repulsion layer. More preferably, it is 15 mass% or more and 25 mass% or less.

  (C) The molecular weight of the ink-repellent liquid can be measured by gel permeation chromatography (GPC) using polystyrene as the preparation described above, and preferably has a weight average molecular weight Mw of 1,000 to 100,000.

  (D) As tetrafunctional silane coupling agents, tetramethoxysilane, tetraethoxysilane, tetranormalpropoxysilane, tetraisopropoxysilane, tetranormalbutoxysilane, tetrakis (2-ethylhexoxy) silane, tetrakis (2-octylde) (Decyloxy) silane, tetraallyloxysilane, tetraphenoxysilane, tetrakis (methoxyethoxy) silane, tetrakis (ethoxyethoxy) silane, tetrakis (1-methoxy-2-propoxy) silane, tetrakis (methoxyethoxyethoxy) silane, tetraacetoxy Examples include silane, tetrakis (trifluoroacetoxy) silane, tetrakis (methylethylketoximino) silane, tetrakis (methylisobutylketoximino) silane, and the like. But it is not limited to these. Of these, tetraacetoxysilane, tetrakis (trifluoroacetoxy) silane, tetrakis (methylethylketoximino) silane, and tetrakis (methylisobutylketoximino) silane are preferable from the viewpoint of curability. Two or more of these may be contained.

  (D) As a content rate of a tetrafunctional silane coupling agent, it is preferable to contain 0.50 mass% or more and 1.50 mass% or less in all the components of the silicone composition for printing plates. If it is 0.50% by mass or more, the curability is good, and if it is 1.50% by mass or less, the scratch resistance is good.

  The silicone composition for a printing plate of the present invention contains a trifunctional silane coupling agent represented by the following general formula (VI) different from the compound represented by (B) the general formula (VII) described above. Is preferable in that the adhesive force to the lower layer can be further improved.

（一般式（ＶＩ）中、Ｒ^３は炭素数１以上の置換もしくは非置換のアルキル基、アルケニル基、アリール基、またはこれらの組み合わされた基を表す。Ｚは加水分解性基を表し、それぞれ同一でも異なってもよい。）

(In general formula (VI), R ³ represents a substituted or unsubstituted alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, or a combination thereof. Z represents a hydrolyzable group, May be the same or different.)

In terms of reactivity, R ³ is preferably an alkenyl group or an aryl group. Z is an acyloxy group such as an acetoxy group, a ketoxime group such as a methylethylketoxime group, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, an alkenyloxy group such as an isopropenoxy group, or an acyl such as an acetylethylamino group. Examples include aminoxy groups such as alkylamino groups and dimethylaminoxy groups.

  Specific compounds include acetoxysilanes such as methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, allyltriacetoxysilane, phenyltriacetoxysilane, methyltris (methylethylketoximino) silane, ethyltris (methylethylketoximino) ) Ketoximinosilanes such as silane, vinyltris (methylethylketoximino) silane, allyltris (methylethylketoximino) silane, phenyltris (methylethylketoximino) silane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, vinyltriisopropoxy Alkoxysilanes such emissions, vinyl tris isopropenoxysilane silane, although such alkenyloxy silanes such as tri-isopropenoxysilane carboxymethyl silanes, but are not limited thereto. Of these, acetoxysilanes and ketoximinosilanes are preferable in terms of reactivity. Two or more of these may be contained.

  (B) As a content rate of the trifunctional silane coupling agent different from the compound represented by the general formula (VII), 1% by mass or more and 10% by mass or less is contained in all components of the silicone composition for printing plates. It is preferable to do. If it is 1 mass% or more, the adhesive force with respect to a lower layer will improve more, and if it is 10 mass% or less, scratch resistance and ink repellency will become favorable.

  (B) a compound represented by the general formula (VII), (D) a tetrafunctional silane coupling agent, and (B) a trifunctional silane coupling agent different from the compound represented by the general formula (VII). As the total content of all silane coupling agents, it is preferable to contain 2% by mass or more and 10% by mass or less in all components of the silicone composition for printing plates. If it is 2% by mass or more, the pot life of the silicone composition for printing plates is good, and if it is 10% by mass or less, scratch resistance and ink resilience are good.

  The silicone composition for printing plates of the present invention may contain a catalyst for the purpose of improving curability. Examples of the catalyst include organic carboxylic acids, acids, alkalis, amines, metal alkoxides, metal diketenates, organic acid salts of metals such as tin, lead, zinc, iron, cobalt, calcium, and manganese. Specific examples include dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, zinc octylate, and iron octylate. Two or more of these may be contained.

  As a content rate of a catalyst, it is preferable to contain 0.01 to 1 mass% in all the components of the silicone composition for printing plates. If it is 0.01 mass% or more, the sclerosis | hardenability of a silicone rubber layer and adhesiveness with a lower layer will become favorable, and if it is 1 mass% or less, the stability of the silicone composition for printing plates will become favorable.

  The silicone composition for a printing plate of the present invention may contain a solvent for the purpose of improving coating properties and ejection properties. In the present invention, a liquid obtained by diluting the printing plate silicone composition with a solvent is referred to as a printing plate silicone composition diluted solution.

Examples of the solvent include aliphatic, alicyclic, and aromatic hydrocarbons, halogenated hydrocarbons, and chain or cyclic ether compounds. Among these, aliphatic or alicyclic hydrocarbons are preferable from the viewpoint of improving economy and safety. In addition, the solubility parameter of the solvent is preferably 16.4 (MPa) ^1/2 or less, more preferably 15.4 (MPa) ^1/2 or less, and 14.4 in terms of improving the solubility of the silicone composition. (MPa) ^1/2 or less is more preferable. Moreover, it is preferable that a boiling point is 60 degreeC or more from the point which improves safety | security and handleability, and it is more preferable that it is 80 degreeC or more. On the other hand, the boiling point is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, from the viewpoint of improving the drying property of the coating liquid. Specific examples of such solvents include linear or branched aliphatic hydrocarbons having 6 to 9 carbon atoms, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and trimethylcyclohexane. And so on. Two or more of these solvents may be intentionally mixed and used, or a commercially available solvent represented by the following in which these solvents are mixed in advance may be used.

  As a mixture of branched aliphatic hydrocarbons, for example, “Marcazole” 8 (manufactured by Maruzen Petrochemical Co., Ltd.), “Isopar” C, “Isopar” E (all manufactured by ExxonMobil Chemical Co.), “IP Solvent” 1016 ( Idemitsu Kosan Co., Ltd.) and “Isolol” 200 (manufactured by JX Nippon Oil & Energy Corporation) are available and are available from each company.

  As a mixture of alicyclic hydrocarbons, for example, “Exor” DSP80 / 100, “Exor” DSP100 / 140, “Exor” D30 (all manufactured by ExxonMobil Chemical), CS volatile oil (JX Nippon Oil & Energy Corporation) )) And is available from each company.

  In addition, a solvent other than the aforementioned aliphatic, alicyclic, and aromatic hydrocarbons, halogenated hydrocarbons, chain or cyclic ether compounds, and the like can be used as a mixture. From the viewpoint of improving the solubility of the composition, the above-mentioned solvent is preferably contained in an amount of 80% by volume or more, more preferably 90% by volume or more in the total solvent.

  In addition to the above-mentioned compounds, the silicone composition for printing plates of the present invention includes known reinforcing agents such as fumed silica and silicone resins having vinyl groups, SiH groups, and silanol groups for the purpose of improving rubber strength. It may contain.

  Further, for the purpose of imparting plate inspection properties to the developed lithographic printing plate, it may contain a colored dye described in JP-A No. 2002-244279 and a colored pigment described in International Publication No. 2008/056588.

  Although the specific preparation method of the silicone composition dilution liquid for printing plates is described below, it is not limited to this.

  For example, a solvent, an organopolysiloxane having a silanol group, and an ink repellent liquid are put into a container, and the mixture is stirred and mixed with a generally known mixer or the like until the components are uniform (stirring is a diluted silicone composition for a printing plate) Continue until completion). The obtained liquid mixture is bubbled with a dry gas (dry air, dry nitrogen, etc.) for 10 minutes or more to remove the water in the liquid. It is preferable in terms of improvement. Into the obtained mixed liquid, a mixed liquid in which a trifunctional silane coupling agent different from the compound represented by the general formula (VII) and a tetrafunctional silane coupling agent are mixed is added. After stirring and mixing, the catalyst is added and mixed with stirring. Finally, a silicone composition diluent for a printing plate can be obtained by adding and stirring and mixing the compound represented by the general formula (VII).

  Next, the planographic printing plate precursor will be described. Here, the lithographic printing plate precursor refers to a precursor of a lithographic printing plate used for producing a lithographic printing plate used for printing. The lithographic printing plate precursor according to the invention has at least a substrate, a heat-sensitive layer, and a silicone rubber layer in this order.

  As the substrate, known dimensionally stable paper, metal, glass, film, etc., which have been conventionally used as a lithographic printing plate substrate, can be used. Specifically, paper; paper laminated with plastic (polyethylene, polypropylene, polystyrene, etc.); metal plate such as aluminum (including aluminum alloy), zinc, copper; glass plate such as soda lime, quartz; silicon wafer; Plastic films such as cellulose acetate, polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal; paper or plastic film on which the above metal is laminated or vapor-deposited. The plastic film may be transparent or opaque, but an opaque film is preferable for improving plate inspection.

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

  The thickness of the substrate is not particularly limited, and a thickness corresponding to a printing machine used for printing may be selected.

  Examples of the heat sensitive layer provided on the substrate include, but are not limited to, the heat sensitive layers described below.

<Heat-sensitive layer-1>: Heat-dissolving heat-sensitive layer The heat-dissolving heat-sensitive layer is a heat-sensitive heat-sensitive layer in which a cross-linking structure is formed by a cross-linking agent in the state of a lithographic printing plate precursor, This is a heat-sensitive layer in which the adhesive strength between the layer and the silicone rubber layer is lowered. Subsequent development processing removes the silicone rubber layer in the portion irradiated with the laser beam. Most of the heat-sensitive layer in the laser-irradiated portion remains even after development. Examples of the heat-dissolving heat-sensitive layer include a composition containing a polymer having active hydrogen, a cross-linking agent and a photothermal conversion substance, a diluted solution thereof or a polymer having active hydrogen, an organic complex compound, a composition containing a photothermal conversion substance, And a layer obtained by applying the diluted solution and drying (heating). The polymer having active hydrogen is preferably a polymer having a phenolic hydroxyl group such as a homopolymer or copolymer of p-hydroxystyrene, a novolac resin, or a resole resin. Examples of the crosslinking agent include organic complex compounds, polyfunctional isocyanates, polyfunctional blocked isocyanates, polyfunctional epoxy compounds, polyfunctional (meth) acrylate compounds, polyfunctional aldehydes, polyfunctional mercapto compounds, polyfunctional alkoxysilyl compounds, Examples include functional amine compounds, polyfunctional carboxylic acids, polyfunctional vinyl compounds, polyfunctional diazonium salts, polyfunctional azide compounds, and hydrazine. Examples of the organic complex compound include acetylacetone complexes and acetoacetate complexes of Al (III), Fe (II), Fe (III), Ti (IV), and Zr (IV). Examples of the photothermal conversion substance include dyes and pigments that absorb infrared rays or near infrared rays. Specific examples of the heat-melting type heat-sensitive layer include, for example, heat-sensitive layers described in JP-A-11-221977, JP-A-2005-309126, and JP-A-2009-014946.

<Thermosensitive layer-2>: Thermal expansion type thermosensitive layer As specific examples of the thermal expansion type thermosensitive layer, for example, a thermosensitive layer having air bubbles described in JP-A-2005-300586 and JP-A-2005-331924, Examples thereof include a heat-sensitive layer having liquid bubbles described in International Publication No. 2010 / 113989A1.

  High-sensitivity direct-drawing lithographic printing plate precursor that has bubbles or liquid bubbles in the heat-sensitive layer (refers to a lithographic printing plate precursor that can write an image directly from a document using laser light), and applies physical force after exposure Just develop. For this reason, in the process of producing a lithographic printing plate by exposing a direct-drawing lithographic printing plate precursor, a phenomenon called “fire blistering” in which the silicone rubber layer in the exposed portion is lifted may occur. When the “fire blister” phenomenon occurs, when the direct-drawing lithographic printing plate precursor after exposure is transported, the lifted silicone rubber layer may be transferred to a transport roller in an exposure machine or an automatic developing machine. The silicone rubber layer transferred to the transport roller is retransferred to the plate surface of the next plate to be processed, which causes exposure inhibition and development inhibition. This blistering phenomenon is more likely to occur as the direct-drawing lithographic printing plate precursor has higher sensitivity and as the exposure amount increases.

  Specific examples of the thermal expansion type heat-sensitive layer for suppressing such a blistering phenomenon include, for example, JP2012-93728A, JP2012-133321A, JP2012-133322A, and International Publication. A heat-sensitive layer containing non-photosensitive particles as described in 2012 / 043282A1 and the like, a novolac resin described in International Publication No. 2012 / 099003A1, polyurethane and a photothermal conversion substance at least, and a phase containing at least a novolak resin And a heat-sensitive layer having a phase separation structure having a phase containing polyurethane.

<Thermosensitive layer-3>: Thermal ablation type thermosensitive layer This is a thermosensitive layer of the type that is thermally ablated by irradiation with a near infrared laser. By subsequent development processing, the silicone rubber layer on the surface is removed together with the destroyed heat-sensitive layer to form an image area. For example, the heat-sensitive layer described in JP-A-7-314934, JP-A-9-086065, JP-A-9-131981, US Pat. No. 5,353,705 and the like can be mentioned.

<Thermosensitive layer-4>: Thermal separation type thermosensitive layer The first layer and the second layer attached thereto are included, and the first layer and the second layer are made of ink and an ink repellent liquid. The first layer is removed from the second layer without heating the printing member having a different affinity for the selected at least one printing liquid to substantially ablate the second layer. An imaging system for irreversibly separating images with a pattern associated with an image; a first layer; a second layer disposed underneath the first layer; and a second layer A third layer disposed on the lower side, wherein at least one of the first layer and the other layer has different affinity for at least one printing liquid selected from the group consisting of ink and ink repellent liquid Heating the printing member having an ablation of the second layer. And an image forming system that irreversibly separates the first layer from the second layer with an image related pattern. In the above system, the second layer on which the printed pattern is formed is a heat separation type heat sensitive layer. For example, the heat-sensitive layer described in US Pat. No. 6,107,001 can be exemplified.

<Thermosensitive layer-5>: Thermosetting thermosensitive layer This is a thermosensitive layer in which a cross-linked structure is formed by a heat-activated cross-linking agent by heat generated by irradiation with a near infrared laser. Subsequent development processing leaves a portion of the silicone rubber layer that has been irradiated with laser light, and removes the silicone rubber layer that has not been irradiated. The heat-sensitive layer in the unirradiated portion of the laser remains even after development. Examples thereof include thermosetting thermosensitive layers described in JP-A-11-157236 and JP-A-11-240271.

The film mass of the heat sensitive layer is preferably 0.5 g / m ² or more from the viewpoint of improving the printing durability, heat sensitivity or photosensitivity of the lithographic printing plate. Moreover, 7 g / m < ² > or less is preferable at the point which is easy to volatilize a dilution solvent and is excellent in productivity.

  The silicone rubber layer can be formed by applying the above-described printing plate silicone composition or the printing plate silicone composition diluent on the heat-sensitive layer provided on the substrate.

The film mass of the silicone rubber layer is preferably within the range of 0.6 to 10 g / m ² . When the film mass of the silicone rubber layer is 0.6 g / m ² or more, the ink repellency, scratch resistance and printing durability of the lithographic printing plate are sufficient, and when it is 10 g / m ² or less, it is disadvantageous from an economic standpoint. In other words, image reproducibility and ink mileage are unlikely to deteriorate. A range of 1 to 5 g / m ² is more preferable.

  In the lithographic printing plate precursor according to the present invention, a heat insulating layer is provided between the substrate and the heat-sensitive layer for the purpose of improving adhesiveness, preventing light halation, improving plate inspection, improving heat insulation, and improving printing durability. You may have. Examples of the heat-insulating layer used in the present invention include, but are not limited to, the heat-insulating layers described in JP-A-2004-199016, JP-A-2004-334025, JP-A-2006-276385, and the like. .

The film mass of the heat insulating layer is preferably 1 g / m ² or more from the viewpoint of improving the printing durability and heat insulating properties of the lithographic printing plate. Moreover, 25 g / m < ² > or less is preferable at the point which the diluting solvent volatilizes easily and is excellent in productivity. A range of ^{2 to 20} g / m ² is more preferable.

  The planographic printing plate precursor of the present invention may be provided with a cover film and / or a slip sheet on the plate surface for the purpose of protecting the plate surface.

  As the cover film, a film having a thickness of 100 μm or less that transmits light of an exposure light source wavelength favorably is preferable. Specific examples include polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, and cellophane. In addition, for the purpose of preventing exposure of the original plate due to exposure, it has various light absorbers, photobleachable substances, and photochromic substances as described in JP-A-2-063050 on the cover film. Also good.

The slip sheet is preferably one weighing 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 laminate of the lithographic printing plate precursor and the paper becomes thin, and workability is improved. Is advantageous. Examples of interleaving paper preferably used include, 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 (manufactured by Oji Paper Co., Ltd.), Kurpack 73 g / m ² (Oji (Manufactured by Paper Manufacturing Co., Ltd.), etc., and can be obtained from each company, but is not limited thereto.

Next, a method for producing a lithographic printing plate precursor will be described.
When providing a heat insulation layer on a board | substrate, a heat insulation layer composition or its dilution liquid is apply | coated on a board | substrate, and a heat insulation layer is formed on a board | substrate by drying and hardening under a heating or non-heating.

  A slit die coater, a gravure coater, a roll coater, a wire bar coater, or the like can be used to apply the heat insulating layer composition or a diluted solution thereof, but a slit die coater is preferable.

  For the heating, a hot air dryer, an infrared dryer or the like can be used, and it is preferable to dry at a temperature of 50 to 250 ° C. for 30 seconds to 5 minutes.

  A heat-sensitive layer composition or a diluted solution thereof is applied on a substrate or a heat insulating layer, and dried and cured under heating or non-heating to form a heat-sensitive layer on the substrate or the heat insulating layer.

  A slit die coater, a gravure coater, a roll coater, a wire bar coater, or the like can be used for coating the heat sensitive layer composition or a diluted solution thereof, but a slit die coater is preferred.

  For the heating, a hot air dryer, an infrared dryer or the like can be used, and it is preferable to dry at a temperature of 50 to 150 ° C. for 30 seconds to 5 minutes.

  Further, when a thin film of metal or the like is used as the heat sensitive layer, the above process can be changed to a process of depositing or sputtering the heat sensitive layer composition on the substrate or a substrate provided with a heat insulating layer.

  Next, a silicone composition for a printing plate or a diluted silicone composition for a printing plate is applied on the heat-sensitive layer, and dried and cured under heating or non-heating to form a silicone rubber layer.

  When applying the printing plate silicone composition or the printing plate silicone composition diluent, it is preferable to remove the water adhering to the surface of the heat sensitive layer as much as possible from the viewpoint of improving the adhesiveness.

  A slit die coater, a gravure coater, a roll coater, a wire bar coater, or the like can be used for coating the printing plate silicone composition or the printing plate silicone composition diluent, but the slit die coater is preferred.

  For the heating, a hot air dryer, an infrared dryer or the like can be used, and it is preferable to dry at a temperature of 50 to 150 ° C. for 30 seconds to 5 minutes.

  For the purpose of protecting the plate surface of the lithographic printing plate precursor, a cover film and / or a slip sheet may be provided on the silicone rubber layer.

  Next, a method for producing a planographic printing plate will be described. Examples of the method for producing a lithographic printing plate include a method including at least a step of exposing the above-described lithographic printing plate precursor (exposure step) and a step of removing either the exposed portion or the unexposed portion of the silicone rubber layer (developing step). It is done.

  First, the exposure process will be described. As a method for exposing the lithographic printing plate precursor according to the present invention, there is a method (CTP) in which an image is directly written on a direct-drawing lithographic printing plate precursor using a laser beam having a specific emission wavelength in accordance with digital data without using an original film. It is done. Examples of the laser light source used for exposure in the CTP method include those having an emission wavelength region in the range of 350 to 1,500 nm.

  Next, the development process will be described. The exposed lithographic printing plate precursor is rubbed in the presence or absence of a liquid to remove either the exposed or unexposed silicone rubber layer. Examples of the friction treatment include (i) a method of rubbing the plate surface with a developing pad, brush, dry cotton pad, etc. in the absence of a liquid, (ii) a nonwoven fabric impregnated with water or water added with a surfactant, absorbent cotton , A method of wiping the plate surface with a cloth, a sponge, etc., (iii) a method of rubbing with a rotating brush while bringing water or surfactant-added water into contact with the plate surface, and (iv) jetting high-pressure water, hot water or water vapor onto the plate surface. The method etc. are mentioned. As the surfactant, those having a pH of 5 to 8 when converted to an aqueous solution are preferable, and the surfactant content is preferably 10% by mass or less of the aqueous solution. Such an aqueous solution has high safety and is preferable from the viewpoint of economy such as disposal cost.

  Prior to development, a pretreatment in which a plate is immersed in a pretreatment solution for a certain time may be performed. Examples of the pretreatment liquid include water, polar water such as alcohol, ketone, ester and carboxylic acid added to water, aliphatic hydrocarbons, aromatic hydrocarbons and the like. A solvent added or a polar solvent is used. Among these, a pretreatment liquid using a glycol compound or a glycol ether compound as a main component is preferable. Moreover, you may add an amine compound, surfactant mentioned above, etc. in a pretreatment liquid.

  The pretreatment liquids are described in JP-A-63-179361, JP-A-4-163557, JP-A-4-343360, JP-A-9-34132, and International Publication No. 1997/017634. A pretreatment liquid etc. can be mentioned. Specific examples of the pretreatment liquid include PP-1, PP-3, PP-F, PP-FII, PTS-1, PH-7N, CP-1, NP-1, DP-1, CP-Y (any And Toray Industries, Inc.).

  In addition, for the purpose of improving the visibility of the image area and the measurement accuracy of halftone dots, dyes such as crystal violet, Victoria Pure Blue, Astrazone Red, etc. are added to water or water with a surfactant added to the image at the same time as development. It is also possible to dye the ink receiving layer at the line part. Furthermore, it can also dye | stain with the liquid which added said dye after image development.

  Part or all of the development process can be automatically performed by an automatic developing machine. As an automatic developing machine, a device having only a developing unit, a device in which a preprocessing unit and a developing unit are provided in this order, a device in which a preprocessing unit, a developing unit and a postprocessing unit are provided in this order, a preprocessing unit, a developing unit, An apparatus or the like provided with a post-processing section and a water washing section in this order can be used. Specific examples of such an automatic developing machine include TWL-650 series, TWL-860 series, TWL-1160 series (all manufactured by Toray Industries, Inc.), JP-A-4-2265, and JP-A-5- Examples thereof include automatic developing machines disclosed in Japanese Patent No. 2272, Japanese Patent Application Laid-Open No. 5-6000, and the like, and these can be used alone or in combination.

  In addition, as another method for producing a lithographic printing plate, the above-described printing plate silicone composition or the printing plate silicone composition dilution liquid is applied to an ink jet or the like on a substrate or another layer provided on the substrate. And a method of directly patterning and drying and curing the silicone rubber layer under heating or non-heating. In the case of heating, it is preferable to dry at a temperature of 50 to 150 ° C. for 30 seconds to 5 minutes using a hot air dryer or an infrared dryer.

  When the obtained lithographic printing plates are stacked and stored, it is preferable to sandwich a slip sheet between the plates for the purpose of protecting the plate surface.

  Next, a method for producing a printed material using a lithographic printing plate and ink will be described. The lithographic printing plate of the present invention can be suitably used for waterless printing in which printing is performed using only ink without using dampening water.

  The method for producing a printed material includes a step of attaching ink to the surface of a lithographic printing plate having at least a silicone rubber layer, and a step of transferring the ink directly or via a blanket to a printing medium.

  An embodiment of a method for producing a printed material according to the present invention will be described with reference to FIG. In the following, an example in which the blanket cylinder 4 is used will be described. However, the present invention is not limited to this, and the ink is applied to the planographic printing plate 2 mounted directly on the plate cylinder 3 from the ink roller 1 without using the blanket cylinder 4. After adhering, the ink may be directly transferred to the printing medium. In the following, an example in which ink is supplied from above the printing medium 5 will be described, but ink may be supplied from below the printing medium 5.

  First, ink is supplied to the ink roller 1. The ink supplied to the ink roller 1 adheres to the planographic printing plate 2 mounted on the plate cylinder 3 at the contact point with the plate cylinder 3. Ink adhering to the planographic printing plate 2 is transferred to the surface of the blanket cylinder 4 at the contact point with the blanket cylinder 4. The ink adhering to the blanket cylinder 4 is transferred to the printing medium 5 at the contact point with the printing medium 5 disposed on the impression cylinder 6. A printed matter is obtained by drying the printing medium 5 as necessary. The rotation speed of the ink roller and each cylinder is not particularly limited, and can be appropriately set according to the quality, delivery date, and ink properties required for the printed matter.

  Examples of the printing machine used for the production of the printed material include generally known direct printing printing machines and offset printing machines such as a sheet-fed system or a rotary printing system. However, the printing machine is more capable of suppressing damage to the lithographic printing plate during printing. An offset printer is preferable from the viewpoint of obtaining a printed matter. The offset printing machine includes a feeder unit, a printing unit, and a delivery unit. The printing unit includes at least an ink supply unit, a plate cylinder, a blanket cylinder, and an impression cylinder.

  As the offset printing machine, an offset printing machine in which a rocking roller and / or a plate cylinder is provided with a cooling mechanism is preferable in terms of improving the soil resistance.

  Examples of the printing medium include, but are not limited to, thin paper, thick paper, film, label, and metal.

  In the case of printing using oil-based ink or water-soluble ink, the ink transferred to the printing medium is dried and / or cured by natural drying or heat treatment to obtain a printed matter.

  In the case of printing using an active energy ray-curable ink, the ink transferred to the printing medium is instantly cured by the active energy ray, and a printed matter is obtained.

  In the case of printing using UV ink which is one of the active energy rays, the ink transferred to the printing medium is instantly cured by ultraviolet light from an ultraviolet irradiation device, and a printed matter is obtained.

  Examples of the ink that can be preferably used in the present invention include, but are not limited to, the following inks.

<Ink-1>: Oil-based ink Examples of the oil-based ink include known oxidation polymerization type oil-based inks disclosed in JP-A-48-004107 and JP-A-01-306482. Further, the solvent components in conventional oil-based inks disclosed in JP-A-2005-336301, JP-A-2005-126579, JP-A-2011-144295, JP-A-2012-224823 and the like are used as mineral oil. Oil-based inks include soy oil ink, vegetable oil ink, non-VOC ink, and the like, which are replaced with (petroleum) component by vegetable oil component.

<Ink-2>: Water-soluble ink Examples of the water-soluble ink include known water-soluble inks that can be washed with water or an aqueous cleaning solution disclosed in Japanese Patent Application Laid-Open No. 2009-57461, Japanese Patent No. 4522094, and the like. It is done.

<Ink-3>: UV ink Examples of the UV ink include known ultraviolet curable inks disclosed in Japanese Patent No. 5158274, Japanese Patent Application Laid-Open No. 2012-211230, and the like. The UV ink includes high-sensitivity UV ink used for power-saving (light-reduction) UV printing and LED-UV printing.

  The lithographic printing plate of the present invention is a UV ink that has a very low content of the soil-restraining component, as well as exhibiting high ink resilience to oil-based inks and water-soluble inks that contain a large amount of the soil-restraining component. High ink resilience is also exhibited for active energy ray-curable inks such as

  Hereinafter, the present invention will be described in more detail with reference to examples. Evaluation in each example and comparative example was performed by the following method.

(1) Evaluation of Silicone Rubber Layer / Heat-Sensitive Interlayer Adhesion (Adhesion to Lower Layer) The reproducibility of the shadow area halftone dot serving as an index of the silicone rubber layer / heat-sensitive interlayer adhesion was evaluated by the following method.
The lithographic printing plate precursor with a laser exposure machine: "PlateRite" 8800E attached to (Dainippon Screen Mfg. Co., Ltd.), an exposure amount: dot percent 70% to 99% under the conditions of 125 mJ / cm ² (1% increments) The shadow halftone dot image (AM175 line (2400 dpi)) was exposed and developed under the following development conditions.
<Development conditions>
Automatic processor: TWL-1160FII (manufactured by Toray Industries, Inc.)
Pretreatment liquid: CP-Y (manufactured by Toray Industries, Inc., liquid temperature: 45 ° C.)
Developer: tap water (solution temperature: 30 ° C)
Post-treatment liquid: PA-1 (liquid temperature: 30 ° C.)
Flushing: tap water (liquid temperature: 30 ° C)
Development speed: 80 cm / min

In the obtained lithographic printing plate, the reproducibility of each halftone dot area ratio was observed with an optical microscope (objective lens: 10 to 50 times, eyepiece lens: 10 times), and the halftone dot area ratio that could be reproduced more than 90% was shadowed. With the dot reproducibility, the silicone rubber layer / thermosensitive interlayer adhesion was evaluated according to the following score.
4 points: halftone dots with an area ratio of 99% can be reproduced, and adhesion is very good. 3 points: halftone dots with an area ratio of 98% can be reproduced, and adhesiveness is two points: halftone dots with an area ratio of 98% can be reproduced. Slightly poor adhesion 1 point: The dot of 95% area ratio cannot be reproduced and the adhesion is poor

(2) Evaluation of scratch resistance An unexposed lithographic printing plate precursor was developed under the same development conditions as in (1) above. The developed lithographic printing plate (6 cm × 6 cm) is attached to a continuous load type friction fastness tester, and a raised pad with a length of about 5 mm, cut into 2 cm × 3 cm: “Caperon” NS5100 (Cambo Create Co., Ltd.) 150 reciprocating rubs at a load of 100 g. The lithographic printing plate after rubbing was affixed to an aluminum plate having a thickness of 0.15 mm, mounted on a printing machine: “OLIVER” 466SD (manufactured by Sakurai Graphic Systems Co., Ltd.), and printed under the printing conditions shown below.
<Printing conditions>
Ink roller: Trust Zeta (manufactured by Technoroll Co., Ltd.)
Blanket: MC1300 (manufactured by Kinyo)
Plate temperature: 28 ° C
Printing speed: 8,000 sheets / hour Printing medium: “OK Topcoat” (registered trademark) (manufactured by Oji Paper Co., Ltd.)
Ink: UV171CT black M-TW (manufactured by T & K TOKA)

The obtained printed matter was visually observed and scratch resistance was evaluated according to the following score.
4 points: no scratches are observed 3 points: light scratches are slightly observed 2 points: thin scratches are observed over the entire surface 1 point: dark scratches are observed over the entire surface

(3) Evaluation of ink resilience An unexposed lithographic printing plate precursor was developed under the same development conditions as in (1) above, and the developed lithographic printing plate was mounted on a printing machine: “OLIVER” 466SD, and the above (2 The printing was performed under the same printing conditions as in (1). The degree of background stain on the non-image area of the obtained printed matter was visually evaluated. When no background stain was observed, printing was performed again at a printing speed of 6,000 sheets / hour, and the background stain was visually evaluated. In the case where scumming was not recognized even at 6,000 sheets / hour, printing was performed again at a printing speed of 4,000 sheets / hour, and the degree of scumming was visually evaluated. The score was as follows.
5 points: No scumming at a printing speed of 4,000 sheets / hour 4 points: No scumming at a printing speed of 6,000 sheets / hour 3 points: No scumming at a printing speed of 8,000 sheets / hour 2 points: Printing speed 8,000 sheets / hour with stains on the gripper 1 point: Print speed is 8,000 sheets / hour with stains on the entire surface

(4) Evaluation of silicone rubber layer curability The curability of the silicone rubber layer immediately after heating was evaluated by a finger rub test. The score was as follows.
5 points: No whitening even when rubbed strongly with fingers (fully cured)
4 points: Slight whitening when rubbed strongly with finger 3 points: Whitening when rubbed strongly with finger 2 points: Whitening even when rubbed weakly with finger 1 point: Oil state

[Example 1]
On the degreased aluminum substrate (manufactured by Mitsubishi Aluminum Co., Ltd.) having a thickness of 0.24 mm, the following heat insulating layer composition diluted solution is applied, dried at 200 ° C. for 90 seconds, and a heat insulating layer having a film mass of 10 g / m ² . Was provided.

<Insulating layer composition diluent>
Add the following component (a) into the container and stir the components (b), (c), (d), (e) slowly while stirring with a three-one motor, and stir and mix until the components are uniform. did. The components (f) and (g) were added to the obtained mixed liquid and stirred and mixed for 10 minutes to obtain a heat insulating layer composition diluted liquid.
(A) The following titanium oxide dispersion: N, N-dimethylformamide dispersion (50% by mass of titanium oxide) of “Taipeku” (registered trademark) CR-50 (manufactured by Ishihara Sangyo Co., Ltd.): 60 parts by mass (b) Epoxy resin: “JER” (registered trademark) 1010 (manufactured by Mitsubishi Chemical Corporation): 35 parts by mass (c) Polyurethane: “Samprene” (registered trademark) LQ-T1331D (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration) : 20% by mass): 375 parts by mass (d) N, N-dimethylformamide: 730 parts by mass (e) Methyl ethyl ketone: 250 parts by mass (f) Aluminum chelate: “Aluminum chelate” ALCH-TR (Kawaken Fine Chemical Co., Ltd.) Manufactured): 10 parts by mass (g) Leveling agent: “Disparon” (registered trademark) LC951 (manufactured by Enomoto Kasei Co., Ltd., solid content: 10% by mass): 1 part by mass

<Preparation of titanium oxide dispersion>
Zirconia beads: “YTZ” (registered trademark) balls (φ1 mm, manufactured by Nikkato Co., Ltd.) 1,600 g filled in a sealable glass standard bottle, N, N-dimethylformamide: 500 g, “Taipeku” (registered) Trademark) CR-50 (Ishihara Sangyo Co., Ltd.): 500 g is charged, sealed, set on a small ball mill rotating base (manufactured by ASONE Co., Ltd.), and dispersed for 7 days at a rotational speed of 0.4 m / sec. As a result, a titanium oxide dispersion was obtained.
Next, the following heat-sensitive layer composition diluted solution was applied onto the heat insulating layer and heated at 140 ° C. for 90 seconds to provide a heat-sensitive layer having a film mass of 1.4 g / m ² . In addition, the thermosensitive layer composition dilution liquid was obtained by stirring and mixing the following components at room temperature.

<Thermosensitive layer composition diluent>
(A) Phenol formaldehyde novolak resin: “Sumilite Resin” (registered trademark) PR53195 (manufactured by Sumitomo Bakelite Co., Ltd.): 45.0 parts by mass (b) Polyurethane solution: “Nipporan” (registered trademark) 5196 (Nippon Polyurethane Co., Ltd., solid concentration: 30% by mass): 62.5 parts by mass (c) Infrared absorbing dye: “PROJET” 825LDI (manufactured by Avecia): 12.0 parts by mass (d) Titanium di-n- Butoxybis (acetylacetonate) solution: “Narsem” (registered trademark) titanium (manufactured by Nippon Chemical Industry Co., Ltd., solid content concentration: 73% by mass): 28.5 parts by mass (e) polyoxypropylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane = 1/3/1 mole of reactant (solid content concentration: 50% by mass) : 22.5 parts by mass (f) Tetrahydrofuran: 717.0 parts by mass (g) Ethanol: 112.5 parts by mass Next, the following silicone composition dilution liquid-1 for printing plate was applied on the heat-sensitive layer, and 140 A silicone rubber layer having a film mass of 2.0 g / m ² was provided by heating at 80 ° C. for 80 seconds.

<Silicone composition diluent for printing plate-1>
The following components (a) and (b) were charged into a container and mixed with stirring until the components were uniform. The obtained liquid was bubbled with dry nitrogen for 20 minutes to remove moisture in the liquid. The component (c) was added to the obtained liquid and stirred and mixed for 1 hour, and then the component (d) was added and stirred and mixed for another 10 minutes. Furthermore, (e) component was thrown in and the silicone composition dilution liquid-1 for printing plates was obtained by stirring and mixing for 10 minutes.
(A) Isoparaffinic solvent: “Isopar” (registered trademark) E (manufactured by ExxonMobil Chemical): 900.00 parts by mass (b) Organopolysiloxane having silanol groups (both ends silanol polydimethylsiloxane): “DMS” -S45 (manufactured by GELEST Inc., weight average molecular weight: 110,000, number of silanol groups in the molecule: 2): 94.65 parts by mass (c) Trifunctional different from the compound represented by the general formula (VII) Silane coupling agent: Vinyltris (methylethylketoximino) silane: 5.00 parts by mass (d) Reaction catalyst: dibutyltin diacetate: 0.05 parts by mass (e) Compound represented by the general formula (VII): 3-aminopropyltrimethoxysilane: 0.30 parts by mass

[Example 2]
Production of the planographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 1 except that the silicone composition dilution liquid-1 for printing plate was changed to the following silicone composition dilution liquid-2 for printing plate. .

<Silicone composition diluent for printing plate-2>
The following components (a), (b), and (c) were charged into a container and stirred and mixed until the components became uniform. The obtained liquid was bubbled with dry nitrogen for 20 minutes to remove moisture in the liquid. The component (d) was added to the obtained liquid and stirred and mixed for 1 hour, and then the component (e) was added and stirred and mixed for another 10 minutes. Furthermore, the component (f) was added and stirred and mixed for 10 minutes to obtain a silicone composition diluent-2 for a printing plate.
(A) "Isopar" (registered trademark) E: 900.00 parts by mass (b) "DMS" -S45: 74.65 parts by mass (c) Ink-repellent liquid: KF-96-50cs (silicone oil, weight Average molecular weight: 3,780, surface tension at 25 ° C .: 20.8 mN / m, mass reduction rate after heating at 150 ° C. for 24 hours under an atmosphere of 1 atm: 0.1% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.) 20.00 parts by mass (d) vinyltris (methylethylketoximino) silane: 5.00 parts by mass (e) dibutyltin diacetate: 0.05 parts by mass (f) 3-aminopropyltrimethoxysilane: 0.30 parts by mass

[Example 3]
Production of the planographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 1 except that the silicone composition diluent for printing plate-1 was changed to the following silicone composition diluent for printing plate-3. .

<Silicone composition diluent for printing plate-3>
The following components (a) and (b) were charged into a container and mixed with stirring until the components were uniform. The obtained liquid was bubbled with dry nitrogen for 20 minutes to remove moisture in the liquid. Into the obtained liquid, a mixed liquid in which the components (c) and (d) were previously mixed was added and stirred and mixed for 1 hour, and then the component (e) was added and stirred and mixed for another 10 minutes. Furthermore, the component (f) was added and stirred and mixed for 10 minutes to obtain a silicone composition diluent-3 for a printing plate.
(A) “Isopar” (registered trademark) E: 900.00 parts by mass (b) “DMS” -S45: 93.65 parts by mass (c) Vinyltris (methylethylketoximino) silane: 5.00 parts by mass (d) Tetrafunctional silane coupling agent: tetrakis (methylethylketoximino) silane: 1.00 parts by mass (e) dibutyltin diacetate: 0.05 parts by mass (f) 3-aminopropyltrimethoxysilane: 0.30 parts by mass

[Example 4]
Production of the planographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 1 except that the silicone composition diluent for printing plate-1 was changed to the following silicone composition diluent for printing plate-4. .

<Silicone composition diluent for printing plate-4>
The following components (a), (b), and (c) were charged into a container and stirred and mixed until the components became uniform. The obtained liquid was bubbled with dry nitrogen for 20 minutes to remove moisture in the liquid. Into the obtained liquid, a mixed liquid in which the components (d) and (e) were mixed in advance was added and stirred and mixed for 1 hour, and then the component (f) was added and stirred and mixed for another 10 minutes. Furthermore, the silicone composition dilution liquid-4 for printing plates was obtained by adding (g) component and stirring and mixing for 10 minutes.
(A) "Isopar" (registered trademark) E: 900.00 parts by mass (b) "DMS" -S45: 73.65 parts by mass (c) KF-96-50cs: 20.00 parts by mass (d) Vinyl tris ( Methylethylketoximino) silane: 5.00 parts by mass (e) Tetrakis (methylethylketoximino) silane: 1.00 parts by mass (f) Dibutyltin diacetate: 0.05 parts by mass (g) 3-Aminopropyltrimethoxysilane : 0.30 parts by mass

[Example 5]
The same as Example 4 except that 3-aminopropyltrimethoxysilane: 0.30 parts by mass of the diluted silicone composition for printing plate-4 was changed to 0.30 parts by mass of 3-aminopropyltriethoxysilane: 0.30 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated by the method.

[Example 6]
The amount of 3-aminopropyltrimethoxysilane: 0.30 parts by mass of the diluted silicone composition for printing plate-4 was changed to 0.30 parts by mass of N- (2-aminoethyl) 3-aminopropyltrimethoxysilane: 0.30 parts by mass. Except for the above, a lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4.

[Example 7]
Silicone composition diluent for printing plate-4: 3-aminopropyltrimethoxysilane: 0.30 parts by mass N, N′-bis [3- (trimethoxysilyl)] propyl] ethylenediamine: 0.30 parts by mass A lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4 except that the changes were made.

[Example 8]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition for printing plate-4 was changed to 73.75 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass was 0.20 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 9]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition for printing plate-4 was changed to 73.55 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass was 0.40 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 10]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plates was changed to 88.65 parts by mass, and KF-96-50cs: 20.00 parts by mass to 5.00 parts by mass. A lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4 except that the changes were made.

[Example 11]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition for printing plate-4 was changed to 83.65 parts by mass, and KF-96-50cs: 20.00 parts by mass to 10.00 parts by mass. A lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4 except that the changes were made.

[Example 12]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 63.65 parts by mass, and KF-96-50cs: 20.00 parts by mass to 30.00 parts by mass A lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4 except that the changes were made.

[Example 13]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 53.65 parts by mass, and KF-96-50cs: 20.00 parts by mass to 40.00 parts by mass A lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4 except that the changes were made.

[Example 14]
Lithographic printing in the same manner as in Example 4 except that tetrakis (methylethylketoximino) silane: 1.00 part by mass of the printing composition silicone composition diluent-4 was changed to tetraacetoxysilane: 1.00 part by mass. Preparation, plate making and evaluation of the plate precursor were performed.

[Example 15]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition for printing plate-4 was changed to 74.15 parts by mass, and tetrakis (methylethylketoximino) silane: 1.00 parts by mass was 0.50 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 16]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 73.15 parts by mass, and 1.50 parts by mass of tetrakis (methylethylketoximino) silane: 1.00 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 17]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 72.65 parts by mass, and tetrakis (methylethylketoximino) silane: 1.00 parts by mass was changed to 2.00 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 18]
"DMS" -S45: 94.65 parts by mass of the diluted silicone composition-1 for printing plate was changed to 94.85 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass was 0.10 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 1 with the exception of changing the part.

[Example 19]
“DMS” -S45: 94.65 parts by mass of the diluted silicone composition for printing plate-1 was changed to 94.45 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass was 0.50 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 1 with the exception of changing the part.

[Example 20]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 73.85 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass was 0.10 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 21]
"DMS" -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 73.70 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass was 0.25 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 22]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition for printing plate-4 was changed to 73.60 parts by mass, and 3-aminopropyltrimethoxysilane: 0.35 parts by mass was 0.35 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 23]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition for printing plate-4 was changed to 73.45 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass was 0.50 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 with the exception of changing the part.

[Example 24]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 78.65 parts by mass, and KF-96-50cs: 20.00 parts by mass to 15.00 parts by mass. A lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4 except that the changes were made.

[Example 25]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 68.65 parts by mass, and KF-96-50cs: 20.00 parts by mass to 25.00 parts by mass A lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4 except that the changes were made.

[Example 26]
The same as Example 1 except that 3-aminopropyltrimethoxysilane: 0.30 parts by mass of Silicone Composition Diluent-1 for Printing Plate was changed to 0.30 parts by mass of 3-ureidopropyltrimethoxysilane: 0.30 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated by the method.

[Example 27]
The same as Example 2 except that 3-aminopropyltrimethoxysilane: 0.30 parts by mass of the silicone composition diluent 2 for printing plate was changed to 3-ureidopropyltrimethoxysilane: 0.30 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated by the method.

[Example 28]
The same as Example 3 except that 3-aminopropyltrimethoxysilane: 0.30 parts by mass of Silicone Composition Diluent-3 for printing plates was changed to 0.30 parts by mass of 3-ureidopropyltrimethoxysilane: 0.30 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated by the method.

[Example 29]
The same as Example 4 except that 3-aminopropyltrimethoxysilane: 0.30 parts by mass of the diluted silicone composition for printing plate-4 was changed to 0.30 parts by mass of 3-ureidopropyltrimethoxysilane: 0.30 parts by mass. The lithographic printing plate precursor was prepared, plate-making, and evaluated by the method.

[Example 30]
Implemented except that 3-aminopropyltrimethoxysilane: 0.30 parts by mass of Silicone Composition Diluent-4 for printing plate was changed to 0.30 parts by mass of methyl [3- (trimethoxysilyl) propyl] carbamate A lithographic printing plate precursor was prepared, made and evaluated in the same manner as in Example 4.

[Example 31]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 73.85 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Trimethoxysilane: Preparation of a lithographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.10 parts by mass.

[Example 32]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 73.75 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Trimethoxysilane: Preparation of a lithographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.20 parts by mass.

[Example 33]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 73.70 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Trimethoxysilane: Preparation of a lithographic printing plate precursor, platemaking and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.25 parts by mass.

[Example 34]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 73.60 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Trimethoxysilane: Preparation of a lithographic printing plate precursor, platemaking and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.35 parts by mass.

[Example 35]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 73.55 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Trimethoxysilane: Preparation of a lithographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.40 parts by mass.

[Example 36]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 73.45 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Trimethoxysilane: Preparation of a lithographic printing plate precursor, platemaking and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.50 parts by mass.

[Example 37]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 73.85 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of methyl [3- (Trimethoxysilyl) propyl] carbamate: Preparation of a lithographic printing plate precursor, platemaking and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.10 parts by mass.

[Example 38]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 73.75 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of methyl [3- (Trimethoxysilyl) propyl] carbamate: Preparation, plate making and evaluation of a lithographic printing plate precursor were carried out in the same manner as in Example 4 except that the amount was changed to 0.20 part by mass.

[Example 39]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 73.70 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of methyl [3- (Trimethoxysilyl) propyl] carbamate: Preparation of a lithographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.25 parts by mass.

[Example 40]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 73.60 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of methyl [3- (Trimethoxysilyl) propyl] carbamate: Preparation of a lithographic printing plate precursor, platemaking and evaluation were carried out in the same manner as in Example 4 except that the amount was changed to 0.35 parts by mass.

[Example 41]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 73.55 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of methyl [3- (Trimethoxysilyl) propyl] carbamate: Preparation, plate making and evaluation of a lithographic printing plate precursor were carried out in the same manner as in Example 4 except that the amount was changed to 0.40 part by mass.

[Example 42]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 73.45 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of methyl [3- (Trimethoxysilyl) propyl] carbamate: Preparation, plate making and evaluation of a lithographic printing plate precursor were carried out in the same manner as in Example 4 except that the amount was changed to 0.50 part by mass.

[Example 43]
“DMS” -S45: 73.65 parts by mass of Silicone Composition Diluent-4 for printing plates was changed to 88.65 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Preparation of lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass, and KF-96-50cs: 20.00 parts by mass was changed to 5.00 parts by mass. Plate making and evaluation were performed.

[Example 44]
“DMS” -S45: 73.65 parts by mass of Silicone Composition Diluent-4 for printing plate was changed to 83.65 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Preparation of lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass, and KF-96-50cs: 20.00 parts by mass was changed to 10.00 parts by mass. Plate making and evaluation were performed.

[Example 45]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 78.65 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Preparation of lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass, and KF-96-50cs: 20.00 parts by mass was changed to 15.00 parts by mass. Plate making and evaluation were performed.

[Example 46]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 68.65 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Preparation of lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass, and KF-96-50cs: 20.00 parts by mass was changed to 25.00 parts by mass. Plate making and evaluation were performed.

[Example 47]
“DMS” -S45: 73.65 parts by mass of the silicone composition diluent for printing plate-4 was changed to 63.65 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Preparation of lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass and KF-96-50cs: 20.00 parts by mass was changed to 30.00 parts by mass. Plate making and evaluation were performed.

[Example 48]
“DMS” -S45: 73.65 parts by mass of Silicone Composition Diluent-4 for printing plates was changed to 53.65 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Preparation of lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass and KF-96-50cs: 20.00 parts by mass was changed to 40.00 parts by mass. Plate making and evaluation were performed.

[Example 49]
Silicone composition dilution liquid-4 for printing plate: 3-aminopropyltrimethoxysilane: 0.30 parts by mass was changed to 3-ureidopropyltrimethoxysilane: 0.30 parts by mass, and tetrakis (methylethylketoximino) silane: The lithographic printing plate precursor was prepared, plate-making, and evaluated in the same manner as in Example 4 except that 1.00 parts by mass was changed to tetraacetoxysilane: 1.00 parts by mass.

[Example 50]
“DMS” -S45: 73.65 parts by mass of Silicone Composition Diluent-4 for printing plate was changed to 74.15 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl A lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass, and tetrakis (methylethylketoximino) silane: 1.00 parts by mass was changed to 0.50 parts by mass. The production, plate making and evaluation were performed.

[Example 51]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition-4 for printing plate was changed to 73.15 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass and tetrakis (methylethylketoximino) silane: 1.00 parts by mass was changed to 1.50 parts by mass. The production, plate making and evaluation were performed.

[Example 52]
“DMS” -S45: 73.65 parts by mass of the diluted silicone composition for printing plate-4 was changed to 72.65 parts by mass, and 3-aminopropyltrimethoxysilane: 0.30 parts by mass of 3-ureidopropyl Lithographic printing plate precursor in the same manner as in Example 4 except that trimethoxysilane was changed to 0.30 parts by mass, and tetrakis (methylethylketoximino) silane: 1.00 parts by mass was changed to 2.00 parts by mass. The production, plate making and evaluation were performed.

[Comparative Example 1]
Preparation of the planographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 1 except that the silicone composition diluent for printing plate-1 was changed to the following silicone composition diluent for printing plate-5. .

<Silicone composition diluent for printing plate-5>
The following components (a) and (b) were charged into a container and mixed with stirring until the components were uniform. The obtained liquid was bubbled with dry nitrogen for 20 minutes to remove moisture in the liquid. The component (c) was added to the obtained liquid and stirred and mixed for 1 hour, and then the component (d) was added and stirred and mixed for 10 minutes to obtain a silicone composition diluent 5 for a printing plate. .
(A) "Isopar" (registered trademark) E: 900.00 parts by mass (b) "DMS" -S45: 94.95 parts by mass (c) Vinyltris (methylethylketoximino) silane: 5.00 parts by mass (d) Dibutyltin diacetate: 0.05 parts by mass

[Comparative Example 2]
Production of the planographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 1 except that the silicone composition diluent for printing plate-1 was changed to the following silicone composition diluent for printing plate-6. .

<Silicone composition diluent for printing plate-6>
The following components (a), (b), and (c) were charged into a container and stirred and mixed until the components became uniform. The obtained liquid was bubbled with dry nitrogen for 20 minutes to remove moisture in the liquid. The component (d) was added to the obtained liquid and stirred and mixed for 1 hour, and then the component (e) was added and stirred and mixed for another 10 minutes to obtain a silicone composition dilution liquid-6 for printing plate. .
(A) "Isopar" (registered trademark) E: 900.00 parts by mass (b) "DMS" -S45: 74.95 parts by mass (c) KF-96-50cs: 20.00 parts by mass (d) Vinyl tris ( (Methylethylketoximino) silane: 5.00 parts by mass (e) Dibutyltin diacetate: 0.05 parts by mass

[Comparative Example 3]
Preparation of the planographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 1 except that the silicone composition diluent for printing plate-1 was changed to the following silicone composition diluent for printing plate-7. .

<Silicone composition diluent for printing plate-7>
The following components (a) and (b) were charged into a container and mixed with stirring until the components were uniform. The obtained liquid was bubbled with dry nitrogen for 20 minutes to remove moisture in the liquid. Into the obtained liquid, a mixed liquid in which the components (c) and (d) are mixed in advance is added and stirred and mixed for 1 hour, and then the component (e) is added and stirred and mixed for another 10 minutes. Silicone composition diluent-7 was obtained.
(A) “Isopar” (registered trademark) E: 900.00 parts by mass (b) “DMS” -S45: 93.95 parts by mass (c) Vinyltris (methylethylketoximino) silane: 5.00 parts by mass (d) Tetrakis (methylethylketoximino) silane: 1.00 parts by mass (e) Dibutyltin diacetate: 0.05 parts by mass

[Comparative Example 4]
Preparation of the planographic printing plate precursor, plate making and evaluation were carried out in the same manner as in Example 1 except that the silicone composition diluent for printing plate-1 was changed to the following silicone composition diluent for printing plate-8. .

<Silicone composition diluent for printing plate-8>
The following components (a), (b), and (c) were charged into a container and stirred and mixed until the components became uniform. The obtained liquid was bubbled with dry nitrogen for 20 minutes to remove moisture in the liquid. Into the obtained liquid, a mixed liquid in which the components (d) and (e) are mixed in advance is added and stirred and mixed for 1 hour, and then the component (f) is added and stirred and mixed for another 10 minutes. Silicone composition dilution liquid-8 was obtained.
(A) "Isopar" (registered trademark) E: 900.00 parts by mass (b) "DMS" -S45: 73.95 parts by mass (c) KF-96-50cs: 20.00 parts by mass (d) Vinyl tris ( Methylethylketoximino) silane: 5.00 parts by mass (e) Tetrakis (methylethylketoximino) silane: 1.00 parts by mass (f) Dibutyltin diacetate: 0.05 parts by mass

  For Examples 1 to 52 and Comparative Examples 1 to 4, Table 1 shows the types of the compound represented by the general formula (VII) and the tetrafunctional silane coupling agent used, and Table 2 shows the evaluation results.

  The silicone composition for a printing plate according to the present invention can be used for the production of any lithographic printing plate precursor and lithographic printing plate that require high adhesion to the lower layer and scratch resistance. In the lithographic printing using the lithographic printing plate, a desired printed matter can be obtained.

DESCRIPTION OF SYMBOLS 1 Ink roller 2 Planographic printing plate 3 Plate cylinder 4 Blanket cylinder 5 Print medium 6 Impression cylinder

Claims (16)

(A) an organopolysiloxane having a silanol group;
(B) A silicone composition for a printing plate containing a compound represented by the following general formula (VII).

(In General Formula (VII), M represents a linear, branched, or cyclic divalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents a linear or branched structure having 1 to 3 carbon atoms. Represents a branched monovalent alkyl group, and L represents a monovalent functional group.) The compound represented by said (B) general formula (VII) is 1 or more types selected from either of the compounds represented by the following general formula (VIII)-(X). Silicone composition for printing plates.

(In the general formulas (VIII) to (X), M represents a linear, branched or cyclic divalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents 1 to 3 carbon atoms. A linear or branched monovalent alkyl group is represented, and X represents any one of hydrogen, a linear, branched, and cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. J represents a linear, branched, or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms.) The said (B) compound represented by general formula (VIII)-(X) is one or more types selected from either of the compounds represented by the following general formula (XI)-(XIII), 2. The silicone composition for printing plates according to 2.

(In General Formulas (XI) to (XIII), X represents hydrogen, a linear, branched, or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents carbon. Represents a linear or branched monovalent alkyl group having 1 to 3 and J represents a linear, branched, or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. Represents.) The compound represented by (B) the general formula (VII) is one or more selected from any of the compounds represented by the following general formulas (XIV) to (XVII),
The compound represented by (B) the general formulas (XIV) to (XVII) is contained in the total components of the printing plate silicone composition in an amount of 0.20% by mass to 0.40% by mass. The silicone composition for printing plates as described.

(In the general formulas (XIV) to (XVII), M represents a linear, branched or cyclic divalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents 1 to 3 carbon atoms. Represents a linear or branched monovalent alkyl group, and R ⁴ represents a linear, branched or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. X represents hydrogen, a straight-chain, branched or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms.) The compound represented by the general formulas (XIV) to (XVII) (B) is one or more selected from any of the compounds represented by the following general formulas (I) to (III). 4. The silicone composition for a printing plate according to 4.

(In the general formulas (I) to (III), X represents hydrogen, a linear, branched, or cyclic monovalent saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R represents carbon. Represents a linear or branched monovalent alkyl group having a number of 1 to 3.)   The silicone composition for a printing plate according to any one of claims 1 to 5, wherein R in the general formulas (VII) to (XVII) and (I) to (III) is a methyl group.   Furthermore, the silicone composition for printing plates in any one of Claims 1-6 containing (C) ink repellent liquid.   8. The printing plate according to claim 7, wherein the (C) ink repellent liquid has a mass reduction rate of 0% by mass or more and 0.5% by mass or less after heating at 150 ° C. for 24 hours under a 1 atm environment. Silicone composition.   The silicone composition for a printing plate according to claim 7 or 8, wherein the (C) ink repellent liquid has a surface tension at 25 ° C of 15 mN / m or more and 30 mN / m or less.   The silicone composition for a printing plate according to any one of claims 7 to 9, wherein the (C) ink repellent liquid is contained in an amount of 10% by mass to 30% by mass in all components of the silicone composition for a printing plate. object.   The silicone composition for printing plates according to any one of claims 1 to 10, further comprising (D) a tetrafunctional silane coupling agent.   The silicone composition for a printing plate according to claim 11, wherein the (D) tetrafunctional silane coupling agent is contained in a total amount of 0.50% by mass or more and 1.50% by mass or less in all components of the printing plate silicone composition. object.   A method for producing a lithographic printing plate precursor having at least a silicone rubber layer on a substrate, comprising a step of curing the silicone composition for a printing plate according to any one of claims 1 to 12 to obtain a cured product, A method for producing a lithographic printing plate precursor.   A method for producing a lithographic printing plate using the lithographic printing plate precursor obtained by the production method according to claim 13.   The manufacturing method of printed matter using the lithographic printing plate obtained by the manufacturing method of Claim 14, and ink.   The method for producing a printed matter according to claim 15, wherein the ink is an active energy ray-curable ink.

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