JP7517063B2 - Printing member, method for manufacturing printing member, and method for manufacturing printed matter using same - Google Patents

Description

The present invention relates to a printing material, a method for manufacturing a printing material, and a method for manufacturing a printed matter using the same.

There are various printing methods, including letterpress printing, intaglio printing, stencil (screen) printing, and planographic printing, and printing is done by taking advantage of the characteristics of each method.

Lithographic printing is particularly advantageous over other printing methods in that it produces highly detailed prints and has low total costs, including running costs.

Lithographic printing is a printing method in which ink-receptive image areas and ink-repellent non-image areas are placed on nearly the same plane on a printing plate, and ink is applied only to the image areas by utilizing the difference in ink adhesion, and then the ink is transferred to a print medium such as paper. Printing plates for lithographic printing (hereafter referred to as lithographic printing plates) are broadly divided into those in which the non-image areas are made ink-repellent by the action of dampening water, and those in which silicone rubber or fluororesin is used for the ink-repellent non-image areas without using dampening water.

As a lithographic printing plate that uses silicone rubber or fluororesin as the ink-repellent non-printing areas, Patent Document 1 describes a waterless lithographic printing plate precursor that uses silicone rubber as the ink-repellent layer.

International Publication No. 2016/076286

The waterless lithographic printing plate precursor described in Patent Document 1 has a multi-layer structure in which a heat-sensitive layer and an ink-repellent silicone rubber layer are laminated in that order on a support, so development processing was required after exposure to obtain a printing plate.

The problem that the present invention aims to solve is to provide a printing member that has excellent ink repellency and ink adhesion, a method for manufacturing the same, and a method for manufacturing a printed matter using the printing member.

In order to solve the above problems, the printing member of the present invention has the following configuration: That is, the printing member has a support and a layer consisting of an ink-repelling portion and an ink-receiving portion, the ink-repelling portion and the ink-receiving portion are present on at least the surface of the layer, the ink-repelling portion contains a diorganosiloxane unit, the ink-receiving portion contains a silsesquioxane structure and/or a glass structure, and the difference between the average elastic modulus of the ink-receiving portion and the average elastic modulus of the ink-repelling portion is 100 to 10,000 MPa .

According to the present invention, it is possible to obtain a printing member with excellent ink repellency and ink adhesion.

1 is a cross-sectional view showing an example of a printing member having an ink-repelling portion and an ink-receiving portion on at least the surface of a layer made of an ink-repelling portion and an ink-receiving portion. 1 is a cross-sectional view showing an example of a printing member having an ink-repelling portion and an ink-receiving portion on at least the surface of a layer made of an ink-repelling portion and an ink-receiving portion. 1A to 1C are cross-sectional views showing an example of a method for producing a printed matter according to the present invention.

The present invention is described in detail below.

The printing member according to the present invention is a printing member having a support and a layer consisting of an ink-repelling portion and an ink-receiving portion, and the ink-repelling portion and the ink-receiving portion are present on at least the surface of the layer.

As the support used in the present invention, known dimensionally stable paper, metal, glass, film, etc. that have been used as substrates for conventional lithographic printing plates can be used. Specific examples include paper such as fine paper, art paper, coated paper, cast paper, synthetic paper, etc.; paper laminated with plastic (polyethylene, polypropylene, polystyrene, etc.); metal plates such as aluminum (including aluminum alloys), iron, steel, zinc, copper, etc.; glass plates such as soda lime and quartz; silicon wafers; plastic films such as cellulose acetate, polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.; paper or plastic film laminated or vapor-deposited with the above-mentioned metals, etc. The plastic film may be transparent or opaque, but opaque films are preferred in terms of improving plate inspection properties.

Among these, it is preferable to use a support whose surface is metal or plastic. As such supports, synthetic paper, metal plate, plastic film, paper or plastic film on which metal is vapor-deposited or laminated, paper or metal plate laminated with plastic film, etc. are preferable, and metal plate and plastic film are more preferable.

In order to increase the adhesive strength between the support and the layer consisting of the ink-repelling portion and the ink-receiving portion, the surface of the support may be subjected to a surface treatment such as a corona discharge treatment or a plasma treatment. Also, a primer layer (adhesive layer) may be provided between the support and the layer consisting of the ink-repelling portion and the ink-receiving portion. Furthermore, these may be used in combination.

There are no particular limitations on the thickness of the support, and a thickness that is compatible with the printing machine used for printing can be selected.

In addition to plate-shaped supports, roll-shaped, cylindrical or columnar supports can also be used. When a cylindrical or columnar support is used, seamless printing or endless printing without seams becomes possible. The plate cylinder of a printing press can also be used as a cylindrical or columnar support.

The printing member according to the present invention has an ink-repelling portion and an ink-receiving portion on at least the surface of the layer consisting of the ink-repelling portion and the ink-receiving portion. Here, the surface refers to the region formed in the direction of the support from the surface layer of the side of the layer consisting of the ink-repelling portion and the ink-receiving portion that does not face the support.

1 and 2 are cross-sectional views showing an example of a printing member having an ink-repelling portion and an ink-applied portion on at least the surface of a layer consisting of the ink-repelling portion and the ink-applied portion. In both of FIG. 1 and FIG. 2, a layer 2 consisting of the ink-repelling portion and the ink-applied portion is provided on a support 1, and at least the surface of the layer has an ink-repelling portion 3 and an ink-applied portion 4. In FIG. 1, the ink-applied portion 4 is formed in a part of the depth direction from the surface layer of the surface that does not face the support 1, and in FIG. 2, the ink-applied portion 4 is formed from the surface layer of the surface that does not face the support 1 to the surface layer of the surface that faces the support. Note that, although FIG. 1 and FIG. 2 show an example in which the layer 2 consisting of the ink-repelling portion and the ink-applied portion is provided directly on the support 1, a primer layer (adhesive layer) may be provided between the support 1 and the layer 2 consisting of the ink-repelling portion and the ink-applied portion in order to increase the adhesive strength between the support 1 and the layer 2 consisting of the ink-repelling portion and the ink-applied portion.

In the present invention, the ink-receiving portion refers to the portion to which ink adheres (the ink adheres) when ink is spread on the surface of the printing material, and the ink-repelling portion refers to the portion to which ink does not adhere (the ink is repelled) when ink is spread on the surface of the printing material. The ink-receiving portion may be formed in a part of the depth direction from the surface layer of the surface that does not face the support, or the ink-receiving portion may be formed from the surface layer of the surface that does not face the support to the surface layer of the surface that faces the support.

In the printing member according to the present invention, the content of particles contained in the ink-repelling portion is preferably 0 to 5% by volume. The particles in the present invention refer to inorganic or organic solids that exhibit a granular shape in an environment of atmospheric pressure and 25°C. In addition, particles such as microcapsules that contain a liquid that exhibits fluidity in an environment of atmospheric pressure and 25°C are also included in the category of particles in the present invention. Specifically, silica particles added to improve film strength, inorganic or organic colored pigments added to impart plate inspection properties, titania particles (photocatalysts) added to change wettability by light irradiation, and fluororesin particles added to improve abrasion resistance are included, but are not limited to these. These particles may be used alone or in combination of two or more types. The average particle size of the particles in the present invention is preferably 5 nm or more and 40 μm or less, and more preferably 10 nm or more and 35 μm or less. The average particle size of the particles contained in the ink-repelling portion is determined by observing the cross section of the printing member with an electron microscope. More specifically, the cross section of the ink-repelling portion of the printing member obtained by the ultrathin section method is observed under an electron microscope, 100 particles are randomly selected, the equivalent circle diameter of each is measured, and the average value is calculated to determine the average particle diameter of the particles contained in the ink-repelling portion.

From the viewpoint of ink repellency, the particle content in the ink repellent portion is preferably 5% by volume or less, more preferably 3% by volume or less, even more preferably 2% by volume or less, and most preferably 0% by volume. The particle content in the ink repellent portion is determined by observing the cross section of the printing member with an electron microscope. More specifically, it can be determined by calculating the particle volume per unit volume from three-dimensional information of the cross section of the ink repellent portion of the printing member obtained by serial ultrathin sectioning. In the vertical direction of the ink repellent portion, the particle volume per unit volume is calculated for the surface layer of the surface facing the support of the ink repellent portion, the surface layer of the surface not facing the support, and 10 arbitrary points inside the layer, and the average value is taken as the particle content in the ink repellent portion.

In the present invention, the average elastic modulus of the ink-receiving portion is preferably 60 MPa or more, more preferably 100 MPa or more, even more preferably 150 MPa or more, and even more preferably 200 MPa or more. In addition, the average elastic modulus of the ink-receiving portion in the present invention is preferably 10,000 MPa or less, more preferably 6,000 MPa or less, even more preferably 2,000 MPa or less, and even more preferably 1,000 MPa or less. If it is 60 MPa or more, it is preferable because the ink receivability is further improved, and if it is 10,000 MPa or less, it is preferable because a tough film is obtained and printing durability is improved.

On the other hand, the average elastic modulus of the ink-repellent portion is preferably 0.001 to 10 MPa. If it is 0.001 MPa or more, printing durability is improved, which is preferable, and if it is 10 MPa or less, ink repellency is further improved, which is preferable. 0.01 to 5 MPa is more preferable, and 0.1 to 3 MPa is even more preferable.

The difference between the average modulus of elasticity of the ink-applied portion and the average modulus of elasticity of the ink-repelling portion is preferably 50 MPa or more, more preferably 100 MPa or more, even more preferably 150 MPa or more, and even more preferably 200 MPa or more. The difference between the average modulus of elasticity of the ink-applied portion and the average modulus of elasticity of the ink-repelling portion in the present invention is preferably 10,000 MPa or less, more preferably 6,000 MPa or less, even more preferably 2,000 MPa or less, and even more preferably 1,500 MPa. If the difference between the average modulus of elasticity of the ink-applied portion and the average modulus of elasticity of the ink-repelling portion is within the above range, both the ink repellency and ink adhesion of the printing member can be further improved, which is preferable.

The elastic modulus of the ink-receiving portion and the ink-repelling portion of the printing member is preferably analyzed by the force volume method using an atomic force microscope, which performs analysis with a very small load using a sharp-tipped probe. By using a silicon or silicon nitride probe with a tip curvature radius of 5 to 20 nm and analyzing with a load of 1 to 20 nN, it is possible to measure the accurate elastic modulus of each portion without the influence of the lower layer or the support. In the force volume method, the probe (cantilever) is moved vertically, pressed against the layer surface, and then released, and the probe is scanned two-dimensionally while repeating a series of operations. At that time, a force curve is obtained for each cycle, so that the mapping of mechanical properties such as the elastic modulus can be investigated by analyzing the force curve. The average elastic modulus can be obtained by calculating the arithmetic mean value of each elastic modulus obtained at 4096 measurement points (vertical: 64 points x horizontal: 64 points) in a measurement range of 25 μm ² (vertical: 5 μm x horizontal: 5 μm).

In the present invention, it is preferable that the ink-repellent portion contains a diorganosiloxane unit, and it is preferable that the ink-receiving portion contains a silsesquioxane structure and/or a glass structure. The ink-repellent portion contains a diorganosiloxane unit, which can further improve the ink repellency, and the ink-receiving portion contains a silsesquioxane structure and/or a glass structure, which is preferable because the ink-receiving portion further improves the ink receptivity. The content of diorganosiloxane units in the ink-repellent portion is preferably 90% by mass or more, more preferably 92% by mass or more, and even more preferably 94% by mass or more. If the diorganosiloxane units in the ink-repellent portion is 90% by mass or more, it is preferable because the ink repellency can be further improved. The content of diorganosiloxane units in the ink-repellent portion can be measured by combining analysis by the FT-IR-ATR method and analysis by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

The diorganosiloxane units in the ink-repelling portion and the silsesquioxane and glass structures in the ink-receiving portion can be confirmed by FT-IR-ATR analysis, in which the diorganosiloxane units show signals in absorption bands around 1256, 1085, and 790 ^cm-1 , and the silsesquioxane and glass structures show signals in absorption bands around 1271, 1133, and 995 ^cm-1 .

In the present invention, the element concentration ratios in the ink-receiving portion are preferably within the ranges of silicon: 23 to 33 atom%, oxygen: 30 to 67 atom%, and carbon: 0 to 47 atom%. If the silicon is 23 atom% or more, oxygen is 30 atom% or more, and carbon is 47 atom% or less, the ink receivability is further improved, and if the silicon is 33 atom% or less, oxygen is 67 atom% or less, and carbon is 0 atom% or more, a tough film is obtained and printing durability is improved, which is preferable. In addition, the ratio of the oxygen concentration to the silicon concentration in the ink-receiving portion (oxygen concentration/silicon concentration) is preferably within the range of 1.3 to 2.0. If it is 1.3 or more, the ink receivability is further improved, and if it is 2.0 or less, a tough film is obtained and printing durability is improved, which is preferable.

On the other hand, the element concentrations in the ink-repellent portion are preferably within the ranges of silicon: 22-26 atom%, oxygen: 24-28 atom%, and carbon: 48-52 atom%, and within these ranges, ink repellency is further improved, which is preferable. Also, the ratio of oxygen concentration to silicon concentration in the ink-repellent portion (oxygen concentration/silicon concentration) is preferably within the range of 0.9-1.2, and within this range, ink repellency is further improved, which is preferable.

The element concentrations in the ink-receiving and ink-repelling areas can be measured by X-ray photoelectron spectroscopy. In addition, the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) can be calculated by dividing the obtained oxygen concentration value by the silicon concentration value.

The silicon concentration in the ink-repellent portion is preferably 25 to 50% by mass. A silicon concentration of 25% by mass or more in the ink-repellent portion is preferable in order to further improve the ink repellency, more preferably 30% by mass or more, and even more preferably 35% by mass or more. A silicon concentration of 50% by mass or less is preferable in order to further improve the ink repellency and printing durability of the ink-repellent portion, more preferably 45% by mass or less, and even more preferably 40% by mass or less. The silicon concentration in the ink-repellent portion can be determined by elemental analysis using the X-ray photoelectron spectroscopy described above.

In the present invention, it is preferable that the spot diameter of 12 microliters of dimethyl silicone oil with a liquid viscosity of 20 centistokes contacted with the surface of the ink-receiving portion 10 minutes after contact is 20 to 37 mm. In the present invention, the spot diameter after 10 minutes of contact means the longest diameter in the spot shape of dimethyl silicone oil after 10 minutes of contact. For example, if the spot shape of dimethyl silicone oil after 10 minutes of contact is a perfect circle, the diameter of the circle is the spot diameter, and if it is an ellipse, the major axis is the spot diameter. This evaluation represents the degree of penetration (swelling) of dimethyl silicone oil into the layer with which it is contacted. When dimethyl silicone oil contacts the ink-repelling portion, it penetrates into the layer quickly, so the dimethyl silicone oil does not spread easily, and the spot diameter after aging becomes smaller. On the other hand, when dimethyl silicone oil contacts the ink-receiving portion, penetration into the layer is greatly suppressed, so the dimethyl silicone oil spreads easily, and the spot diameter after aging becomes larger. If the spot diameter after 10 minutes is 20 mm or more, good ink adhesion is obtained, more preferably 22 mm or more, and even more preferably 24 mm or more. Also, if the spot diameter after 10 minutes is 37 mm or less, good printing durability is obtained, more preferably 35 mm or less, and even more preferably 33 mm or less.

Commercially available dimethyl silicone oils with a liquid viscosity of 20 centistokes include KF-96-20cs (Shin-Etsu Chemical Co., Ltd.), DOWSIL (registered trademark) SH200 Fluid 20CS (Dow Corning Toray Co., Ltd.), WACKER (registered trademark) SILICONE FLUID AK 20 (Wacker Asahi Kasei Silicone Co., Ltd.), Element14 (registered trademark) PDMS 20-JC (Momentive Performance Materials Japan LLC), and DMS-T12 (Gelest Inc.). When any of these dimethyl silicone oils is used for evaluation, the spot diameter after aging is the same.

The average thickness of the layer consisting of the ink-repelling portion and the ink-applied portion is preferably 4 to 30 μm. By making the average thickness of the layer consisting of the ink-repelling portion and the ink-applied portion 4 μm or more, the ink repellency, scratch resistance, and printing durability of the printing member are sufficient, and by making it 30 μm or less, it is unlikely to be disadvantageous from an economic point of view. The average thickness of the layer consisting of the ink-repelling portion and the ink-applied portion can be determined by cross-sectional TEM observation. More specifically, a sample is prepared from the printing member by the ultra-thin section method, and TEM observation is performed under conditions of an acceleration voltage of 100 kV and a magnification of 2000 times. In a TEM photograph of a vertical cross section, the thickness is measured at 10 randomly selected points from the layer consisting of the ink-repelling portion and the ink-applied portion, and the average thickness can be obtained by calculating the number average value.

Silicone rubber is preferred as the ink-repellent portion in the present invention. Silicone rubber in the present invention refers to a layer in which 60% by mass or more is composed of crosslinked siloxane compounds. The content of crosslinked siloxane compounds in the ink-repellent portion can be measured by combining analysis by the FT-IR-ATR method and analysis by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

In terms of increasing the productivity of the printing member, it is preferable that the ink-repellent portion has vinyl groups. By including an excess number of vinyl groups over the total number of SiH groups in the total solid content contained in the diorganosiloxane unit-containing layer forming composition described below, an ink-repellent portion having vinyl groups can be obtained. The vinyl group concentration in the ink-repellent portion is preferably 0.5 to 15 mass%. If the vinyl group concentration in the ink-repellent portion is 0.5 mass% or more, the productivity of the printing member can be improved, and if it is 15 mass% or less, it is preferable because the decrease in ink repellency can be suppressed. 1 to 12 mass% is more preferable, and 1.5 to 10 mass% is even more preferable. The presence of vinyl groups in the ink-repellent portion can be confirmed by analyzing the ink-repellent portion by the FT-IR-ATR method.

Next, we will explain the printing member precursor according to the present invention.

The printing member precursor has a support and a diorganosiloxane unit-containing layer. More preferably, the diorganosiloxane unit-containing layer is a single layer containing diorganosiloxane units. As the diorganosiloxane unit-containing layer according to the present invention, a conventional ink-repellent silicone rubber layer of an addition reaction type, a condensation reaction type, or a combined addition reaction-condensation reaction type that has been disclosed as an ink-repellent layer for a waterless lithographic printing plate precursor can be used.

Specific examples of the diorganosiloxane unit-containing layer-forming composition used in the present invention are given below, but are not limited to these.

The composition for forming the addition reaction type diorganosiloxane unit-containing layer used in the present invention preferably contains a siloxane compound having two or more vinyl groups in the molecule, a siloxane compound having three or more SiH groups in the molecule, and a reaction catalyst. It may further contain a reaction inhibitor and a silane coupling agent.

Examples of siloxane compounds having two or more vinyl groups in the molecule include diorganopolysiloxanes having vinyl groups at both molecular terminals, organovinylpolysiloxanes, organovinylsiloxane-diorganosiloxane copolymers, and compounds having two or more diorganovinylsiloxy groups in the molecule. Among these, diorganopolysiloxanes having vinyl groups at both molecular terminals and organovinylsiloxane-diorganosiloxane copolymers are preferred. Two or more of these may be contained.

Diorganopolysiloxanes and organovinylsiloxane-diorganosiloxane copolymers having vinyl groups at both ends of the molecule have linear, cyclic, branched, or network molecular structures. The organic groups bonded to the silicon atoms may be the same or different, and each represents a monovalent organic group that does not contain an aliphatic unsaturated bond. Examples of monovalent organic groups that do not contain an aliphatic unsaturated bond include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl.

In terms of the ink repellency of the printing material, it is preferable that 50 mol% or more of the monovalent organic groups not containing aliphatic unsaturated bonds are methyl groups. In addition, the weight average molecular weight of a siloxane compound having two or more vinyl groups in the molecule is preferably 30,000 or more in terms of improving printing durability and scratch resistance, and is preferably 300,000 or less in terms of improving coating properties. The weight average molecular weight can be obtained by measuring using GPC in terms of polystyrene.

The content of the siloxane compound having two or more vinyl groups in the molecule is preferably 60% by mass or more of the total solid content contained in the composition for forming the diorganosiloxane unit-containing layer in order to improve the ink repellency in the ink repellent portion, more preferably 70% by mass or more, and even more preferably 80% by mass or more. In addition, in order to ensure the curability of the diorganosiloxane unit-containing layer, it is preferably 99% by mass or less.

Here, the total solid content contained in the diorganosiloxane unit-containing layer-forming composition refers to the components remaining after the diorganosiloxane unit-containing layer-forming composition is applied and dried (volatile components are removed).

Examples of siloxane compounds having three or more SiH groups in the molecule include organohydropolysiloxanes, organohydrosiloxane-diorganosiloxane copolymers, and compounds having three or more diorganohydrosiloxy groups in the molecule. Of these, organohydropolysiloxanes and organohydrosiloxane-diorganosiloxane copolymers are preferred. Two or more of these may be contained. The number of SiH groups in the molecule is preferably 5 or more, more preferably 6 or more, in order to improve the curability of the diorganosiloxane unit-containing layer.

Organohydropolysiloxanes and organohydrosiloxane-diorganosiloxane copolymers have linear, cyclic, branched, or network molecular structures. The organic groups bonded to the silicon atoms may be the same or different, and each represents a monovalent organic group that does not contain an aliphatic unsaturated bond. Examples of monovalent organic groups that do not contain an aliphatic unsaturated bond include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl.

The content of the siloxane compound having three or more SiH groups in the molecule is preferably 0.5% by mass or more in the total solid content contained in the composition for forming the diorganosiloxane unit-containing layer in order to improve the curing properties of the diorganosiloxane unit-containing layer, and more preferably 1% by mass or more. In addition, a content of 10% by mass or less is preferable in order to improve ink repellency, and more preferably 5% by mass or less.

In addition, the H group concentration derived from the SiH group in the total solid content contained in the diorganosiloxane unit-containing layer-forming composition according to the present invention is preferably 0.001 to 0.04 mass%. If the H group concentration derived from the SiH group in the total solid content contained in the diorganosiloxane unit-containing layer-forming composition is 0.001 mass% or more, this is preferable in terms of improving the curability of the diorganosiloxane unit-containing layer. In addition, if the H group concentration derived from the SiH group in the total solid content contained in the diorganosiloxane unit-containing layer-forming composition is 0.04 mass% or less, this is preferable in terms of improving the ink repellency in the ink repellent portion.

In terms of the relationship between the concentration of H groups derived from SiH groups in the total solid content contained in the diorganosiloxane unit-containing layer-forming composition and the average elastic modulus of the ink-repelling portion described above, when the concentration of H groups derived from SiH groups in the total solid content contained in the diorganosiloxane unit-containing layer-forming composition is 0.001 mass%, the average elastic modulus is approximately 0.001 MPa. Also, when the concentration of H groups derived from SiH groups in the total solid content contained in the diorganosiloxane unit-containing layer-forming composition is 0.04 mass%, the average elastic modulus is approximately 10 MPa.

As the reaction catalyst, a known hydrosilylation reaction catalyst can be used, but it is preferable that the catalyst contains platinum or rhodium because of its high reactivity.Specific examples of the reaction catalyst include platinum alone, solid platinum supported on a carrier (alumina, silica, carbon black, etc.), chloroplatinic acid, platinum-olefin complexes, platinum-vinylsilane complexes, platinum-vinylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, platinum-acetylacetone complexes, platinum-alkyl acetoacetate complexes, platinum-dialkyl malonate complexes, platinum-hydrocarbon complexes described in U.S. Pat. Nos. 3,159,601 and 3,159,662 to Ashby et al., and platinum alcoholate catalysts described in U.S. Pat. No. 3,220,972 to Lamoreaux et al. Examples _{of catalysts} other than platinum compounds include RhCl( _PPh3 ) ₃ , _RhCl3 , _RhAl2O3 , _RuCl3 , _IrCl3 , _FeCl3 , _AlCl3 , _PdCl2.2H2O , _NiCl2 , _TiCl4 , etc. These reaction catalysts may be used alone or in combination of two or more.

The content of the reaction catalyst is preferably 0.0001% by mass or more of the total solid content contained in the composition for forming a diorganosiloxane unit-containing layer in order to improve the curing properties of the diorganosiloxane unit-containing layer, and more preferably 0.001% by mass or more. In addition, in order to improve the pot life of the composition for forming a diorganosiloxane unit-containing layer, the content of the reaction catalyst is preferably 1% by mass or less of the total solid content contained in the composition for forming a diorganosiloxane unit-containing layer, and more preferably 0.1% by mass or less.

As the reaction inhibitor, those known as hydrosilylation reaction inhibitors or reaction retarders can be used. Amine compounds and acetylene compounds are preferred, and more preferred examples include pyridine, picoline, 2,2'-dipyridyl, 2-butanone oxime, acetylene alcohol, and acetylene silane. Examples of acetylene alcohol include 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-hexanol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl-1-pentyn-3-ol. Two or more of these may be contained. By containing these reaction inhibitors, the pot life of the diorganosiloxane unit-containing layer-forming composition is improved.

The content of the reaction inhibitor is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the total solids contained in the composition for forming a diorganosiloxane unit-containing layer, in order to improve the pot life of the composition for forming a diorganosiloxane unit-containing layer. Also, in order to ensure the curability of the diorganosiloxane unit-containing layer, the content is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, per 100 parts by mass of the total solids contained in the composition for forming a diorganosiloxane unit-containing layer.

Examples of silane coupling agents include, but are not limited to, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, toluyltriacetoxysilane, xylyltriacetoxysilane, methyltris(methylethylketoximino)silane, ethyltris(methylethylketoximino)silane, phenyltris(methylethylketoximino)silane, toluyltris(methylethylketoximino)silane, xylyltris(methylethylketoximino)silane, vinyltriacetoxysilane, allyltriacetoxysilane, 3-acryloxypropyltriacetoxysilane, 3-methacryloxypropyltriacetoxysilane, vinyltris(methylethylketoximino)silane, allyltris(methylethylketoximino)silane, 3-acryloxypropyltris(methylethylketoximino)silane, 3-methacryloxypropyltris(methylethylketoximino)silane, and the like. Among these, vinyltriacetoxysilane and vinyltris(methylethylketoximino)silane are preferred in terms of improving reactivity with siloxane compounds having three or more SiH groups in the molecule, improving adhesion to the lower layer, and preventing a decrease in ink repellency.

The content of the silane coupling agent is preferably 0.5% by mass or more of the total solid content contained in the composition for forming the diorganosiloxane unit-containing layer in order to improve adhesion to the primer layer or support (adhesion to the lower layer), and more preferably 1% by mass or more. Also, in order to improve ink repellency, the content is preferably 10% by mass or less, and more preferably 5% by mass or less.

The condensation reaction type diorganosiloxane unit-containing layer-forming composition used in the present invention preferably contains a siloxane compound having two or more silanol groups in the molecule, and a silane coupling agent. It may further contain a reaction catalyst.

An example of a siloxane compound having two or more silanol groups in a molecule is a diorganopolysiloxane having silanol groups at both ends of the molecule.

Diorganopolysiloxanes having silanol groups at both ends of the molecule have a linear, cyclic, branched, or network molecular structure. The organic groups bonded to the silicon atoms may be the same or different, and each represents a monovalent organic group that does not contain an aliphatic unsaturated bond. Examples of monovalent organic groups that do not contain an aliphatic unsaturated bond include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl.

In terms of the ink repellency of the printing material, it is preferable that 50 mol % or more of the monovalent organic groups not containing aliphatic unsaturated bonds are methyl groups. In addition, the weight average molecular weight of a siloxane compound having two or more silanol groups in the molecule is preferably 30,000 or more in terms of improving printing durability and scratch resistance, and is preferably 300,000 or less in terms of improving coating properties. The weight average molecular weight can be obtained by measuring using GPC in terms of polystyrene.

The content of the siloxane compound having two or more silanol groups in the molecule is preferably 60% by mass or more of the total solid content contained in the composition for forming the diorganosiloxane unit-containing layer in order to improve the ink repellency in the ink repellent portion, more preferably 70% by mass or more, and even more preferably 80% by mass or more. In addition, in order to ensure the curability of the diorganosiloxane unit-containing layer, it is preferably 99% by mass or less.

Examples of the silane coupling agent include the silane coupling agents exemplified above in the composition for forming the layer containing diorganosiloxane units of the addition reaction type.

The content of the silane coupling agent is preferably 0.5% by mass or more, and more preferably 1% by mass or more, of the total solid content contained in the composition for forming the diorganosiloxane unit-containing layer in order to improve curability and adhesion to the lower layer. Also, in order to improve ink repellency, the content is preferably 10% by mass or less, and more preferably 5% by mass or less.

Examples of reaction catalysts include organic carboxylic acids, acids, alkalis, amines, metal alkoxides, metal diketenates, and 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.

The content of the reaction catalyst is preferably 0.01% by mass or more and 1% by mass or less of the total solid content of the composition for forming the diorganosiloxane unit-containing layer. If it is 0.01% by mass or more, the curability of the diorganosiloxane unit-containing layer and the adhesion to the lower layer will be good, and if it is 1% by mass or less, the stability of the composition for forming the diorganosiloxane unit-containing layer will be good.

The composition for forming the diorganosiloxane unit-containing layer of the addition reaction-condensation reaction combination type used in the present invention preferably contains a siloxane compound having two or more silanol groups in the molecule, a silane coupling agent having one or more vinyl groups in the molecule, a siloxane compound having three or more SiH groups in the molecule, and a reaction catalyst. It may further contain a reaction inhibitor.

Examples of siloxane compounds having two or more silanol groups in the molecule include the siloxane compounds exemplified above in the composition for forming a layer containing condensation reaction type diorganosiloxane units.

The content of the siloxane compound having two or more silanol groups in the molecule is preferably 60% by mass or more of the total solid content contained in the composition for forming the diorganosiloxane unit-containing layer in order to improve the ink repellency in the ink repellent portion, more preferably 70% by mass or more, and even more preferably 80% by mass or more. In addition, in order to ensure the curability of the diorganosiloxane unit-containing layer, it is preferably 99% by mass or less.

Examples of silane coupling agents having one or more vinyl groups in the molecule include silane coupling agents having one or more vinyl groups in the molecule, among the silane coupling agents exemplified in the composition for forming the layer containing diorganosiloxane units of the addition reaction type.

The content of the silane coupling agent having one or more vinyl groups in the molecule is preferably 0.5% by mass or more, and more preferably 1% by mass or more, of the total solid content contained in the composition for forming the diorganosiloxane unit-containing layer in order to improve curability and adhesion to the lower layer. Also, in order to improve ink repellency, the content is preferably 10% by mass or less, and more preferably 5% by mass or less.

Examples of siloxane compounds having three or more SiH groups in the molecule include the siloxane compounds exemplified above in the composition for forming the layer containing diorganosiloxane units of the addition reaction type.

The content of the siloxane compound having three or more SiH groups in the molecule is preferably 0.5% by mass or more in the total solid content contained in the composition for forming the diorganosiloxane unit-containing layer in order to improve the curing properties of the diorganosiloxane unit-containing layer, and more preferably 1% by mass or more. In addition, a content of 10% by mass or less is preferable in order to improve ink repellency, and more preferably 5% by mass or less.

Examples of reaction catalysts include the reaction catalysts exemplified above for the composition for forming the layer containing diorganosiloxane units of the addition reaction type.

The content of the reaction catalyst is preferably 0.0001% by mass or more of the total solid content contained in the composition for forming a diorganosiloxane unit-containing layer in order to improve the curing properties of the diorganosiloxane unit-containing layer, and more preferably 0.001% by mass or more. In addition, in order to improve the pot life of the composition for forming a diorganosiloxane unit-containing layer, the content of the reaction catalyst is preferably 1% by mass or less of the total solid content contained in the composition for forming a diorganosiloxane unit-containing layer, and more preferably 0.1% by mass or less.

Examples of reaction inhibitors include the reaction inhibitors exemplified above in the composition for forming the layer containing diorganosiloxane units of the addition reaction type.

The content of the reaction inhibitor is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the total solids contained in the composition for forming a diorganosiloxane unit-containing layer, in order to improve the pot life of the composition for forming a diorganosiloxane unit-containing layer. Also, in order to ensure the curability of the diorganosiloxane unit-containing layer, the content is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, per 100 parts by mass of the total solids contained in the composition for forming a diorganosiloxane unit-containing layer.

In order to further improve the ink repellency of the addition reaction type, condensation reaction type, or combination of addition reaction and condensation reaction type diorganosiloxane unit-containing layer, the diorganosiloxane unit-containing layer-forming composition may contain a liquid having a surface tension of 30 mN/m or less at 25°C. If the surface tension of the liquid is 30 mN/m or less, the liquid having a surface tension of 30 mN/m or less at 25°C appears on the surface of the ink repellent portion of the layer consisting of the ink repellent portion and the ink-receiving portion, which helps the ink to peel off, improving the ink repellency and increasing the scumming start temperature. In terms of improving the ink repellency, it is more preferable for the liquid to have a surface tension of 22 mN/m or less at 25°C, and even more preferable for it to be 21 mN/m or less. Surface tension can be measured by the Wilhelmy method (sometimes called the plate method or vertical plate method) using a platinum plate, which is a known measurement method.

A liquid with a surface tension of 30 mN/m or less at 25°C preferably has a mass loss of 0 to 0.5% by mass after being left to stand at 150°C for 24 hours in an atmospheric pressure environment. If the mass loss is 0 to 0.5% by mass after being left to stand at 150°C for 24 hours in an atmospheric pressure environment, the liquid is less likely to volatilize during the manufacture or storage of the printing member precursor or printing member, and is less likely to lose its ink repellency effect.

The content of the liquid having a surface tension of 30 mN/m or less at 25°C is preferably 5 to 40 mass% of the total solids contained in the composition for forming the diorganosiloxane unit-containing layer. If it is 5 mass% or more, the ink repellency is significantly improved, and if it is 40 mass% or less, the strength of the diorganosiloxane unit-containing layer can be sufficiently ensured, so that printing durability can be maintained.

The liquid having a surface tension of 30 mN/m or less at 25°C is preferably a silicone compound, and more preferably a silicone oil. The silicone oil in the present invention refers to a polysiloxane component that is not involved in the crosslinking of the diorganosiloxane unit-containing layer. Specifically, dimethyl silicone oils such as polydimethylsiloxane having a trimethylsilyl group at the molecular chain end, cyclic polydimethylsiloxane, dimethylsiloxane-methylphenylsiloxane copolymer having a trimethylsilyl group at the molecular chain end, and dimethylsiloxane-diphenylsiloxane copolymer having a trimethylsilyl group at the molecular chain end, as well as modified silicone oils in which various organic groups have been introduced into some of the methyl groups in the molecule, such as 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, carbamate-modified silicone oil, and higher fatty acid-modified silicone oil, can be mentioned.

The molecular weight of a liquid having a surface tension of 30 mN/m or less at 25°C is preferably a weight average molecular weight of 200 to 100,000. If the weight average molecular weight is 200 or more, evaporation of the liquid having a surface tension of 30 mN/m or less at 25°C during production and storage of the printing member is suppressed, and if it is 100,000 or less, bleeding out from the diorganosiloxane unit-containing layer is suppressed. 1,000 to 10,000 is more preferable. The weight average molecular weight can be obtained by measuring using GPC in terms of polystyrene.

The above-mentioned addition reaction type, condensation reaction type, and combination addition reaction-condensation reaction type diorganosiloxane unit-containing layer forming composition may also contain known reinforcing agents such as silica particles and silicone resins having functional groups such as vinyl groups, SiH groups, and silanol groups in order to improve rubber strength.

Furthermore, the above-mentioned addition reaction type, condensation reaction type, and combination addition reaction-condensation reaction type diorganosiloxane unit-containing layer forming composition may contain a solvent to improve coatability.

Examples of the solvent include aliphatic, alicyclic, and aromatic hydrocarbons, halogenated hydrocarbons, and linear or cyclic ether compounds. Among them, aliphatic or alicyclic hydrocarbons are preferred from the viewpoint of improving economic efficiency and safety. In addition, from the viewpoint of improving the solubility of the solid content contained in the diorganosiloxane unit-containing layer forming composition, 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 even more preferably 14.4 (MPa) ^1/2 or less. The solubility parameter can be calculated using the Fedors estimation method. In addition, from the viewpoint of improving safety and ease of handling, the boiling point at 1 atmospheric pressure is preferably 60° C. or more, and more preferably 80° C. or more. On the other hand, from the viewpoint of improving the drying property of the coating liquid, the boiling point at 1 atmospheric pressure is preferably 150° C. or less, and more preferably 120° C. or less. 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, trimethylcyclohexane, etc. Two or more of these solvents may be mixed and used, or commercially available solvents in which these solvents are mixed in advance, such as those typified below, may be used.

Mixtures of branched aliphatic hydrocarbons: For example, Marukasol 8 (manufactured by Maruzen Petrochemical Co., Ltd.), "Isopar" (registered trademark) C, "Isopar" (registered trademark) E (all manufactured by ExxonMobil Chemical Co.), IP Solvent 1016 (manufactured by Idemitsu Kosan Co., Ltd.), and "Isosol" (registered trademark) 200 (manufactured by JX Nippon Oil & Energy Corporation) are available from the respective companies.

Alicyclic hydrocarbon mixtures: For example, Exxol DSP 80/100, Exxol DSP 100/140, Exxol D30 (all manufactured by ExxonMobil Chemical Corporation), and CS volatile oil (manufactured by JX Nippon Oil & Energy Corporation) are available from various companies.

In addition, solvents other than the above-mentioned solvents can be mixed and used, but in order to improve the solubility of the diorganosiloxane unit-containing layer-forming composition, it is preferable that the above-mentioned solvents account for 80 volume % or more of the total solvent, and more preferably 90 volume % or more.

The specific method for preparing the composition for forming the diorganosiloxane unit-containing layer is described below, but is not limited thereto.

For example, a solvent, a siloxane compound having two or more vinyl groups in the molecule, a siloxane compound having three or more SiH groups in the molecule, a liquid having a surface tension of 30 mN/m or less at 25°C, a reaction inhibitor, and a silane coupling agent are added to a container and stirred until the components are uniform. Furthermore, a reaction catalyst is added and the components are stirred until they are uniform, thereby obtaining a composition for forming a layer containing diorganosiloxane units.

From the viewpoint of maintaining curability, it is preferable to add the reaction catalyst immediately before applying the composition for forming the diorganosiloxane unit-containing layer.

The diorganosiloxane unit-containing layer can be formed by applying the above-mentioned diorganosiloxane unit-containing layer-forming composition to a support or to another layer provided on a support.

The printing member precursor of the present invention may also have a primer layer between the support and the diorganosiloxane unit-containing layer for the purpose of improving adhesion, plate inspection properties, scratch resistance, printing durability, etc.

Examples of primer layers include, but are not limited to, the primer layers described as heat insulating layers in JP-A-2004-199016, JP-A-2004-334025, and JP-A-2006-276385.

The average thickness of the primer layer is preferably 0.1 μm or more, as this improves the scratch resistance, printing durability, and plate inspection properties of the printing material. In addition, the average thickness of the primer layer is preferably 30 μm or less, and more preferably 0.2 to 20 μm, as this improves the productivity of the printing material by making it easier for the dilution solvent to volatilize.

Next, we will explain the method for producing the printing member precursor.

When providing a primer layer on a support, a primer layer-forming composition is applied onto the support, and the composition is dried and cured with or without heating to form a primer layer on the support.

A slit die coater, gravure coater, roll coater, wire bar coater, etc. can be used to apply the composition for forming the primer layer, but a slit die coater is preferred.

When heating, a hot air dryer, infrared dryer, etc. can be used, and it is preferable to dry at a temperature of 50 to 250°C for 30 seconds to 10 minutes.

The diorganosiloxane unit-containing layer is formed by applying the diorganosiloxane unit-containing layer-forming composition onto a support or onto a primer layer provided on a support, and then drying and curing the composition with or without heating.

When applying the diorganosiloxane unit-containing layer-forming composition, it is preferable to remove as much moisture as possible from the support surface and primer layer surface in order to improve adhesion.

A slit die coater, gravure coater, roll coater, wire bar coater, etc. can be used to apply the composition for forming the diorganosiloxane unit-containing layer, but a slit die coater is preferred.

When heating, a hot air dryer, infrared dryer, etc. can be used, and it is preferable to dry at a temperature of 50 to 200°C for 30 seconds to 10 minutes.

The printing member precursor of the present invention may have a cover film or interleaf paper, or both, provided on the diorganosiloxane unit-containing layer for the purpose of protecting the surface of the diorganosiloxane unit-containing layer.

The cover film is preferably a film with a thickness of 100 μm or less. Specific examples include polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, cellophane, etc.

The slip paper preferably has a basis weight of 30 to 120 g/m ² , more preferably 30 to 90 g/m ^2. If the basis 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 printing member precursor or the printing member and the slip paper becomes thin, and workability is advantageous. Examples of the slip paper that is preferably used include, for example, information recording base paper 40 g/m ² (manufactured by Nagoya Pulp Co., Ltd.), metal slip 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.), and Clupac 73 g/m ² (manufactured by Oji Paper Co., Ltd.), which are available from each company, but are not limited thereto.

Next, a method for producing a printing member from the printing member precursor will be described. If a cover film or interleaf paper is provided on the diorganosiloxane unit-containing layer of the printing member precursor, these are removed in advance before producing the printing member. The printing member according to the present invention can be obtained by irradiating the printing member precursor with electron beams or ultraviolet light having a wavelength of 125 to 260 nm. The wavelength of the ultraviolet light is more preferably 125 nm to 200 nm. Here, ultraviolet light having a wavelength of 125 to 260 nm refers to ultraviolet light having a peak wavelength in the wavelength range of 125 to 260 nm. When the ink-repelling portion is irradiated with electron beams or ultraviolet light having a wavelength of 125 to 260 nm, at least the surface of the diorganosiloxane unit-containing layer in the irradiated portion changes to a structure containing a silsesquioxane structure and/or a glass structure, thereby changing the ink repellency to ink receptivity.

Among these, it is preferable to directly draw the pattern of the ink-receiving area using an electron beam drawing device or an ultraviolet laser drawing device with a wavelength of 125 to 260 nm, since this eliminates the need for a mask for plate making.

Electron beam irradiation devices can be classified into a scanning type scan beam system and a non-scanning type area beam system, and either system can be suitably used. In general, the scan beam system is used for high energy devices of 300 keV or more, and the area beam system is often used for low energy devices of 300 keV or less.

Electron beam lithography devices include a spot beam system, a variable shaped beam (rectangular beam) system, and a character projection system, and any of these systems can be suitably used. These systems may also be combined. The greatest advantage of the spot beam system is that it can perform ultra-high definition patterning (tens to hundreds of nm), but it has the disadvantage of lowering the productivity (throughput) of printed materials. In the manufacture of printed materials, even at 4000 dpi, which is considered to be a high resolution, the minimum dot size is about 6 μm, so even if a variable shaped beam system, which has lower definition than the spot beam system, is used, the definition is sufficient, and this can increase the productivity of printed materials.

The dose of the electron beam is preferably 100 to 3000 kGy, and more preferably 500 to 2000 kGy. A dose of 100 kGy or more is preferable because it further improves the ink receptivity of the electron beam irradiated area, and a dose of 3000 kGy or less is preferable because it provides excellent productivity and printing durability.

The acceleration voltage of the electron beam is preferably 50 to 150 kV, and more preferably 75 to 125 kGy. A voltage of 50 kGy or more is preferable because it provides excellent productivity, while a voltage of 150 kGy or less is preferable because it further improves ink adhesion at a low dose and reduces the penetration depth of the electron beam, thereby suppressing damage to the support and primer layer.

Examples of ultraviolet irradiation devices with a wavelength of 125 to 260 nm include high-pressure mercury lamps, low-pressure mercury lamps, and excimer lamps, which have a peak wavelength of irradiation light in the range of 125 to 260 nm. Among these, low-pressure mercury lamps and excimer lamps are preferred. Examples of excimer lamps with a wavelength of 125 to 260 nm include rare gas excimer lamps and rare gas halogen excimer lamps such as Ar ₂ (126 nm), Kr ₂ (146 nm), F ₂ (153 nm), ArBr (165 nm), Xe ₂ (172 nm), ArCl (175 nm), ArF (193 nm), KrBr (207 nm), KrCl (222 nm), KrF (248 nm), XeI (253 nm), HgXe (254 nm), and Cl ₂ (259 nm), but are not limited to these. Among these, from the viewpoint of improving the productivity of printing members, it is more preferable to use a vacuum ultraviolet excimer lamp having a wavelength of 125 to 200 nm, such as Ar ₂ (126 nm), Kr ₂ (146 nm), F ₂ (153 nm), ArBr (165 nm), Xe ₂ (172 nm), ArCl (175 nm), or ArF (193 nm).

Examples of ultraviolet lasers with a wavelength of 125 to 260 nm include solid lasers such as the third harmonic of an Alexandrite laser (252 nm), the fifth harmonic of an Nd:YAG laser (213 nm), the fifth harmonic of an Nd: _YVO4 laser (213 nm), and the fifth harmonic of an Nd:YLF laser (211 nm), and gas lasers such as an _F2 laser (157 nm), an ArF laser (193 nm), a KCl laser (222 nm), and a KrF laser (248 nm), but are not limited thereto. Among these, in terms of improving the productivity of printing members, it is more preferable to use vacuum ultraviolet lasers with a wavelength of 125 to 200 nm, such as an _F2 laser (157 nm) and an ArF laser (193 nm).

The exposure dose of ultraviolet light having a wavelength of 125 to 260 nm is preferably 300 to 3000 mJ/ ^cm2 , and more preferably 500 to 2000 mJ/ ^cm2 . If it is 300 mJ/ ^cm2 or more, the ink receptivity of the ultraviolet irradiated portion is further improved, and if it is 3000 mJ/ ^cm2 or less, the productivity and printing durability are excellent, and therefore it is preferable.

Irradiation with electron beams or ultraviolet rays with wavelengths of 125 to 200 nm is preferably carried out in nitrogen gas or vacuum to prevent ozone generation and energy loss of the irradiation rays due to oxygen, etc.

When the resulting printing members are stacked for storage, it is preferable to place interleaf paper between the printing members in order to protect the surface of the layer consisting of the ink-repelling portion and the ink-receiving portion.

Next, we will explain a method for producing a printed matter using a printing member, ink, and a print medium. The printing member according to the present invention can be suitably used for waterless printing.

The method for producing a printed matter according to the present invention uses the printing member, ink, and print medium according to the present invention. Specifically, it is preferable that the method includes a step of applying ink to the surface of the printing member, and a step of transferring the ink to the print medium directly or via a blanket.

One embodiment of the method for producing a printed matter according to the present invention will be described using Figure 3. Note that, although an example using a blanket cylinder 8 will be described below, the present invention is not limited to this, and it is also possible to transfer ink directly to the print medium after applying ink from an ink roller 5 to a printing member 6 mounted on a plate cylinder 7 without using a blanket cylinder 8. Also, although an example will be described below in which ink is supplied from above the print medium 9, ink may also be supplied from below the print medium 9.

First, ink is supplied to the ink roller 5. The ink supplied to the ink roller 5 adheres to the printing material 6 attached to the plate cylinder 7 at the contact point with the plate cylinder 7. The ink adhered to the printing material 6 is transferred to the surface of the blanket cylinder 8 at the contact point with the blanket cylinder 8. The ink adhered to the blanket cylinder 8 is transferred to the print medium 9 placed on the impression cylinder 10 at the contact point with the print medium 9. A print is obtained by drying the print medium 9 as necessary. There are no particular limitations on the rotation speed of the ink rollers and each cylinder, and it can be set appropriately depending on the quality required for the print and the properties of the ink, etc.

Printing machines used to produce the printed matter according to the present invention include, for example, known direct printing machines such as sheet-fed or rotary printing machines and offset printing machines, but offset printing machines are preferred because they can produce more printed matter by minimizing damage to the printing material during printing. An offset printing machine is composed of a feeder section, a printing section, and a delivery section. The printing section has at least an ink supply section, a plate cylinder, a blanket cylinder, and an impression cylinder.

As for offset printing machines, offset printing machines equipped with a cooling mechanism for the oscillating roller and/or plate cylinder are preferred in terms of improving the resistance to scumming.

When printing with oil-soluble or water-soluble oxidative polymerization ink, the ink transferred to the print medium is dried and/or hardened by natural drying or heat treatment to obtain a printed product.

On the other hand, when printing with oil-soluble or water-soluble active energy ray-curable ink, the ink transferred to the print medium is instantly cured by the active energy rays from the active energy ray irradiation device, resulting in a printed product, which is preferable.

Examples of active energy rays include visible light, ultraviolet light (UV), electron beams (EB), X-rays, and particle beams, but ultraviolet light and electron beams are preferred from the standpoint of ease of handling the radiation source.

When curing with ultraviolet light, ultraviolet irradiation devices such as high-pressure mercury lamps, xenon lamps, metal halide lamps, and LEDs are preferably used, but when using a metal halide lamp, for example, it is preferable from the viewpoint of productivity to cure with a lamp having an illuminance of 80 to 150 W/cm ² and a conveyor transport speed of 50 to 150 m/min. In particular, when using a print medium containing a plastic film or metal as the print medium, the print medium is likely to expand or contract due to heat generated by active energy rays, so that an ultraviolet irradiation device using an electron beam that generates less heat or an LED (LED-UV) can be preferably used.

When curing with electron beams, an electron beam irradiation device with an energy beam of 100 to 500 eV is preferably used.

Inks that can be preferably used in the present invention include, but are not limited to, the inks listed below.

<Ink-1> Oil-soluble oxidative polymerization type ink Examples of the oil-soluble oxidative polymerization type ink include known oil-soluble oxidative polymerization type inks that can be washed with an oil-based washing liquid, as disclosed in, for example, JP-A-48-004107, JP-A-01-306482, etc. Also included in the oil-soluble oxidative polymerization type inks are soybean oil inks and vegetable oil inks, in which the solvent component is replaced from the conventional mineral oil (petroleum) component with a vegetable oil component, as well as environmentally low-load inks known as Non-VOC inks, as disclosed in, for example, JP-A-2005-336301, JP-A-2005-126579, JP-A-2011-144295, and JP-A-2012-224823.

<Ink-2> Water-soluble oxidative polymerization ink Examples of the water-soluble oxidative polymerization ink include known water-soluble oxidative polymerization inks that can be washed with water or an aqueous cleaning solution, as disclosed in JP-A-2009-57461, Japanese Patent No. 4,522,094, and the like.

<Ink-3> Oil-soluble active energy ray-curable ink Examples of the oil-soluble active energy ray-curable ink include known active energy ray-curable inks that can be washed with an oil-based washing liquid, such as those disclosed in Japanese Patent No. 5158274, JP-A No. 2012-211230, etc. Active energy ray-curable inks also include high-sensitivity UV inks used in power-saving (reduced lighting) UV printing and LED-UV printing.

<Ink-4> Water-soluble active energy ray-curable ink Examples of the water-soluble active energy ray-curable ink include known water-soluble active energy ray-curable inks that can be washed with water or an aqueous cleaning solution, as disclosed in, for example, JP2017-52817A, WO2017/047817A, WO2017/090663A, and the like.

Among the above inks, oil-soluble or water-soluble active energy ray curable inks are preferred because they have the advantage that conventional oxidative polymerization inks do not have, that is, they are instantly cured by irradiation with active energy rays after being transferred to the printing medium, and therefore printing on the back side and post-processing can be performed immediately. However, unlike conventional oxidative polymerization inks, active energy ray curable inks have the disadvantage that they are prone to background scumming during printing because they contain no or only a small amount of ingredients to prevent background scumming. Since the printing member of the present invention has high ink repellency, oil-soluble active energy ray curable inks and water-soluble active energy ray curable inks can be suitably used. In addition, when cleaning ink attached to various rollers, blankets, printing members, etc. of a printing machine, oil-soluble inks such as oil-soluble oxidative polymerization inks and oil-soluble active energy ray curable inks use highly volatile and harmful organic solvents, which put a large burden on the human body and the environment. In contrast, water-soluble inks such as water-soluble oxidative polymerization inks and water-soluble active energy ray curable inks can be washed off with water alone or with a cleaning solution mainly composed of water, making it unnecessary to use highly volatile and harmful organic solvents, and thus favorable in that the burden on the human body and the environment can be significantly reduced. In particular, water-soluble active energy ray curable inks can be used more preferably.

Printing media include, but are not limited to, papers such as fine paper, art paper, coated paper, cast paper, synthetic paper, and newsprint; metals such as aluminum, aluminum alloys, iron, steel, zinc, and copper; plastic films such as polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal; and composites of these papers, metals, and plastic films (paper or plastic film vapor-deposited or laminated with metal, paper or metal laminated with plastic film, and metal or plastic film laminated with paper).

In particular, the method for producing printed matter according to the present invention is suitable for printing on print media that do not absorb ink components, such as synthetic paper, metals, plastic films, paper or plastic film on which metal is vapor-deposited or laminated, and paper or metal laminated with plastic film, whose print surface is made of metal or plastic film.

Of the above, the printing surface of the printing medium, such as synthetic paper, plastic films, paper laminated with plastic film, or metal, whose printing surface is made of plastic film, may be coated with a primer resin or subjected to a surface treatment such as a corona discharge treatment or plasma treatment to improve adhesion.

The printing medium can be in either sheet or roll form. When printing on thin film for flexible packaging, it is preferable to use rolled film and print by roll-to-roll.

The thickness of the ink coating (cured ink film) on the printing medium is preferably 0.1 to 50 μm. By keeping the thickness of the ink coating within the above range, it is possible to reduce ink costs while maintaining good print quality.

The printing member of the present invention does not require a development process, and there is no need to use pre-treatment chemicals or post-treatment chemicals used in conventional development processes. Therefore, pre-treatment chemicals and post-treatment chemicals do not adhere to or penetrate the printing member, and these chemicals do not migrate from the printing member to the printed matter during the printing process, making it particularly suitable for use in printing for food packaging applications, which have strict chemical content requirements.

The present invention will be described in more detail below with reference to examples. Each example and comparative example was evaluated using the following methods.

<Evaluation methods for each example and comparative example>
(1) Average elastic modulus and difference in average elastic modulus between a portion irradiated with an electron beam or ultraviolet light having a wavelength of 125 to 260 nm (ink-applied portion) and a portion not irradiated with an electron beam or ultraviolet light (ink-repelling portion) The average elastic modulus of a portion irradiated with an electron beam or ultraviolet light having a wavelength of 125 to 260 nm and a portion not irradiated with an electron beam or ultraviolet light of the printing members obtained by the methods described in each Example and Comparative Example were evaluated and calculated by the following analytical method.
Analytical device: Scanning probe microscope (SPM): NanoScope V dimension Icon (manufactured by Bruker)
Probe: Silicon cantilever (spring constant = 6 N/m)
Tip curvature radius: 8nm
Load: 5 to 20 nN
Scanning mode: Force volume (contact mode)
Scanning range: 25 μm ² (length: 5 μm × width: 5 μm) of each of the area irradiated with electron beam or ultraviolet light with a wavelength of 125 to 260 nm and the area not irradiated with electron beam or ultraviolet light
Measurement points within the scanning range: 4096 points (vertical: 64 points x horizontal: 64 points)
Measurement environment: Room temperature, in air.

The arithmetic mean value of the elastic modulus at all measurement points (4096 points) was taken as the average elastic modulus, and the average elastic modulus difference was calculated by dividing the average elastic modulus of the area irradiated with the electron beam or ultraviolet light with a wavelength of 125 to 260 nm by the average elastic modulus of the area not irradiated with the electron beam or ultraviolet light.

(2) Measurement of spot diameter A printing member was placed on a hot plate (plate temperature: 30°C) that was leveled using a level. After confirming that the surface temperature of the printing member was 30°C, 12 microliters of dimethyl silicone oil: KF-96-20cs (manufactured by Shin-Etsu Chemical Co., Ltd., liquid viscosity: 20 centistokes) was brought into contact with any one location on the surface of the printing member that was irradiated with electron beams or ultraviolet rays with a wavelength of 125 to 260 nm, and the spot diameter was measured 10 minutes after the contact. The spot diameter was determined by measuring the length of the spot shape of the dimethyl silicone oil 10 minutes after the contact, at the point where the diameter was the longest.

(3) Printing Method The printing members obtained by the methods described in each of the Examples and Comparative Examples were mounted on an LED-UV offset rotary printing press: MHL13A (manufactured by Miyakoshi Co., Ltd.), and 20,000 m of printing was carried out under the conditions shown below.

<Printing conditions>
Ink roller: #8000 (manufactured by Meiwa Rubber Industries Co., Ltd.)
Blanket: T626W (Kinyosha Co., Ltd.)
Water-soluble UV ink: UV171 NH TBS ink (manufactured by T&K TOKA Co., Ltd.)
Ink component non-absorbent print medium: "EMBLET" (registered trademark) PTM-12 (rolled biaxially stretched PET film, thickness: 12 μm, printing surface: easy-adhesion treatment, manufactured by Unitika Ltd.)
Plate surface temperature: 25-28℃
Printing speed: 100m/min.

<Ink curing conditions>
UV wavelength: 385nm
UV irradiation intensity: 8 W/cm ² .

(3-1) Evaluation of ink receptivity in areas irradiated with electron beams or ultraviolet rays with wavelengths of 125 to 260 nm A printed matter approximately 500 m from the start of printing was cut out and placed on a five-ply coated paper: OK "Topcoat" (registered trademark) + (manufactured by Oji Paper Co., Ltd.), and the ink reflection density of the solid area was measured with a spectrodensitometer "Spectroeye" (manufactured by X-Rite Inc.). The ink receptivity was scored as follows:
A: Black reflection density 1.4 or more. B: Black reflection density 1.1 or more and less than 1.4. C: Black reflection density 0.8 or more and less than 1.1. D: Black reflection density 0.5 or more and less than 0.8. E: Black reflection density less than 0.5.

(3-2) Evaluation of ink repellency in areas not irradiated with electron beam or ultraviolet ray A printed matter was cut out from about 500 m from the start of printing, placed on a 5-ply OK "Topcoat" (registered trademark) +, and the ink reflection density of the white solid area was measured with a "Spectroeye." The lower the reflection density, the better the ink repellency, and a reflection density of 0.00 is the best. When the reflection density is 0.01 or more, background scumming occurs in the white solid area, and the higher the value, the worse the degree of background scumming becomes.

(3-3) Evaluation of printing durability in the area irradiated with electron beam or ultraviolet light with a wavelength of 125 to 260 nm Printed matter was cut out every 5,000 m from the start of printing, placed on a 5-ply OK "Topcoat" (registered trademark) +, and the ink reflection density of the solid area was measured with a "Spectroeye". The printing durability in the area irradiated with electron beam or ultraviolet light with a wavelength of 125 to 260 nm was evaluated as follows.
A: No decrease in ink reflection density even at 20,000 m. B: No decrease in ink reflection density at 15,000 m, but decrease in ink reflection density at 20,000 m. C: No decrease in ink reflection density at 10,000 m, but decrease in ink reflection density at 15,000 m. D: No decrease in ink reflection density at 5,000 m, but decrease in ink reflection density at 10,000 m. E: decrease in ink reflection density at 5,000 m.

(3-4) Evaluation of printing durability in areas not irradiated with electron beams or ultraviolet rays Prints were cut out every 5,000 m from the start of printing, placed on a stack of 5 OK "Topcoat" (registered trademark) +, and the black reflection density of the white solid area was measured with a "Spectroeye". The printing durability in areas not irradiated with electron beams or ultraviolet rays was evaluated as follows.
A: No increase in ink reflection density even at 20,000 m. B: No increase in ink reflection density at 15,000 m, but increase in ink reflection density at 20,000 m. C: No increase in ink reflection density at 10,000 m, but increase in ink reflection density at 15,000 m. D: No increase in ink reflection density at 5,000 m, but increase in ink reflection density at 10,000 m. E: Increase in ink reflection density at 5,000 m.

(4) Elemental Analysis of the Area Irradiated with Electron Beam or UV Light with a Wavelength of 125 to 260 nm and the Area Not Irradiated with Electron Beam or UV Light (4-1) Elemental Concentration Elemental analysis of the area irradiated with electron beam or UV light with a wavelength of 125 to 260 nm and the area not irradiated with electron beam or UV light of the printing members obtained by the methods described in each of the Examples and Comparative Examples was evaluated and calculated by the following analytical method.
Analyzer: Scanning X-ray photoelectron spectrometer (ESCA system ULVAC PHI 5700 (manufactured by ULVAC-PHI))
Degree of vacuum: 1.33×10-6 Pa or less X-ray source: Mg source Scan: Narrow scan Measurement elements: C1s, O1s, Si2p, Ti2p
X-ray incident angle: 45 degrees.

Measurements were taken at one arbitrary location on each of the areas irradiated with electron beam or ultraviolet light with a wavelength of 125 to 260 nm and the areas not irradiated with electron beam or ultraviolet light. The obtained measurement data was analyzed using data analysis software "PHI MultiPak" (trademark) (ULVAC-PHI), with smoothing correction at Point 9 and background correction OFF SET, to display the spectrum of each element, and the concentration value (atom%) of each element was calculated from the spectral area obtained by subtracting the baseline.

(4-2) Ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration)
The oxygen concentration value obtained in (4-1) above was divided by the silicon concentration value to calculate the ratio of the oxygen concentration to the silicon concentration (oxygen concentration/silicon concentration).

(5) Analysis by FT-IR-ATR Method Infrared absorption was analyzed by the following method for any one location of a portion irradiated with electron beam or ultraviolet light having a wavelength of 125 to 260 nm and a portion not irradiated with electron beam or ultraviolet light of the printing member obtained by the method described in each Example and Comparative Example.
Analytical device: FTS-55A (manufactured by Bio-Rad Diglab)
Light source: Special ceramics Detector: MCT
Purge: Nitrogen gas Resolution: 4 ^cm
Accumulation count: 512 times
Measurement method: ATR (attenuated total reflection) method Measurement wavelength range: 4000 to 600 ^cm
Attached equipment: Single reflection type ATR measurement accessory equipment (The SeagullTM)
Polarization: None IRE: Ge (Refractive index: 4.0)
Incident angle: 45 degrees.

[Example 1]
The following primer layer forming composition-1 was applied onto a degreased aluminum substrate (manufactured by Mitsubishi Aluminum Co., Ltd.) having a thickness of 0.24 mm and dried at 200° C. for 90 seconds to provide a primer layer having an average thickness of 10 μm.

<Primer layer forming composition-1>
The following component (a-1) was added to a container, and while stirring with a three-one motor, components (b-1), (c-1), (d-1), and (e-1) were added slowly in sequence and stirred and mixed until the components were uniform. Components (f-1) and (g-1) were added to the resulting mixture and stirred and mixed for 10 minutes to obtain a primer layer-forming composition-1.
(a-1) Titanium oxide dispersion: N,N-dimethylformamide dispersion of "Tipaque" (registered trademark) CR-50 (manufactured by Ishihara Sangyo Kaisha, Ltd.) (titanium oxide 50% by mass): 60.0 parts by mass (b-1) Epoxy resin: "jER" (registered trademark) 1010 (manufactured by Mitsubishi Chemical Corporation): 35.0 parts by mass (c-1) Polyurethane: "Sanprene" (registered trademark) LQ-T1331D (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration: 20% by mass): 375.0 parts by mass (d-1) N,N-dimethylformamide: 730.0 parts by mass (e-1) Methyl ethyl ketone: 250.0 parts by mass (f-1) Aluminum chelate: "Aluminum chelate" ALCH-TR (manufactured by Kawaken Fine Chemical Co., Ltd.): 10.0 parts by mass (g-1) Leveling agent: "Disparlon" (registered trademark) LC951 (manufactured by Kusumoto Chemical Co., Ltd., solid content: 10% by mass): 1.0 part by mass.

<(a-1) Preparation of titanium oxide dispersion liquid>
Into a sealable standard glass bottle filled with 1,600.0 g of zirconia beads: "YTZ" (registered trademark) balls (φ1 mm, manufactured by Nikkato Corporation), 700.0 g of N,N-dimethylformamide and 700.0 g of "TYPAQUE" (registered trademark) CR-50 were placed. After sealing, the bottle was set on a small ball mill rotating stand (manufactured by AS ONE Corporation) and dispersed at a rotation speed of 0.4 m/sec for 7 days, thereby obtaining (a-1) a titanium oxide dispersion liquid.

Then, the following composition-1 for forming a diorganosiloxane unit-containing layer was applied onto the primer layer and heated at 140°C for 80 seconds to provide a diorganosiloxane unit-containing layer with an average thickness of 20.0 μm, thereby obtaining a printing member precursor.

<Diorganosiloxane unit-containing layer-forming composition-1>
The following components (a-2) and (b-2) were added to a container and mixed with stirring until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. Components (c-2) and (d-2) were added to the resulting solution and mixed with stirring for 10 minutes. Just before coating, component (e-2) was added and mixed with stirring to obtain a diorganosiloxane unit-containing layer-forming composition-1.
(a-2) Isoparaffin solvent: "Isopar" (registered trademark) E (manufactured by ExxonMobil Chemical Company): 299.00 parts by mass (b-2) Siloxane compound having two or more silanol groups in the molecule (dimethylhydroxysiloxy-polydimethylsiloxane at both ends): DMS-S35 (manufactured by GELEST Inc., weight average molecular weight: 49,000, number of silanol groups in the molecule: 2.0): 95.98 parts by mass (c-2) Silane coupling agent: vinyltris(methylethylketoximino)silane (manufactured by GELEST Inc.): 3.0 parts by mass (d-2) Silane coupling agent: tetrakis(methylethylketoximino)silane (solid content concentration: 50% by mass): 2.0 parts by mass (e-2) Reaction catalyst (organotin compound): dibutyltin diacetate: 0.02 parts by mass.

A mask with openings in the shape of a printing pattern was placed on the diorganosiloxane unit-containing layer of the resulting printing member precursor, and an electron beam was irradiated in a pattern in a nitrogen atmosphere at an acceleration voltage of 100 kV and a dose of 1,200 kGy to obtain a printing member having a layer consisting of an ink-repelling portion and an ink-receiving portion.

The ink-repelling portion (portion not irradiated with electron beam) was analyzed by FT-IR-ATR method, and signals were detected in the absorption bands (1256, 1085, 790 ^{cm -1} ) assigned to dimethylsiloxane units, confirming the presence of diorganosiloxane units. Furthermore, no signals were detected in the absorption bands (3055, 1599, 1408, 960 cm ^-1 ) assigned to vinyl groups, and the presence of vinyl groups could not be confirmed. On the other hand, the ink-receiving portion (portion irradiated with electron beam) was analyzed by FT-IR-ATR, and signals were detected in the absorption bands (1271, 1133, 995 cm ^-1 ) assigned to silsesquioxane structures and/or glass structures, confirming the presence of silsesquioxane structures and/or glass structures.

The diorganosiloxane unit concentration in the portion not irradiated with the electron beam was 99% by mass, and the silicon concentration was 36.7% by mass.

The average elastic modulus of the electron beam irradiated area was 890 MPa, and the average elastic modulus of the non-electron beam irradiated area was 1 MPa, with a difference of 889 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 38 atom%, and carbon: 38 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.6. The element concentration ratios of the non-electron beam irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the electron beam irradiated area was 31 mm.

[Example 2]
A printing member was produced and evaluated in the same manner as in Example 1, except that the diorganosiloxane unit-containing layer-forming composition-1 was changed to the diorganosiloxane unit-containing layer-forming composition-2 described below.

<Diorganosiloxane Unit-Containing Layer-Forming Composition-2>
The following components (a-3), (b-3), and (c-3) were added to a container and mixed with stirring until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. Component (d-3) was added to the resulting solution and mixed with stirring for 10 minutes. Just before coating, component (e-3) was added and mixed with stirring to obtain a diorganosiloxane unit-containing layer-forming composition-2.
(a-3) "Isopar" (registered trademark) E: 295.00 parts by mass (b-3) Siloxane compound having two or more vinyl groups in the molecule (dimethylvinylsiloxy-polydimethylsiloxane at both ends): DMS-V35 (GELEST Inc., weight average molecular weight: 49,500, number of vinyl groups in the molecule: 2.0): 91.00 parts by mass (c-3) Siloxane compound having three or more SiH groups in the molecule (trimethylsiloxy-methylhydrosiloxane-dimethylsiloxane copolymer at both ends): HMS-301 (GELEST Inc.) (d-3) Vinyltris(methylethylketoximino)silane: 3.0 parts by mass (e-3) Reaction catalyst (platinum mixture): XC94-C4326 (manufactured by Momentive Performance Materials Japan, LLC, solid content concentration: 1% by mass): 5.0 parts by mass.

FT-IR-ATR analysis of the non-irradiated area detected signals at 1256, 1085, and 790 cm ^-1 , confirming the presence of dimethylsiloxane units. No signals were detected at 3055, 1599, 1408, and 960 cm ^-1 , confirming the presence of vinyl groups. On the other hand, FT-IR-ATR analysis of the irradiated area detected signals at 1271, 1133, and 995 cm ^-1 , confirming the presence of a silsesquioxane structure and/or a glass structure.

The diorganosiloxane unit concentration in the area not irradiated with electron beam was 97% by mass, and the silicon concentration was 36.8% by mass.

The average elastic modulus of the electron beam irradiated area was 870 MPa, and the average elastic modulus of the non-electron beam irradiated area was 1 MPa, with a difference of 869 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 38 atom%, and carbon: 38 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.6. The element concentration ratios of the non-electron beam irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the electron beam irradiated area was 30 mm.

[Example 3]
A printing member was produced and evaluated in the same manner as in Example 1, except that the diorganosiloxane unit-containing layer-forming composition-1 was changed to the diorganosiloxane unit-containing layer-forming composition-3 described below.

<Diorganosiloxane Unit-Containing Layer-Forming Composition-3>
The following components (a-4), (b-4), (c-4), and (d-4) were added to a container and mixed with stirring until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. Just before coating, component (e-4) was added and mixed with stirring to obtain a diorganosiloxane unit-containing layer-forming composition-3.
(a-4) "Isopar" (registered trademark) E: 293.5 parts by mass (b-4) Siloxane compound having 3 or more vinyl groups in the molecule (both terminal trimethylsiloxy-vinylmethylsiloxane-dimethylsiloxane copolymer): VDT-954 (manufactured by GELEST Inc., weight average molecular weight: 225,000, vinyl group concentration: 4.29% by mass, number of vinyl groups in the molecule: 357.2): 94.0 parts by mass (c-4) Siloxane compound having 3 or more SiH groups in the molecule (both terminal trimethylsiloxy-polymethylhydrosiloxane): HMS-993 (GELEST Manufactured by: Ajinomoto Co., Inc., weight average molecular weight: 2,250, H group concentration derived from SiH group: 1.56 mass%, number of SiH groups in molecule: 35.2): 6.0 parts by mass (d-4) Reaction inhibitor: 2-methyl-3-butyn-2-ol: 1.5 parts by mass (e-4) XC94-C4326: 5.0 parts by mass.

As a result of FT-IR-ATR analysis of the part not irradiated with the electron beam, signals were detected at 1256, 1085, and 790 cm ^-1 , confirming the presence of dimethylsiloxane units. In addition, signals were detected at 3055, 1599, 1408, and 960 cm ^-1 , confirming the presence of vinyl groups. The vinyl group concentration was 1.5 mass%. On the other hand, as a result of FT-IR-ATR analysis of the part irradiated with the electron beam, signals were detected at 1271, 1133, and 995 cm ^-1 , confirming the presence of a silsesquioxane structure and/or a glass structure.

The diorganosiloxane unit concentration in the area not irradiated with electron beam was 92% by mass, and the silicon concentration was 37.7% by mass.

The average elastic modulus of the electron beam irradiated area was 1160 MPa, and the average elastic modulus of the non-electron beam irradiated area was 2 MPa, with a difference of 1158 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 40 atom%, and carbon: 36 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The element concentration ratios of the non-electron beam irradiated area were silicon: 24 atom%, oxygen: 25 atom%, and carbon: 51 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.0. The spot diameter of the electron beam irradiated area was 33 mm.

[Example 4]
A printing member was produced and evaluated in the same manner as in Example 1, except that the diorganosiloxane unit-containing layer-forming composition-1 was changed to the diorganosiloxane unit-containing layer-forming composition-4 described below.

<Diorganosiloxane Unit-Containing Layer-Forming Composition-4>
The following components (a-5), (b-5), and (c-5) were added to a container and mixed with stirring until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. Component (d-5) was added to the resulting solution and mixed with stirring for 30 minutes. Just before coating, component (e-5) was added and mixed with stirring to obtain a diorganosiloxane unit-containing layer-forming composition-4.
(a-5) "Isopar" (registered trademark) E: 295.00 parts by mass (b-5) DMS-S35: 91.00 parts by mass (c-5) HMS-301: 6.0 parts by mass (d-5) Vinyl tris (methyl ethyl ketoximino) silane: 3.0 parts by mass (e-5) XC94-C4326: 5.0 parts by mass.

FT-IR-ATR analysis of the non-irradiated area detected signals at 1256, 1085, and 790 cm ^-1 , confirming the presence of dimethylsiloxane units. No signals were detected at 3055, 1599, 1408, and 960 cm ^-1 , confirming the presence of vinyl groups. On the other hand, FT-IR-ATR analysis of the irradiated area detected signals at 1271, 1133, and 995 cm ^-1 , confirming the presence of a silsesquioxane structure and/or a glass structure.

The diorganosiloxane unit concentration in the area not irradiated with electron beam was 98% by mass, and the silicon concentration was 37.1% by mass.

The average elastic modulus of the electron beam irradiated area was 870 MPa, while the average elastic modulus of the ink repelling area (area not irradiated with the electron beam) was 1 MPa, with a difference of 869 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 38 atom%, carbon: 38 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.6. The element concentration ratios of the non-electron beam irradiated area were silicon: 24 atom%, oxygen: 26 atom%, carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the electron beam irradiated area was 30 mm.

[Example 5]
A printing member was produced and evaluated in the same manner as in Example 2, except that the dose of the electron beam was changed from 1,200 kGy to 800 kGy.

As a result of FT-IR-ATR analysis of the electron beam irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the portion contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the electron beam irradiated area was 150 MPa, and the average elastic modulus of the non-electron beam irradiated area was 1 MPa, with a difference of 149 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 32 atom%, and carbon: 44 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.3. The spot diameter of the electron beam irradiated area was 21 mm.

[Example 6]
A printing member was produced and evaluated in the same manner as in Example 3, except that the dose of the electron beam was changed from 1,200 kGy to 800 kGy.

As a result of FT-IR-ATR analysis of the electron beam irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the portion contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the electron beam irradiated area was 720 MPa, and the average elastic modulus of the non-electron beam irradiated area was 2 MPa, with a difference of 718 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 36 atom%, and carbon: 40 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.5. The spot diameter of the electron beam irradiated area was 28 mm.

[Example 7]
A printing member precursor was prepared in the same manner as in Example 2.

Using an electron beam lithography device, the diorganosiloxane unit-containing layer of the above printing member precursor was subjected to electron beam lithography in a nitrogen atmosphere at an acceleration voltage of 100 kV and a dose of 1200 kGy to obtain a printing member.

As a result of FT-IR-ATR analysis of the electron beam irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the portion contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the electron beam irradiated area was 870 MPa, and the average elastic modulus of the non-electron beam irradiated area was 1 MPa, with a difference of 869 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 38 atom%, and carbon: 38 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.6. The spot diameter of the electron beam irradiated area was 30 mm.

When the printout was extracted and observed about 500m from the start of printing, it was confirmed that 0.5 to 99.5% of the dots in the AM 600 lpi (resolution: 8500 dpi) dot area were faithfully reproduced, making it possible to reproduce images with significantly higher resolution than with conventional offset printing materials (AM 175 lpi, resolution: 2400 dpi, reproducible dots: 1 to 99%).

[Example 8]
A printing member precursor was prepared in the same manner as in Example 1.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and ultraviolet light having a wavelength of 172 nm was irradiated in a pattern shape at an exposure dose of 600 mJ/ ^cm2 using a _Xe2 excimer lamp (manufactured by Ushio Electric Co., Ltd.) in a vacuum to obtain a printing member having a layer consisting of ink-repelling portions and ink-receiving portions.

As a result of FT-IR-ATR analysis of the inked portion (ultraviolet irradiated portion), signals were detected at 1271, 1133 and 995 cm ^-1 , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 730 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 729 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The spot diameter of the UV-irradiated area was 28 mm.

[Example 9]
A printing member precursor was prepared in the same manner as in Example 2.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern with ultraviolet light having a wavelength of 172 nm at an exposure dose of 600 mJ/ ^cm2 using a _Xe2 excimer lamp in a vacuum to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The spot diameter of the UV-irradiated area was 28 mm.

[Example 10]
A printing member precursor was prepared in the same manner as in Example 3.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern with ultraviolet light having a wavelength of 172 nm at an exposure dose of 600 mJ/ ^cm2 using a _Xe2 excimer lamp in a vacuum to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 740 MPa, and the average elastic modulus of the non-UV-irradiated area was 2 MPa, with a difference of 738 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 42 atom%, and carbon: 33 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The spot diameter of the UV-irradiated area was 28 mm.

[Example 11]
A printing member precursor was prepared in the same manner as in Example 4.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern with ultraviolet light having a wavelength of 172 nm at an exposure dose of 600 mJ/ ^cm2 using a _Xe2 excimer lamp in a vacuum to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The spot diameter of the UV-irradiated area was 28 mm.

[Example 12]
A printing member precursor was prepared in the same manner as in Example 2.

Using an _F2 excimer laser imaging device (wavelength: 157 nm), ultraviolet imaging was performed on the diorganosiloxane unit-containing layer of the printing member precursor in a vacuum at an exposure dose of 300 mJ/ _cm2 to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 1870 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 1869 MPa. The element concentration ratios of the UV-irradiated area were silicon: 29 atom%, oxygen: 57 atom%, and carbon: 14 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 2.0. The spot diameter of the UV-irradiated area was 35 mm.

When the printout was extracted and observed about 500m from the start of printing, it was confirmed that 0.5 to 99.5% of the dots in the AM 600 lpi (resolution: 8500 dpi) dot area were faithfully reproduced, making it possible to reproduce images with significantly higher resolution than with conventional offset printing materials (AM 175 lpi, resolution: 2400 dpi, reproducible dots: 1 to 99%).

[Example 13]
A printing member precursor was prepared in the same manner as in Example 2.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern shape with ultraviolet light having a wavelength of 126 nm at an exposure dose of 600 mJ/ _cm2 in a vacuum using an _Ar2 excimer lamp (manufactured by Ushio Electric Co., Ltd.) to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The spot diameter of the UV-irradiated area was 28 mm.

[Example 14]
A printing member precursor was prepared in the same manner as in Example 2.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern shape with ultraviolet light having a wavelength of 146 nm at an exposure dose of 600 mJ/ ^cm2 in a vacuum using a _Kr2 excimer lamp (manufactured by Ushio Electric Co., Ltd.) to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The spot diameter of the UV-irradiated area was 28 mm.

[Example 15]
A printing member precursor was prepared in the same manner as in Example 2.

A mask having openings in the shape of a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the pattern was irradiated with ultraviolet light having a wavelength of 193 nm at an exposure dose of 600 mJ/ ^cm2 in a vacuum using an ArF excimer lamp (manufactured by Ushio Electric Co., Ltd.) to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 650 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 649 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 42 atom%, and carbon: 33 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The spot diameter of the UV-irradiated area was 27 mm.

[Example 16]
A printing member was produced and evaluated in the same manner as in Example 9, except that the ultraviolet ray irradiation was changed from a vacuum to atmospheric pressure (N ₂ : 100%).

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 700 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 699 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 42 atom%, and carbon: 33 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The spot diameter of the UV-irradiated area was 28 mm.

[Example 17]
A printing member was produced and evaluated in the same manner as in Example 9, except that the ultraviolet irradiation was changed from a vacuum to atmospheric pressure (atmosphere: 100%).

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 110 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 109 MPa. The element concentration ratios of the UV-irradiated area were silicon: 24 atom%, oxygen: 31 atom%, and carbon: 45 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.3. The spot diameter of the UV-irradiated area was 21 mm.

[Example 18]
A printing member was produced and evaluated in the same manner as in Example 9, except that the average thickness of the diorganosiloxane unit-containing layer was changed from 20.0 μm to 40.0 μm.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The element concentration ratios of the non-UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 28 mm.

[Example 19]
A printing member was produced and evaluated in the same manner as in Example 9, except that the average thickness of the diorganosiloxane unit-containing layer was changed from 20.0 μm to 10.0 μm.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The element concentration ratios of the non-UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 28 mm.

[Example 20]
A printing member was produced and evaluated in the same manner as in Example 9, except that the average thickness of the diorganosiloxane unit-containing layer was changed from 20.0 μm to 5.0 μm.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The element concentration ratios of the non-UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 28 mm.

[Example 21]
A printing member was produced and evaluated in the same manner as in Example 9, except that the average thickness of the diorganosiloxane unit-containing layer was changed from 20.0 μm to 2.5 μm.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The element concentration ratios of the non-UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 28 mm.

[Example 22]
The following primer layer-forming composition-2 was applied onto a 0.25 mm-thick degreased polyethylene terephthalate film: "Lumirror (registered trademark)"#250-X10s (manufactured by Toray Industries, Inc.), and dried at 100°C for 30 seconds to provide a primer layer with an average thickness of 0.5 µm.

<Primer layer forming composition-2>
The following components (a-6), (b-6), and (c-6) were added to a container and stirred until the components were uniformly mixed. Component (d-6) was added to the resulting mixture and stirred for 5 minutes to obtain a primer layer-forming composition-2.
(a-6) Methyl ethyl ketone: 900.0 parts by mass (b-6) Epoxy resin: "jER" (registered trademark) 1007 (manufactured by Mitsubishi Chemical Corporation): 90.0 parts by mass (c-6) Hexamethylene diisocyanate: 10.0 parts by mass (d-6) Dibutyltin diacetate: 0.1 parts by mass.

Next, the diorganosiloxane unit-containing layer forming composition-2 described in Example 2 was applied onto the primer layer and heated at 100°C for 60 seconds to provide a diorganosiloxane unit-containing layer with an average thickness of 20.0 μm, thereby obtaining a printing member precursor.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern with ultraviolet light having a wavelength of 172 nm at an exposure dose of 600 mJ/ ^cm2 using a _Xe2 excimer lamp in a vacuum to obtain a printing member.

FT-IR-ATR analysis of the UV-unirradiated portion detected signals at 1256, 1085, and 790 cm ^-1 , confirming the presence of dimethylsiloxane units. No signals were detected at 3055, 1599, 1408, and 960 cm ^-1 , confirming the presence of vinyl groups. On the other hand, FT-IR-ATR analysis of the UV-irradiated portion detected signals at 1271, 1133, and 995 cm ^-1 , confirming the presence of a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 720 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 719 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 43 atom%, and carbon: 32 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The element concentration ratios of the non-UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 28 mm.

[Example 23]
The primer layer-forming composition-1 described in Example 1 was applied to the surface of a cylindrical aluminum alloy support using a cylindrical slit die coater (manufactured by Toray Engineering Co., Ltd.), and dried at 200°C for 300 seconds to provide a primer layer with an average thickness of 10 µm.

Next, the diorganosiloxane unit-containing layer-forming composition-2 described in Example 2 was applied onto the primer layer using a cylindrical slit die coater and heated at 140°C for 300 seconds to provide a diorganosiloxane unit-containing layer with an average thickness of 20.0 μm, thereby obtaining a printing member precursor.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern with ultraviolet light having a wavelength of 172 nm at an exposure dose of 600 mJ/ ^cm2 using a _Xe2 excimer lamp in a vacuum to obtain a printing member.

Except for using the above printing member as the plate cylinder and using a cylindrical blanket (surface rubber: NBR, manufactured by Kinyosha Co., Ltd.) as the blanket, printing was performed under the same conditions as in (3) Printing method in <Evaluation method for each Example and Comparative Example> above, and the printed matter was evaluated.

In this embodiment, because both the blanket and the printing member are seamless cylindrical members, seamless printing was possible using a normal continuous printing method without using a step-back printing method (intermittent method).

[Example 24]
A printing member was produced and evaluated in the same manner as in Example 8, except that the diorganosiloxane unit-containing layer-forming composition-1 was changed to the diorganosiloxane unit-containing layer-forming composition-5 described below.

<Diorganosiloxane Unit-Containing Layer-Forming Composition-5>
The following components (a-7) and (b-7) were added to a container and mixed with stirring until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. Components (c-7) and (d-7) were added to the resulting solution and mixed with stirring for 10 minutes. Just before coating, component (e-7) was added and mixed with stirring to obtain a diorganosiloxane unit-containing layer-forming composition-5.
(a-7) "Isopar" (registered trademark) E: 299.00 parts by mass (b-7) Siloxane compound having two or more silanol groups in the molecule (dimethylhydroxysiloxy-polydimethylsiloxane at both ends): TF-13 (manufactured by Dow Corning Toray Co., Ltd., weight average molecular weight: 400,000, number of silanol groups in the molecule: 2.0): 99.98 parts by mass (c-7) Vinyl tris (methyl ethyl ketoximino) silane: 0.75 parts by mass (d-7) Tetrakis (methyl ethyl ketoximino) silane (solid concentration: 50% by mass): 0.25 parts by mass (e-7) Dibutyltin diacetate: 0.02 parts by mass.

FT-IR-ATR analysis of the UV-unirradiated portion detected signals at 1256, 1085, and 790 cm ^-1 , confirming the presence of dimethylsiloxane units. No signals were detected at 3055, 1599, 1408, and 960 cm ^-1 , confirming the presence of vinyl groups. On the other hand, FT-IR-ATR analysis of the UV-irradiated portion detected signals at 1271, 1133, and 995 cm ^-1 , confirming the presence of a silsesquioxane structure and/or a glass structure.

The diorganosiloxane unit concentration in the area not irradiated with ultraviolet light was 100% by mass, and the silicon concentration was 40.8% by mass.

The average elastic modulus of the UV-irradiated area was 710 MPa, and the average elastic modulus of the non-UV-irradiated area was 0.004 MPa, with a difference of 709.996 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 42 atom%, and carbon: 33 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.7. The element concentration ratios of the non-UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 28 mm.

[Example 25]
A printing member was produced and evaluated in the same manner as in Example 9, except that the diorganosiloxane unit-containing layer-forming composition-2 was changed to the diorganosiloxane unit-containing layer-forming composition-6 described below.

<Diorganosiloxane Unit-Containing Layer-Forming Composition-6>
The following components (a-8), (b-8), (c-8) and (d-8) were added to a container and mixed with stirring until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. Component (e-8) was added to the resulting solution and mixed with stirring for 10 minutes. Just before coating, component (f-8) was added and mixed with stirring to obtain a diorganosiloxane unit-containing layer-forming composition-6.
(a-8) "Isopar" (registered trademark) E: 295.00 parts by mass (b-8) DMS-V35: 75.26 parts by mass (c-8) HMS-301: 4.96 parts by mass (d-8) Titania particles: ST-21 (manufactured by Ishihara Sangyo Kaisha, Ltd., X-ray particle size: 20 nm): 17.3 parts by mass (e-8) Vinyl tris (methyl ethyl ketoximino) silane: 2.48 parts by mass (f-8) XC94-C4326: 5.0 parts by mass.

In this embodiment, the titania particle content in the diorganosiloxane unit-containing layer is 5% by volume.

FT-IR-ATR analysis of the UV-unirradiated portion detected signals at 1256, 1085, and 790 cm ^-1 , confirming the presence of dimethylsiloxane units. No signals were detected at 3055, 1599, 1408, and 960 cm ^-1 , confirming the presence of vinyl groups. On the other hand, FT-IR-ATR analysis of the UV-irradiated portion detected signals at 1271, 1133, and 995 cm ^-1 , confirming the presence of a silsesquioxane structure and/or a glass structure.

The diorganosiloxane unit concentration in the area not irradiated with ultraviolet light was 80% by mass, and the silicon concentration was 30.4% by mass.

The average elastic modulus of the UV-irradiated area was 740 MPa, and the average elastic modulus of the non-UV-irradiated area was 13 MPa, with a difference of 727 MPa. The element concentration ratios of the UV-irradiated area were silicon: 23 atom%, oxygen: 45 atom%, carbon: 28 atom%, titanium: 4 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.9. The element concentration ratios of the non-UV-irradiated area were silicon: 22 atom%, oxygen: 30 atom%, carbon: 44 atom%, titanium: 4 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.4. The spot diameter of the UV-irradiated area was 28 mm.

[Example 26]
A printing member was produced and evaluated in the same manner as in Example 3, except that the dose of the electron beam was changed from 1200 kGy to 100 kGy.

As a result of FT-IR-ATR analysis of the electron beam irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the portion contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the electron beam irradiated area was 210 MPa, and the average elastic modulus of the non-electron beam irradiated area was 2 MPa, with a difference of 208 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 30 atom%, and carbon: 46 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.3. The spot diameter of the electron beam irradiated area was 20 mm.

[Example 27]
A printing member was produced and evaluated in the same manner as in Example 2, except that the dose of the electron beam was changed from 1200 kGy to 3000 kGy.

As a result of FT-IR-ATR analysis of the electron beam irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the portion contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the electron beam irradiated area was 9700 MPa, and the average elastic modulus of the non-electron beam irradiated area was 1 MPa, with a difference of 9699 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 32 atom%, oxygen: 64 atom%, and carbon: 4 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 2.0. The spot diameter of the electron beam irradiated area was 37 mm.

[Example 28]
A printing member was produced and evaluated in the same manner as in Example 2, except that the accelerating voltage of the electron beam was changed from 100 kV to 50 kV.

As a result of FT-IR-ATR analysis of the electron beam irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the portion contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the electron beam irradiated area was 900 MPa, and the average elastic modulus of the non-electron beam irradiated area was 1 MPa, with a difference of 899 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 39 atom%, and carbon: 37 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.6. The spot diameter of the electron beam irradiated area was 31 mm.

[Example 29]
A printing member was produced and evaluated in the same manner as in Example 2, except that the accelerating voltage of the electron beam was changed from 100 kV to 150 kV.

As a result of FT-IR-ATR analysis of the electron beam irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the portion contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the electron beam irradiated area was 690 MPa, and the average elastic modulus of the non-electron beam irradiated area was 1 MPa, with a difference of 689 MPa. The element concentration ratios of the electron beam irradiated area were silicon: 24 atom%, oxygen: 36 atom%, and carbon: 40 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.5. The spot diameter of the electron beam irradiated area was 28 mm.

[Example 30]
A printing member was produced and evaluated in the same manner as in Example 9, except that the exposure dose of ultraviolet light was changed from 600 mJ/cm ² to 300 mJ/cm ² .

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 120 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 119 MPa. The element concentration ratios of the UV-irradiated area were silicon: 25 atom%, oxygen: 32 atom%, and carbon: 43 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.3. The spot diameter of the UV-irradiated area was 21 mm.

[Example 31]
A printing member was produced and evaluated in the same manner as in Example 9, except that the exposure dose of ultraviolet light was changed from 600 mJ/cm ² to 3000 mJ/cm ² .

As a result of FT-IR-ATR analysis of the UV-irradiated portion, signals were detected at 1271, 1133 and 995 cm ⁻¹ , confirming that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 9,500 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 9,499 MPa. The element concentration ratios of the UV-irradiated area were silicon: 31 atom%, oxygen: 62 atom%, and carbon: 7 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 2.0. The spot diameter of the UV-irradiated area was 37 mm.

[Comparative Example 1]
A printing member precursor was prepared in the same manner as in Example 2.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern shape with ultraviolet light having a wavelength of 283 nm at an exposure dose of 3000 mJ/ ^cm2 in a vacuum using a XeBr excimer lamp (manufactured by Ushio Electric Co., Ltd.) to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, no signals were detected at 1271, 1133, and 995 cm ⁻¹ , and it was not possible to confirm that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 3 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 2 MPa. The element concentration ratios of the UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 8 mm.

When the obtained printing material was used for printing, no ink was found adhering to the UV-irradiated parts of the printing material, and no ink-receiving areas were formed within the printing material.

[Comparative Example 2]
A printing member precursor was prepared in the same manner as in Example 2.

A mask having openings in the shape of a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the pattern was irradiated with ultraviolet light having a wavelength of 308 nm at an exposure dose of 3,000 mJ/ ^cm2 in a vacuum using a XeCl excimer lamp (manufactured by Ushio Electric Co., Ltd.) to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, no signals were detected at 1271, 1133, and 995 cm ⁻¹ , and it was not possible to confirm that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 2 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 1 MPa. The element concentration ratios of the UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 8 mm.

When the obtained printing material was used for printing, no ink was found adhering to the UV-irradiated parts of the printing material, and no ink-receiving areas were formed within the printing material.

[Comparative Example 3]
A printing member precursor was prepared in the same manner as in Example 2.

A mask having openings in a printing pattern was placed on the diorganosiloxane unit-containing layer of the obtained printing member precursor, and the layer was irradiated in a pattern shape with ultraviolet light having a wavelength of 253 nm at an exposure dose of 3000 mJ/ ^cm2 using a XeI excimer lamp (manufactured by Ushio Electric Co., Ltd.) in a vacuum to obtain a printing member.

As a result of FT-IR-ATR analysis of the UV-irradiated portion, no signals were detected at 1271, 1133, and 995 cm ⁻¹ , and it was not possible to confirm that the film contained a silsesquioxane structure and/or a glass structure.

The average elastic modulus of the UV-irradiated area was 2 MPa, and the average elastic modulus of the non-UV-irradiated area was 1 MPa, with a difference of 1 MPa. The element concentration ratios of the UV-irradiated area were silicon: 24 atom%, oxygen: 26 atom%, and carbon: 50 atom%, and the ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) was 1.1. The spot diameter of the UV-irradiated area was 8 mm.

When the obtained printing material was used for printing, no ink was found adhering to the UV-irradiated parts of the printing material, and no ink-receiving areas were formed within the printing material.

The evaluation results for Examples 1 to 31 and Comparative Examples 1 to 3 are shown in Table 1.

REFERENCE SIGNS LIST 1 Support 2 Layer consisting of ink-repelling portion and ink-receiving portion 3 Ink-repelling portion 4 Ink-receiving portion 5 Ink roller 6 Printing member 7 Plate cylinder 8 Blanket cylinder 9 Printed medium 10 Impression cylinder

Claims (17)

A printing member having a support and a layer consisting of an ink-repellent portion and an ink-receiving portion, the layer having the ink-repellent portion and the ink-receiving portion on at least a surface thereof, the ink-repellent portion containing a diorganosiloxane unit, the ink-receiving portion containing a silsesquioxane structure and/or a glass structure, and a difference between an average modulus of elasticity of the ink-receiving portion and an average modulus of elasticity of the ink-repellent portion being 100 to 10,000 MPa . 2. The printing member according to claim 1, wherein the ratio of oxygen concentration to silicon concentration in the inked portion is 1.3 to 2.0. 3. The printing member according to claim 1, wherein the element concentrations in the ink-receiving portion are as follows: silicon: 23 to 33 atom %, oxygen: 30 to 67 atom %, and carbon: 0 to 47 atom %. 4. The printing member according to claim 1, wherein the ink-receiving portion has an average elastic modulus of 100 to 10,000 MPa. 5. The printing member according to claim 1, wherein the ratio of oxygen concentration to silicon concentration in the ink repellent portion is 0.9 to 1.2. 6. The printing member according to claim 1, wherein the element concentrations in the ink-repelling portion are as follows: silicon: 22 to 26 atom %, oxygen: 24 to 28 atom %, and carbon: 48 to 52 atom %. 7. The printing member according to claim 1, wherein the ink-repelling portion has an average elastic modulus of 0.001 to 10 MPa. 8. A method for producing the printed member according to claim 1, comprising irradiating an electron beam onto a layer made of ink-repelling parts to draw a pattern of ink-receiving parts. The method for producing a printing member according to claim 8, wherein the dose of the electron beam is 100 to 3000 kGy. The method for producing a printing member according to claim 8 or 9, wherein the accelerating voltage of the electron beam is 50 to 150 kV. A method for producing the printed member according to any one of claims 1 to 7, comprising irradiating a layer made of an ink-repelling portion with ultraviolet light having a wavelength of 125 to 200 nm to draw a pattern of an ink-receiving portion. The exposure dose of the ultraviolet light having a wavelength of 125 to 200 nm is 300 to 3000 mJ/cm ² The method of claim 11 , wherein A method for producing a printed matter using the printing member, ink, and print medium according to any one of claims 1 to 7. The method for producing a printed matter according to claim 13, wherein the ink is an active energy ray-curable ink. The method for producing a printed matter according to claim 13 or 14, wherein the ink is a water-soluble ink. The method for producing a printed matter according to any one of claims 13 to 15, wherein the print medium does not absorb ink components. The method for producing a printed matter according to any one of claims 13 to 16, wherein the medium to be printed is a food packaging substrate.

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