JP2019093613A - Method for manufacturing printed matter - Google Patents

Abstract

To provide a method for manufacturing a printed matter excellent in printing resistance even when a lithographic printing plate having a heat-sensitive layer containing a melamine resin and an ink repelling layer is used on a substrate.SOLUTION: A method for manufacturing a printed matter includes: a step of attaching an ink for lithographic printing to a lithographic printed plate 2 having (A) a heat-sensitive layer containing a photothermal conversion substance and a melamine resin and (B) an ink repelling layer containing a silicone rubber derived from an addition reaction of a hydrosilyl group-containing compound and a vinyl group-containing polysiloxane, in which the rubber contains a dimethylsiloxane unit and a siloxane unit, and a peak intensity ratio is 0.0005 or more and 0.0090 or less, on a substrate; and a step of transferring the attached ink to a body 5 to be printed directly or through a blanket 4.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a printed matter using a lithographic printing plate having a heat-sensitive layer and an ink repellent layer, and an active energy ray-curable water-soluble ink for lithographic printing.

  Lithographic printing is widely known as a system for supplying prints at high speed, in large quantities, and inexpensively. Generally, in lithographic printing, non-image areas are formed by retaining dampening water in hydrophilic portions, and oil ink is adhered to the image areas of hydrophobic portions to perform image formation. However, from the viewpoint of environmental problems and working environment preservation in recent years, waterless lithographic printing without using dampening water has attracted attention in various printing fields in order to reduce volatile organic compounds. In waterless lithographic printing, instead of dampening water, silicone rubber or fluorocarbon resin is used as an ink repellent layer, and the ink receptive layer forming an image area and the ink repellent layer forming a non-image area are almost flat. This is a lithographic printing method that is a printing plate that exists, and after depositing ink only in the image area using the difference in ink adhesion, transfers the ink to a printing material such as paper to print.

  In order to obtain the printed matter excellent in printing quality, in order to improve the ink receptivity of the printing plate line area, techniques using melamine resin for the heat-sensitive layer to be the ink receiving layer have been proposed (Patent Documents 1 and 2) . In addition to this, as a technology for improving the ink repulsion property of the non-image area, a technology using an ink with high surface tension has been proposed (Patent Document 3).

  As a method of reducing volatile organic compounds in the printing step and the washing step in lithographic printing, a technology using a water-soluble UV ink has been proposed (Patent Document 4).

International Publication No. 2014-31828 JP 2004-4604 A JP 2007-112965 A JP, 2017-52817, A

However, when a melamine resin is used for the heat sensitive layer, the printing durability may be insufficient.
An object of the present invention is to provide a method for producing a printed matter excellent in printing durability even when a lithographic printing plate having a heat-sensitive layer containing a melamine resin and an ink repelling layer on a substrate is used.

That is, the present invention relates to a silicone derived from the addition reaction of (A) a photothermal conversion substance and a melamine resin on a substrate, and (B) (a) a hydrosilyl group-containing compound and (b) a vinyl group-containing polysiloxane. A rubber is contained, and the rubber contains a dimethylsiloxane unit represented by the following general formula (I) and a siloxane unit represented by (II), and the peak intensity of (II) Si ^** / (I) Si ^* Ink repellent layer having a peak intensity ratio represented by a peak intensity of 0.0005 or more and 0.0090 or less-Si ^* (CH ₃ ) ₂ -O- (I)
_{-Si (CH 3) 2 -CH 2} -CH 2 -Si ** (CH 3) 2 -O- (II)
The present invention relates to a method for producing a printed matter, comprising the steps of: attaching a lithographic printing ink to a lithographic printing plate having the step of: and transferring the attached ink to a substrate to be printed directly or via a blanket.

  According to the method for producing a printed matter of the present invention, it is possible to obtain a lithographic printing method and a printed matter which are excellent in ink repulsion and ink receptivity, have good print quality, and are also excellent in environmental aspect.

Sectional drawing which shows an example of the manufacturing method of the printed matter of this invention.

  Hereinafter, the present invention will be specifically described.

<Thermosensitive layer (A)>
The lithographic printing plate used in the present invention has a heat sensitive layer (A) on a substrate. The heat sensitive layer (A) has a function of efficiently absorbing the laser beam used for drawing and converting it into heat (photothermal conversion), and at least the surface of the heat sensitive layer is decomposed by the heat, or the developer It is preferable that the solubility in the ink be increased or the adhesion to the ink repellent layer be decreased. Therefore, the heat-sensitive layer (A) of the lithographic printing plate used in the present invention contains a photothermal conversion material. As the light-to-heat conversion substance, the light energy is converted into kinetic energy of atoms or molecules by absorbing laser light, and heat is generated at 200 ° C. or more on the surface of the heat-sensitive layer instantaneously to form a crosslinked structure of the heat-sensitive layer. Those having the function of thermally decomposing are preferred. In particular, pigments, dyes, and metal complexes that absorb infrared rays or near infrared rays are preferably used. Specific examples of the pigment include black pigments such as carbon black, aniline black and cyanine black, phthalocyanines, green pigments of naphthalocyanine series, carbon graphite, iron powder and the like. As metal complexes, diamine metal complexes, dithiol metal complexes, phenol thiol metal complexes, mercaptophenol metal complexes, water of crystallization containing inorganic compounds, copper sulfate, chromium sulfide, silicate compounds, titanium oxide, vanadium oxide, manganese oxide And metal oxides such as iron oxide, cobalt oxide and tungsten oxide, and hydroxides of these metals, sulfates, bismuth, iron, magnesium, metal powders of aluminum and the like.

  Further, as dyes that absorb infrared rays or near infrared rays, dyes for electronics and recording, cyanine dyes, azulenium dyes, squalilium dyes, croconium dyes, azo dyes having a maximum absorption wavelength in the range of 700 nm to 1500 nm Disperse dyes, bisazostilbene dyes, naphthoquinone dyes, anthraquinone dyes, perylene dyes, phthalocyanine dyes, naphthalocyanine metal complex dyes, polymethine dyes, dithiol nickel complex dyes, indoaniline metal complex dyes, molecules Interstitial CT dyes, benzothiopyran-based spiropyrans, nigrosine dyes and the like are preferably used.

Among these dyes, those having a large molar absorption coefficient ε are preferably used. Specifically, ε is preferably 1 × 10 ⁴ L / (mol · cm) or more, more preferably 1 × 10 ⁵ L / (mol · cm) or more. If ε is 1 × 10 ⁴ L / (mol · cm) or more, the initial sensitivity can be further improved. The coefficient here is for the active energy ray to be irradiated. If a specific wavelength is indicated, attention should be paid to 780 nm, 830 nm or 1064 nm. Two or more of these photothermal conversion substances may be contained. By containing two or more types of photothermal conversion materials having different absorption wavelengths, it is possible to cope with two or more types of lasers having different emission wavelengths.

  Among these, from the viewpoints of light-to-heat conversion, economy and handling, carbon black and dyes that absorb infrared rays or near infrared rays are preferable.

  The content of these light-to-heat conversion substances is preferably 0.1% by weight to 70% by weight, and more preferably 0.5% by weight to 40% by weight, in the heat-sensitive layer (A). By setting the content of the photothermal conversion substance to 0.1% by weight or more, the sensitivity to laser light can be further improved. On the other hand, by setting the content to 70% by weight or less, the high printing durability of the lithographic printing plate can be maintained.

  The heat-sensitive layer (A) of the lithographic printing plate used in the method for producing a printed matter of the present invention can contain an organic complex compound for the purpose of improving the interlayer adhesion by forming a crosslinked structure. Here, the organic complex compound in the present invention refers to an organic complex salt in which an organic ligand is coordinated to a metal, an organic-inorganic complex salt in which an organic ligand and an inorganic ligand are coordinated to a metal, and oxygen in a metal and an organic molecule. And metal alkoxides which are covalently bonded to each other. Among these, metal chelate compounds in which the ligand has two or more donor atoms and forms a ring containing a metal atom are the stability of the organic complex compound itself, the stability of the heat-sensitive layer composition solution, etc. It is preferably used from the aspect of The main metals forming the organic complex compound include Al (III), Ti (IV), Mn (II), Mn (III), Fe (II), Fe (III), Co (II), Co (III) ), Ni (II), Ni (IV), Cu (I), Cu (II), Zn (II), Ge, In, Sn (II), Sn (IV), Zr (IV), Hf (IV) Is preferred. Al (III) is particularly preferable in that the sensitivity improvement effect can be easily obtained, and Ti (IV) is particularly preferable in that the resistance to the printing ink and the ink detergent is easily exhibited.

Moreover, as a ligand, the compound which has a coordination group which has oxygen, nitrogen, sulfur etc. as a donor atom is mentioned. As specific examples of the coordination group, those having oxygen as a donor atom include —OH (alcohol, enol and phenol), —COOH (carboxylic acid),> C = O (aldehyde, ketone, quinone), —O - (ether), - COOR (ester, R: represents an aliphatic or aromatic hydrocarbon), - N = O (nitroso compounds), - NO ₂ (nitro compound),> NO (N-oxide), -NH ₂ (primary amine, hydrazine),> NH (secondary amine, hydrazine) as those having nitrogen as a donor atom, such as -SO ₃ H (sulfonic acid) and -PO ₃ H ₂ (phosphorous acid) ),> N- (tertiary amine), -N = N- (azo compound, heterocyclic compound), = N-OH (oxime), -NO ₂ (nitro compound), -N = O (nitroso compound), > C = N-(Schiff salt And heterocyclic compounds),> C = NH (aldehydes, ketone imines, enamines), —NCS (isothiocyanato), etc., having sulfur as a donor atom, such as —SH (thiol), —S— (thioether), C = S (thioketone, thioamide), = S- (heterocyclic compound), -C (= O) -SH, -C (= S) -OH, -C (= S) -SH (thiocarboxylic acid),- SCN (thiocyanate) etc. are mentioned.

  Among the organic complex compounds formed from the metal and the ligand as described above, preferred compounds are Al (III), Ti (IV), Fe (II), Fe (III), Mn (III) , Co (II), Co (III), Ni (II), Ni (IV), Cu (I), Cu (II), Zn (II), Ge, In, Sn (II), Sn (IV), Examples include β-diketones of metals such as Zr (IV) and Hf (IV), amines, alcohols, complexes with carboxylic acids, and further, Al (III), Fe (II), Fe (III) And acetylacetone complexes of Ti (IV), Zr (IV), acetoacetic acid ester complexes, etc. are mentioned as particularly preferable complex compounds.

  Specific examples of such compounds include, for example, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum bis (acetylacetonate) mono ( Ethyl acetoacetate), aluminum dibutoxide mono (acetylacetonate), aluminum diisopropoxide mono (acetylacetonate), aluminum diisopropoxide mono (ethylacetoacetate), aluminum-s-butoxide bis (ethylacetoacetate) Titanium triisopropoxide mono (allylacetoacetate), titanium diisopropoxide bis (triethanolamine), titanium di-n-butoxide bis ( Ethanolamine), trilactate zirconate, iron (III) acetylacetonate, dibenzoylmethaneiron (II), tropolone iron, tristropolono iron (III), hinokitiol iron, tris hinokichioro iron (III), acetoacetate ester iron Mention may be made of compounds such as (III), iron (III) benzoylacetonate, iron (III) diphenylpropanedionate, iron (III) tetramethylheptanedionate, iron (III) trifluoropentanedionate and the like. Two or more of these may be contained.

  The proportion of such an organic complex compound in the heat-sensitive layer (A) is preferably 0.5 to 50% by weight, more preferably 3 to 30% by weight, and 10 to 20% by weight of the heat-sensitive layer. Being particularly preferred. By setting the content of the organic complex compound to 0.5% by weight or more, the effect of improving the interlayer adhesion due to the formation of the crosslinked structure can be expected, and by setting the content to 50% by weight or less, the printing durability of the printing plate The effect of improvement can be expected.

  The heat-sensitive layer (A) of the lithographic printing plate used in the method for producing a printed matter of the present invention contains a melamine resin. The melamine resin is an amino-based thermosetting resin obtained by the polycondensation reaction of melamine and formaldehyde, and has a feature that the polarity of the resin is high because it takes a nitrogen-containing heterocyclic structure. For this reason, since compatibility with the ink with high surface tension, ie, the ink with high polarity, is good, the ink receptivity can be improved by using the resin for the heat-sensitive layer. As a melamine resin, for example, butylated urea resin, butylated melamine resin, butylated benzoguanamine resin, butylated urea melamine condensation resin, amino alkyd resin, iso-butylated melamine resin, methylated melamine resin, hexamethoxymethylol melamine, Methylated benzoguanamine resin, diethylene triamine and the like can be mentioned. These melamine resins may be used alone or in combination of two or more. The content of the melamine resin is preferably 20 to 95% by weight, more preferably 30 to 80% by weight, and particularly preferably 40 to 70% by weight in the heat-sensitive layer (A). If the content of the melamine resin is within the above range, good ink receptivity and printing durability can be obtained.

  The weight average molecular weight (Mw) of the melamine resin is 1000 or more, preferably 10000 or more, more preferably 30000 or more, and further 1000000 or less, preferably 300000 or less, more preferably 100000 or less. When the weight average molecular weight is within the above range, a printing plate having good ink receptivity, solvent resistance and printing durability can be obtained.

  The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC method). Specifically, after filtering the sample through a membrane filter with a pore size of 0.45 μm, GPC apparatus (HLC-82A manufactured by Tosoh Corp.) under predetermined conditions (developing solvent: cyclohexane, developing speed: 1.0 ml / min, column: Tosoh Corp. The value determined by polystyrene conversion using TSKgel G2000 HXL (manufactured by TSKgel G2000 HXL) is the weight average molecular weight in the present invention.

  A curing catalyst of melamine resin may be added to the heat sensitive layer (A). Specifically, sulfonic acid compounds such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and nonionic naphthalenesulfonic acid, neutralization salts of the sulfonic acid compounds with amines, and neutralization with phosphoric acid ester compounds Salt etc. can be mentioned. These can also be used in mixture of 2 or more types.

  The preferable addition amount of the curing catalyst is 0.05 parts by weight or more, more preferably 10 parts by weight or more, further 30 parts by weight or less, preferably 50 parts by weight with respect to 100 parts by weight of the resin of the heat sensitive layer (A). It is below. If it is in the said range, the weight average molecular weight of the melamine resin in a thermosensitive layer (A) can be controlled in a desired range.

  The heat-sensitive layer (A) of the lithographic printing plate used in the present invention may further contain a thermosetting resin (D) different from the melamine resin. Specific examples of the thermosetting resin (D) include novolak resin obtained by condensation reaction of phenol resin such as phenol, cresol and xylenol with formaldehyde, resole resin, urea resin, guanamine resin, epoxy resin, diallyl phthalate resin, Although a saturated polyurethane resin, a polyimide precursor, etc. can be mentioned, it is not limited to these. Moreover, as a thermosetting resin (D), you may use these copolymer resin, and what mixed 2 or more types among these may be used. Among these resins, novolak resin and urea resin can be suitably used from the viewpoint of compatibility with the melamine resin.

  The content of the thermosetting resin (D) is preferably 0.1 parts by weight or more and 2000 parts by weight or less, and 5 parts by weight or more and 500 parts by weight or less, based on 100 parts by weight of the content of the melamine resin. And more preferably 10 parts by weight or more and 100 parts by weight or less. If the thermosetting resin (D) is in the above range, the printing durability can be improved.

  The heat-sensitive layer (A) of the lithographic printing plate used in the present invention can contain various additives, if necessary. Specific examples include silicone surfactants and fluorosurfactants in order to improve coating properties, and silane coupling agents and titanium coupling agents in order to enhance the adhesion to the ink repelling layer. Not limited to these. The content of these additives varies depending on the purpose of use, but generally, it is preferably 0.1% by weight or more and 30% by weight or less in the heat-sensitive layer (A).

  The average film thickness of the heat sensitive layer (A) is preferably 0.1 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. On the other hand, 10 micrometers or less are preferable, 8 micrometers or less are more preferable, and 3 micrometers or less are especially preferable. If the average film thickness of the heat sensitive layer (A) is in the above range, good image reproducibility can be obtained. The average film thickness of the heat sensitive layer (A) can be determined by TEM observation. More specifically, a sample is prepared from a lithographic printing plate by an ultrathin slice method, and TEM observation is performed under the conditions of an acceleration voltage of 100 kV and a direct magnification of 2000 times. In the TEM photograph of the vertical cross section, the film thickness is measured at 10 locations randomly selected from the heat sensitive layer of the smooth portion without the film thickness reduction region, and the average film thickness is calculated by calculating its number average value. It can be asked.

  The heat-sensitive layer (A) can be prepared by applying and drying a solution or dispersion containing various components such as the light-to-heat conversion substance, the organic complex compound and the resin described above on a substrate. Drying may be performed at normal temperature or may be heated.

<Ink Repellent Layer (B)>
The lithographic printing plate used in the present invention has an ink repellent layer (B). The ink repellent layer (B) is preferably hydrophobic in order to repel water-soluble ink. The hydrophobicity said here means that a contact angle with water is 60 degrees or more. The ink repellent layer (B) contains (a) a hydrosilyl group-containing compound and (b) a silicone rubber derived from an addition reaction of a vinyl group-containing polysiloxane, and as a crosslinking point by the addition reaction, A siloxane unit represented by II) is newly formed.
_{-Si (CH 3) 2 -CH 2} -CH 2 -Si ** (CH 3) 2 -O- (II)
Since the base component of silicone rubber is a dimethylsiloxane unit represented by the following general formula (I), the crosslink density of the ink repellent layer (B) can be estimated by the molar ratio of both siloxane units.
^{_{-Si * (CH 3) 2 -O-}} (I)
The molar ratio can be calculated by solid ²⁹ Si-NMR analysis. As a specific measuring device, AVANCE400 (made by Bruker) is mentioned, for example. The calculation method is as follows: silicone rubber is removed from the lithographic printing plate and measured nucleus: ²⁹ Si, spectrum width: 40 kHz, pulse width: 4.2 μsec, pulse repetition time: ACQTM 0.02049 sec, PD 140 sec, by DD / MAS method Point: 8192, standard substance: Solid state ²⁹ Si-NMR measurement is conducted under the conditions of hexamethylcyclotrisiloxane (external standard: -9.66 ppm), temperature: 22 ° C., sample rotation number: 4 kHz. The peak of chemical shift -22 ppm of the obtained ²⁹ Si DD / MAS NMR spectrum belongs to the dimethylsiloxane unit which is the base component of silicone rubber: General formula (I), and the peak of around 7-8 ppm is a crosslinking point Siloxane unit which is: belonging to the general formula (II). The ^{Si **} peak intensity of formula (II), by dividing the Si ^* peak intensity of the general formula (I), can be calculated the molar ratio.

  The above peak intensity ratio is preferably 0.0005 or more, more preferably 0.0010 or more, and still more preferably 0.0015 or more from the viewpoint of developability and printing durability. It is preferably 0.0090 or less, more preferably 0.0050 or less, and still more preferably 0.0023 or less, from the viewpoint of suppressing brittle fracture during printing and obtaining printing durability.

  Examples of the (a) hydrosilyl group-containing compound include organohydrogenpolysiloxanes and organic polymers having diorganohydrogensilyl groups, with preference given to organohydrogenpolysiloxanes. Two or more of these may be contained.

  The organohydrogenpolysiloxane can have a linear, cyclic, branched or network molecular structure. Specifically, polymethyl hydrogen siloxanes in which both ends of the molecular chain are blocked with trimethylsiloxy groups, dimethylsiloxane / methyl hydrogen siloxane copolymers in which both ends of molecular chains are blocked with trimethylsiloxy groups, both chain ends Is a dimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer; both molecular chain ends are dimethylpolysiloxane blocked by dimethylhydrogensiloxy group; and both molecular chain ends are dimethylhydrogensiloxy Group-blocked dimethylsiloxane / methylphenylsiloxane copolymers, dimethylhydrogensiloxy-terminated methylphenylpolysiloxanes having molecular chains, and the like can be mentioned.

Further, as organohydrogenpolysiloxane, a siloxane structural unit represented by the formula: R ₃ SiO _1/2 and a siloxane structural unit represented by the formula: R ₂ HSiO _1/2 and a siloxane structure represented by the formula: SiO _4/2 An organopolysiloxane copolymer comprising units, an organopolysiloxane copolymer comprising a siloxane structural unit represented by the formula R ₂ HSiO _1/2 and a siloxane structural unit represented by the formula SiO _4/2 , the formula: An organopolysiloxane copolymer comprising a siloxane structural unit represented by RHSiO _2/2 , a siloxane structural unit represented by the formula: RSiO _3/2 , and a siloxane structural unit represented by the formula: HSiO _3/2 may, for example, be mentioned. Two or more of these organopolysiloxanes may be used. In the above formulae, each R is independently a monovalent hydrocarbon group other than an alkenyl group and may be substituted. For example, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; aryls such as phenyl, tolyl, xylyl and naphthyl; and benzyl and phenethyl Aralkyl groups include halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group and the like.

  Examples of the organic polymer having a diorganohydrogensilyl group include the following. Dimethylhydrogensilyl group-containing (meth) acrylic monomers such as dimethylhydrogensilyl (meth) acrylate and dimethylhydrogensilylpropyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate ( ) An oligomer obtained by copolymerizing a monomer such as butyl acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, styrene, α-methylstyrene, maleic acid, vinyl acetate, allyl acetate and the like.

  (B) The vinyl group-containing polysiloxane preferably has a structure represented by the following general formula (III), and has a vinyl group at the end of the main chain or in the main chain. Among them, those having a vinyl group at the main chain terminal are more preferable. Moreover, you may contain 2 or more types of structures of different General formula (III) in the molecule | numerator of (b) vinyl group containing polysiloxane.

_{^{- (SiR 1 R 2 -O-)}} n - (III)
In the general formula (III), n represents an integer of 2 or more. Each of R ¹ and R ² independently represents a saturated or unsaturated hydrocarbon group having 1 to 50 carbon atoms. The hydrocarbon group may be linear, branched or cyclic, and may contain an aromatic ring. Plural R ¹ 's in the polysiloxane of the general formula (III) may be the same or different. In addition, a plurality of R ^{2 s} present in the polysiloxane of the general formula (III) may be the same as or different from each other.

In the above general formula (III), it is preferable that R ¹ and R ² be methyl groups at 50% or more of the whole in terms of ink repellency of the lithographic printing plate. The weight average molecular weight of the (b) vinyl group-containing polysiloxane is preferably 30,000 or more and 100,000 or less from the viewpoints of image reproducibility, ink repellency of a lithographic printing plate, and scratch resistance.

  The ink repellent layer (B) in the lithographic printing plate used in the present invention can contain a curing catalyst to control the addition reaction of (a) a hydrosilyl group-containing compound and (b) a vinyl group-containing polysiloxane. . The curing catalyst can be selected from known ones, but platinum-based compounds are preferably used. Specific examples include platinum alone, platinum chloride, chloroplatinic acid, olefin-coordinated platinum, alcohol-modified complexes of platinum, and methylvinylpolysiloxane complexes of platinum. Two or more of these may be contained. From the viewpoint of the curability of the ink repellent layer (B), the content of the curing catalyst is preferably 0.001% by weight or more, more preferably 0.01% by weight or more in the ink repellent layer (B). In addition, from the viewpoint of the stability of the silicone rubber contained in the ink repellent layer (B) and the stability of the ink repellent layer composition solution, 20% by weight or less in the ink repellent layer (B) is preferable, and 15% by weight or less is more preferable.

  The ink repellent layer (B) is a hydroxyl group-containing organopolysiloxane, a hydrolyzable functional group-containing silane, a hydrolyzable functional group-containing siloxane, a filler such as silica, or the like to control the strength of the silicone rubber in the layer. In order to control adhesion with the layer (A), known silane coupling agents such as alkoxysilanes, acetoxysilanes, ketoximinosilanes and the like can also be contained.

  The hydroxyl group-containing organopolysiloxane has a structure represented by the general formula (III) and has a hydroxyl group at the main chain terminal or in the main chain. Among them, those having a hydroxyl group at the main chain terminal are preferable. Two or more of these may be used.

  The ink repellent layer (B) can also contain a crosslinking agent represented by the following general formula (IV). Among them, silicon compounds such as deacetic acid type, deoxime type, dealcoholization type, deacetone type, deamidation type, dehydroxylamine type and the like can be mentioned.

(R ³ ) _4-m SiX _m (IV)
In the general formula (IV), m represents an integer of 2 to 4, and each R ³ independently represents a substituted or unsubstituted alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, or a combination thereof Indicates a group. Each X independently represents a hydrolyzable group. As the hydrolyzable group, acyloxy group such as acetoxy group, ketoxime group such as methyl ethyl ketoxime group, alkoxy group such as methoxy group, ethoxy group, propoxy group and butoxy group, alkenyloxy group such as isopropenoxy group, acetylethylamino group And an aminoalkyl group such as an dimethylamino group. In the above formula, the number m of hydrolyzable groups is preferably 3 or 4. Specifically, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, allyltriacetoxysilane, phenyltriacetoxysilane, acetoxysilanes such as tetraacetoxysilane, vinyl methyl bis (methyl ethyl ketoximino) silane, methyl tris (Methylethyl ketoximino) silane, ethyltris (methylethyl ketoximino) silane, vinyltris (methylethyl ketoximino) silane, allyltris (methylethyl ketoximino) silane, phenyltris (methylethyl ketoximino) silane, tetrakis (methylethyl ketoximino) silane, etc. Siminosilanes, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , Alkoxysilanes such as tetraethoxysilane, tetrapropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, vinyltriisopropoxysilane, vinyltrisisopropenoxysilane, diisopropenoxydimethylsilane, Examples thereof include alkenyloxysilanes such as triisopropenoxymethylsilane, tetraaryloxysilane, and the like.

  Among these, acetoxysilanes and ketoximinosilanes are preferably used from the viewpoint of the curing speed of the ink repellent layer (B), the handleability and the like. Two or more of these may be contained.

  The crosslinking agent may be mixed with the hydroxyl group-containing organopolysiloxane to react with the crosslinking agent and the hydroxyl group to form an organosiloxane in which the crosslinking agent is bonded instead of the hydroxyl group.

  From the viewpoint of the stability of the ink repellent layer (B) and the ink repellent layer composition solution, the addition amount of the crosslinking agent is preferably 0.5% by weight or more, more preferably 1% by weight or more in the ink repellent layer (B). . In addition, from the viewpoint of the strength of the ink repellent layer (B) and the scratch resistance in a lithographic printing plate, 20% by weight or less in the ink repellent layer (B) is preferable, and 15% by weight or less is more preferable.

  In the ink repellent layer (B) of the lithographic printing plate used in the present invention, the ink is used to improve the ink repellent property or to reduce the plate surface elastic modulus to suppress the brittle fracture of the ink repellent layer (B). It can contain a repulsive liquid. The ink repellent liquid preferably has a boiling point of 150 ° C. or higher at 1 atm. When the printing plate is pressurized at the time of printing, the ink repellent liquid is exposed on the surface of the ink repellent layer (B), and the ink repellent property is improved by assisting the peeling of the ink. When the boiling point is 150 ° C. or higher, the lithographic printing plate precursor is less volatilized during production, and the ink repellent effect obtained by the addition of the ink repellent liquid is not lost. The boiling point as referred to herein is defined as a temperature at which the amount of weight loss after standing for 1 hour in an environment of 1 atm becomes 0.5% by weight or more. In other words, the ink repellent liquid has a weight loss of less than 0.5% by weight after standing at 150 ° C. and 1 atm for 1 hour. If so, the addition of the ink repellent liquid is less likely to lose the ink repellent effect.

  The surface tension of the ink repellent liquid at 25 ° C. is preferably 15 mN / m or more and 30 mN / m or less. When the surface tension is 15 mN / m or more, the affinity to other ink repellent layer compositions is higher, and the stability of the ink repellent layer composition solution is improved. When the surface tension is 30 mN / m or less, the ink is easily peeled off, and the ink repulsion can be further improved.

  By adding the ink repellent liquid to the ink repellent layer (B), the cross-linking can be partially inhibited and the plate surface elastic modulus can be reduced. The content of the ink repellent liquid in the ink repellent layer (B) is preferably 4% by weight or more, more preferably 4.5% by weight or more, from the viewpoint of reducing the plate surface elastic modulus and suppressing printing defects due to brittle fracture. preferable. Moreover, in the ink repellent layer (B), the content of the ink repellent liquid is preferably 40% by weight or less, more preferably 14% by weight or less, and still more preferably 10% by weight or less in order to maintain the plate surface elastic modulus. .

  The ink repellent liquid is preferably a silicone compound, and more preferably silicone oil. The silicone oil referred to in the present invention refers to a polysiloxane component which is not involved in the crosslinking of the ink repellent layer. Thus, dimethylsilicone oils such as terminal dimethylpolydimethylsiloxane, cyclic polydimethylsiloxane, terminal dimethyl-polydimethyl-polymethylphenylsiloxane copolymer, terminal dimethyl-polydimethyl-polydiphenylsiloxane copolymer, also alkyl modified silicone oils, 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 , Carbanana-modified silicone oil, higher fatty acid-modified silicone oil, etc. Modified silicone oils obtained by introducing various organic groups to a part of the group.

  The molecular weight of these silicone oils is preferably one having a weight average molecular weight Mw of 1,000 to 100,000.

  The average film thickness of the ink repellent layer (B) is preferably 0.5 μm or more, more preferably 1.5 μm or more, and particularly preferably 2.0 μm or more. On the other hand, 10.0 micrometers or less are preferable, 5.0 micrometers or less are more preferable, and 3.0 micrometers or less are especially preferable. If the average film thickness of the ink repellent layer (B) is in the above range, good ink repulsion can be obtained. The average film thickness of the ink repellent layer (B) can be determined by the same operation as the measurement of the average film thickness of the heat sensitive layer (A).

  The lithographic printing plate used in the present invention has a heat sensitive layer (A) and an ink repellent layer (B) on or above the substrate. Although any of the heat sensitive layer (A) and the ink repellent layer (B) may be present near the substrate, it is preferable that the substrate, the heat sensitive layer (A) and the ink repellent layer (B) be disposed in this order. The substrate of the lithographic printing plate is not particularly limited as long as it has a plate shape with good dimensional stability. For example, paper, paper (eg, polyethylene, polypropylene, polystyrene etc.) laminated, metal plate (eg, aluminum, zinc, copper etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) , Cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal and the like), paper or plastic film laminated or vapor-deposited with the above-mentioned metals, and the like. Among them, an aluminum plate having good dimensional stability and relatively inexpensive is preferably used. The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign element, or a laminate of plastic on a thin film of aluminum or an aluminum alloy. The different elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of foreign elements in the alloy is preferably 10% by weight or less. Although a pure aluminum plate is preferable for the substrate, a completely pure aluminum may be slightly contained because it is difficult to manufacture in terms of refining technology. The composition of the aluminum plate is not specified, and known materials can be appropriately used.

  The thickness of the substrate is preferably 0.1 mm or more and 0.6 mm or less, more preferably 0.15 mm or more and 0.4 mm or less, and still more preferably 0.2 mm or more and 0.3 mm or less.

  It is preferable to have a metal layer and / or a metal oxide layer between the substrate and the heat sensitive layer (A). By having the metal and / or the metal oxide layer, the adhesion between the substrate and the heat sensitive layer (A) can be improved. As a specific example, when using an aluminum plate for a board | substrate, it is preferable to have an aluminum oxide layer between a board | substrate and a thermosensitive layer (A). Such a metal oxide layer can be formed by various known methods, but from the viewpoint of in-plane uniformity, anodizing treatment is preferable. As the electrolyte used for the anodizing treatment, although various electrolytes for forming a porous oxide film can be used, generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined by the type of electrolyte. When using a paper, a plastic film or the like in which a plastic is laminated on a substrate, it is preferable to have a metal layer between the substrate and the heat sensitive layer (A). Aluminum is preferable for the metal layer from the viewpoint of adhesion to the aluminum oxide. Such an aluminum layer can be formed by various known methods, but metal deposition is preferred.

The conditions of the anodizing treatment vary depending on the electrolyte used and can not be uniquely specified. Generally, however, the solution has an electrolyte concentration of 1 to 80% by weight, a solution temperature of 5 to 70 ° C., and a current density of 5 to 60 A / It is preferable that it is dm < ² >, voltage 1-100V, and electrolysis time 10 second-5 minutes.

  The average film thickness of the anodized film formed on the substrate is preferably 0.1 μm or more and 3.0 μm or less, preferably 0.5 μm or more and 3.0 μm or less, as measured using the same method as the heat sensitive layer (A). More preferably, it is 5 μm or less. If the average film thickness of the film is within the above range, the adhesion between the substrate and the heat sensitive layer (A) can be improved.

  After the anodizing treatment, if necessary, the surface of the aluminum plate may be subjected to a hydrophilization treatment. The hydrophilization treatment is described in US Patent Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734, respectively. There is an alkali metal silicate method that In this method, the substrate is immersed or electrolytically treated with an aqueous solution such as sodium silicate. In addition, a method of treating with potassium fluoride zirconate described in Japanese Patent Publication No. 36-22063, U.S. Patent Nos. 3,276,868, 4,153,461 and 4,689, The method etc. which are processed with the polyvinyl phosphonic acid as described in each specification of 272 are mentioned.

  The surface roughness on the heat sensitive layer (A) side in the aluminum oxide layer is 0.01 μm or more and 1.0 μm or less in arithmetic mean roughness (Ra), and preferably 0.1 μm or more and 0.5 μm. The measuring method of arithmetic mean roughness (Ra) says the value measured based on JISB0601-1994.

  The lithographic printing plate used in the present invention may have a protective film and / or an interleaf on the surface of the ink repellent layer (B) for the purpose of protecting the ink repellent layer (B).

  As the protective film, a film having a thickness of 100 μm or less that transmits light of the exposure light source wavelength favorably is preferable. Representative examples of the material of the film include polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, cellophane and the like. Further, for the purpose of preventing the sensitization of the original plate by exposure, various light absorbing agents, photochromic substances, photobleachable substances as described in Japanese Patent No. 2938886 may be provided on the protective film.

The slip sheet is preferably one weighing 30 to 120 g / ^{m 2,} and more preferably from 30~90g / ^{m 2.} If the paper has a weight of 30 g / m ² or more, the mechanical strength is sufficient, and if it is 120 g / m ² or less, it is not only economically advantageous, but the laminate of the lithographic printing plate precursor and the paper becomes thin. Workability is advantageous. As an example of interleaf preferably used, for example, information recording base paper 40 g / m ² (made by Nagoya Pulp Co., Ltd.), metal intercalated paper 30 g / m ² (made by Nagoya Pulp Co., Ltd.), unbleached kraft paper 50 g / m ² (manufactured by Chuetsu Pulp Industry Co., Ltd.), NIP paper 52 g / m ² (manufactured by Chuetsu Pulp Industry Co., Ltd.), pure white roll paper 45 g / m ² (manufactured by Oji Paper Co., Ltd.), Kurupak 73 g / m ² (Oji Paper-making Co., Ltd. product etc. are mentioned, However, It is not limited to these.

<Method for producing lithographic printing plate precursor>
The method for producing an original plate of a lithographic printing plate used in the present invention includes the step of forming a heat-sensitive layer (A) in order on the substrate and the step of forming an ink repellent layer (B). Other steps may also be provided. For example, the heat-sensitive layer (A) can be formed by applying a heat-sensitive layer composition or a heat-sensitive layer composition solution on a substrate and optionally drying it. In addition, an ink repellent layer composition can be formed by applying an ink repellent layer composition or an ink repellent layer composition solution obtained by adding a solvent to the ink repellent layer composition, and drying it as necessary. .

  Examples of the apparatus used for coating include a slit die coater, direct gravure coater, offset gravure coater, reverse roll coater, natural roll coater, air knife coater, roll blade coater, barber roll blade coater, toe stream coater, rod coater, A dip coater, a curtain coater, a spin coater, etc. are mentioned. Slit die coaters, gravure coaters and roll coaters are particularly preferably used in view of coating film accuracy, productivity and cost.

  Thereafter, a protective film may be laminated, or a protective layer may be formed, as necessary.

<Plate-making of a lithographic printing plate>
Next, a method of producing a lithographic printing plate used in the present invention from the lithographic printing plate precursor produced by the above method will be described. The method for producing a lithographic printing plate is not particularly limited, but a step of irradiating a lithographic printing plate precursor having at least a heat-sensitive layer (A) and an ink repellent layer (B) with a laser beam (hereinafter referred to as exposure The method including the step is preferably used. As a laser light source used at an exposure process, what has a transmission wavelength area | region in the range of 300 nm-1500 nm is used preferably. For example, various lasers such as argon ion, krypton ion, helium-neon, helium-cadmium, ruby, glass, YAG, titanium sapphire, dye, nitrogen, metal vapor, excimer, free electron, semiconductor and the like are used. Among these, for the purpose of making the printing plate precursor of the present invention, a semiconductor laser having an emission wavelength region in the vicinity of the near infrared region is preferable, and a high-power semiconductor laser is particularly preferably used.

  The lithographic printing plate precursor according to the present invention can be used in the method for producing a printed material according to the present invention only by the exposure step, but the step of developing by exposing the exposed lithographic printing plate precursor by physical stimulation (hereinafter referred to as development It is more preferable to include a process). Since the ink repellent layer in the exposed area can be removed by the development step, the receptivity of the water-soluble ink to the heat sensitive layer can be improved. The physical stimulation in the developing step may be, for example, non-woven fabric, absorbent cotton, cloth, sponge or the like impregnated with the developer in the presence of water, an aqueous solution obtained by adding a surfactant to water, or a developer comprising an organic solvent. There are a method of wiping the printing plate, a method of pre-treating the printing plate with a developing solution and rubbing with a rotating brush while showering tap water etc., a method of spraying high pressure water or hot water or steam onto the printing plate. As a solution used in the development step, an aqueous solution obtained by adding a surfactant to water and water is preferably used from the advantage of easy processing.

  Prior to development, pretreatment may be performed by immersing the plate in the pretreatment liquid for a certain period of time. The pretreatment liquid may be, for example, water or water to which a polar solvent such as alcohol, ketone, ester or carboxylic acid is added, or a solvent consisting of at least one solvent such as aliphatic hydrocarbons or aromatic hydrocarbons. Solvents can be used as well as polar solvents. Moreover, surfactant can also be added to said developing solution composition. As the surfactant, those having a pH of 5 to 8 when made into an aqueous solution are preferable from the viewpoint of safety, cost in discarding, and the like. The content of the surfactant in the developer is preferably 0.1% by mass or more from the viewpoint of wettability to the printing plate precursor, and 10% by mass or less from the viewpoint of permeability to the printing plate precursor Is preferred. Such a developing solution is highly safe, and is preferable in terms of economy such as disposal cost. Furthermore, it is preferable to use a glycol compound or a glycol ether compound as a main component, and it is more preferable to coexist an amine compound.

  For example, water, alcohol or paraffin hydrocarbon can be used as the pretreatment liquid and the developer. Mixtures of propylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, propylene glycol derivatives such as alkylene oxide adducts to polypropylene glycol, and water can also be used. As a specific example of a developing solution, HP-7N, WH-3 (all are Toray Co., Ltd. product) etc. can be mentioned. As the pretreatment liquid, for example, as described in Japanese Patent No. 4839987, a specific example of the pretreatment liquid that can use a pretreatment liquid containing polyethylene ether diol and a diamine compound having two or more primary amino groups Examples include PP-1, PP-3, PP-F, PP-FII, PTS-1, PH-7N, CP-1, NP-1 and DP-1 (all from Toray Industries, Inc.), etc. It can be mentioned.

  In addition, in order to improve the visibility of the image area of the printing plate and the measurement accuracy of the halftone dots, dyes such as Crystal Violet, Victoria Pure Blue, Astrazone Red, etc. are added to these developers, and the ink receiving layer is developed simultaneously with development. The heat sensitive layer can also be dyed. Furthermore, it can also be dye | stained by the liquid which added said dye after image development.

  Some or all of the above development steps can also be performed automatically by an automatic processor. As an automatic developing machine, an apparatus having only a developing section, an apparatus having a pre-processing section, a developing section provided in this order, an apparatus having a pre-processing section, a developing section, and a post-processing section provided in this order, a pre-processing section, a developing section, An apparatus or the like provided with a post-processing unit and a water washing unit in this order can be used. Specific examples of such an automatic developing machine are disclosed in TWL-650 series, TWL-860 series, TWL-1160 series (both manufactured by Toray Industries, Inc.), and JP-A-5-6000. There may be mentioned an automatic developing machine in which a pedestal is indented on a curved surface in order to suppress the occurrence of scratches on the back surface of the plate. You may use combining these. In preparation for stacking and storing developed lithographic printing plates, an interleaf may be sandwiched between the plates for the purpose of plate surface protection.

<Production method of printed matter>
The method for producing a printed matter according to the present invention comprises the steps of: attaching a lithographic printing ink to the surface of a lithographic printing plate having a heat-sensitive layer (A) and an ink repellent layer (B) on a substrate; The step of transferring the ink to the printing material directly or through a blanket causes the lithographic printing ink to exhibit good ink repulsion and to be superior to the heat-sensitive layer (A) in the printing area. Because of the ink receptivity, good print quality can be obtained without scumming. The printing material as used herein refers to all printing media such as thin paper, cardboard, labels, synthetic paper, plastic film, plastic laminated paper, metal, metal-deposited plastic film, etc., and is not particularly limited. Plastic film, plastic laminated paper, metal, metal-deposited plastic film is preferably used.

  One embodiment of the method for producing a printed matter of the present invention will be described with reference to FIG. Although the example which uses blanket 4 below is explained, the present invention is not limited to this, and it does not use blanket 4 and the above-mentioned on the surface of planographic printing plate 2 attached to plate cylinder 3 directly from ink roller 1 After the lithographic printing ink is attached, the lithographic printing ink may be directly transferred to the printing medium 5. Moreover, although the example which supplies the ink for lithographic printing from the upper direction of the to-be-printed body 5 below is demonstrated, you may supply the ink for lithographic printing from the downward direction of the to-be-printed body 5. FIG.

  First, a lithographic printing plate is prepared. The lithographic printing plate 2 used in the present invention has an ink repellent layer (B) and a heat sensitive layer (A) on its surface in a desired pattern. Lithographic printing ink is supplied to the ink roller 1. The lithographic printing ink supplied to the ink roller 1 adheres to the surface of the heat-sensitive layer on the surface of the lithographic printing plate 2 mounted on the plate cylinder 3. The lithographic printing ink does not adhere to the ink repellent layer (B). The lithographic printing ink deposited on the surface of the heat sensitive layer of the lithographic printing plate 2 is transferred to the surface of the blanket 4 at the point of contact with the blanket 4. The lithographic printing ink adhered to the blanket 4 is transferred to the printing medium 5 at the point of contact with the printing medium 5 disposed on the support roller 6. Printed matter can be obtained by drying the printing medium 5 as required.

  The rotation speed of each roller in the above-mentioned manufacturing method is not particularly limited, and can be appropriately set according to the quality required for the printed matter, the delivery date, and the nature of the ink.

  In the production method of the present invention, in order to obtain good print quality, it is preferable to improve the ink repulsion in the non-image area of the lithographic printing plate. Specifically, the surface tension of the lithographic printing ink is in the range of 45 to 70 mN / m, preferably 50 to 65 mN / m, and more preferably 55 to 60 mN / m. When the surface tension of the ink is in the above range, excellent ink repulsion can be obtained in a lithographic printing plate. Furthermore, since the heat sensitive layer contains a melamine resin, the polarity (surface free energy) of the image area is as high as 40 to 70 mN / m. Since the compatibility is better as the surface free energy difference between the ink and the ink adheres to a smaller surface free area, good ink receptivity can be obtained by using the ink in the above range.

  The lithographic printing ink in the present invention may be any ink that can be used for lithographic printing. Specific examples thereof include oil-based inks, soybean oil inks, vegetable oil inks, and active energy ray-curable water-soluble inks for lithographic printing. From the viewpoint of environmental problems and preservation of the working environment, active energy ray-curable water-soluble inks for lithographic printing (hereinafter referred to as water-soluble inks) are preferably used.

  The water-soluble ink is preferably one showing solubility or dispersibility in water. In order to obtain the ink properties necessary for lithographic printing, it is preferable to include at least a pigment, a water-soluble resin, a diluent and a photopolymerization initiator.

  The pigment is not particularly limited, and inorganic or organic pigments generally used in lithographic printing inks can be used.

  Specific examples of the inorganic pigment include titanium dioxide, calcium carbonate, barium sulfate, bengala, organic bentonite, alumina white, iron oxide, carbon black and the like. Examples of the organic pigment include phthalocyanine pigments, soluble azo pigments, insoluble azo pigments, quinacridone pigments and isoindoline pigments.

  Examples of the organic pigment include phthalocyanine pigments, soluble azo pigments, insoluble azo pigments, lake pigments, quinacridone pigments, isoindoline pigments, slen pigments, metal complex pigments and the like, and specific examples thereof include phthalocyanine Blue, phthalocyanine green, azo red, monoazo red, monoazo yellow, disazo red, disazo yellow, quinacridone red, quinacridone magenta, isoindoline yellow, etc. may be mentioned. These pigments may be used alone or in combination of two or more.

  The content of the pigment is preferably 5% by weight or more, and more preferably 10% by weight or more, so as to obtain the printing paper surface density to be obtained, and the ink supply amount is not excessive. Also, it is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 25% by weight or less, at which the flowability of the ink necessary for lithographic printing can be obtained.

  The water soluble resin makes the water soluble ink a viscosity characteristic suitable for lithographic printing. It also interacts with the pigment in the ink to disperse the pigment. In addition, it forms a strong film on printed matter.

  Specific examples of such water-soluble resin include acrylic resin, maleic acid resin, polyester resin, polyurethane resin and the like, but it is not particularly limited as long as it is water-soluble or water-dispersible resin, and commercially available resins Can also be suitably used. From the viewpoint of pigment dispersibility and ink storage stability, acrylic resin and maleic resin are preferable.

  Acrylic resin refers to a resin obtained by addition polymerization of one or more monomers selected from acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester, and the above-mentioned monomer and one or more kinds of unsaturated It refers to a resin obtained by copolymerizing a group-containing compound. Examples of the monomer include (meth) acrylic acid alkyl ester monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate. Examples of the unsaturated group-containing compounds include maleic acid dialkyl esters such as dimethyl maleate, diethyl maleate and dibutyl maleate, styrene, α-methylstyrene, vinyl toluene and derivatives thereof. Specific examples include styrene-acrylic acid copolymer, styrene-methyl acrylate-acrylic acid copolymer, styrene-butyl acrylate-acrylic acid copolymer, styrene-methyl methacrylate-acrylic acid copolymer, styrene Butyl methacrylate-acrylic acid copolymer and the like.

  A maleic acid resin is a resin obtained by addition polymerization of one or more monomers selected from maleic anhydride, maleic anhydride which is partially modified with a hydroxyl group-containing compound and an amino group-containing compound, and It refers to a resin obtained by copolymerizing a body and one or more types of unsaturated group-containing monomers.

  Examples of maleic acid monomers include maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and the like. Examples of the unsaturated group-containing compounds include maleic acid dialkyl esters such as dimethyl maleate, diethyl maleate and dibutyl maleate, styrene, α-methylstyrene, vinyl toluene and derivatives thereof. Specific examples include styrene-maleic acid copolymer, styrene-methyl acrylate-maleic acid copolymer, styrene-butyl acrylate-maleic acid copolymer, styrene-methyl methacrylate-maleic acid copolymer, styrene -Butyl methacrylate-maleic acid copolymer can be mentioned.

  These water-soluble resins can be used alone or in combination of two or more.

  The content of the water-soluble resin in the water-soluble ink is preferably 5% by weight or more at which a viscosity suitable for lithographic printing can be obtained, more preferably 10% by weight or more, and still more preferably 15% by weight or more. Also, the ink is preferably 35% by weight or less, more preferably 30% by weight or less, and further preferably 25% by weight or less.

  Any diluent can be used as long as it dissolves the other components in the water-soluble ink. Furthermore, after printing, it may be polymerized and cured by hot air drying, natural drying, oxidative polymerization, or active energy ray irradiation. Examples of such a diluent include water, a water-soluble solvent, a water-soluble acrylic monomer, and the like. However, the water-soluble acrylic monomer is preferably used because it is less likely to corrode the heat-sensitive layer (A). Furthermore, since the water-soluble acrylic monomer is a monomer containing an ethylenically unsaturated group, it is polymerized and cured by irradiation with active energy rays, so that an ink cured film having good water resistance and strength can be obtained. preferable. In addition, a water-soluble acrylic monomer is preferable because it hardly corrodes while exhibiting good compatibility with the heat-sensitive layer (A).

  Specific examples of the water-soluble solvent include alcohols, amides, ketones, polyhydric alcohols, alkyl ethers of polyhydric alcohols, and the like.

  As the alcohols, methanol, ethanol, n-propanol, isopropanol, n-butanol and the like can be mentioned. Examples of the amides include dimethyl formaldehyde and dimethyl acetamide. Examples of ketones include acetone and methyl ethyl ketone. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and the like. Examples of alkyl ethers of polyhydric alcohols include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl and the like of polyhydric alcohols. Other examples include N-methyl-pyrrolidone and the like.

  In particular, polyhydric alcohols and alkyl ethers of polyhydric alcohols are preferable because they have a boiling point of 150 ° C. or higher and can prevent drying on a printing press and can improve the on-press stability. These water-soluble solvents can be used alone or in combination of two or more. It can also be used mixed with water.

  Any water-soluble acrylic monomer may be used as long as it has a solubility in water of 100 g at 25 ° C. of 1 g or more, and is compatible with a water-soluble resin, and any monomer having an ethylenically unsaturated group. Preferred examples thereof include ethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate and 1,3-butylene glycol di (meth) acrylate Ethylene oxide modified glycerin tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) Acrylate, although dipentaerythritol penta (meth) acrylate and the like, but is not limited thereto.

  These water-soluble acrylic monomers can be used alone or in combination of two or more.

  The content of the diluent contained in the water-soluble ink is preferably 10% by weight or more, more preferably 15% by weight or more, and still more preferably 20% by weight or more, in order to give the ink appropriate fluidity. Moreover, in order to obtain the viscosity of the ink required for lithographic printing, 90 weight% or less is preferable, 80 weight% or less is more preferable, and 70 weight% or less is more preferable.

  There are various types of photopolymerization initiators such as single molecule direct cleavage type, ion pair electron transfer type, hydrogen abstraction type, and bimolecular complex type, and they can be selected from them.

  As the photopolymerization initiator (e) used in the present invention, one capable of generating an active radical species is preferable. Specific examples thereof include benzophenone, methyl o-benzoylbenzoate and 4,4-bis (dimethylamine) benzophenone 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2- Phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Photoreducible dyes such as dildimethylketanol, benzyl methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butyl anthraquinone, benzoin peroxide and eosin peroxide, methylene blue, ascorbic acid, triethanolamine, etc. And combinations of reducing agents.

  A sensitizer may be included to assist the effect of the photopolymerization initiator. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-Bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) 2.) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone , 1,3-Carbonyl-bis (4-diethylamide) Benzal) acetone, 3,3-carbonyl-bis (7-diethylamino coumarin), N-phenyl-N-ethyl ethanolamine, N-phenyl ethanolamine, N-tolyl diethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like can be mentioned.

  In the present invention, one or more photopolymerization initiators and sensitizers can be used.

  The addition amount of the photopolymerization initiator in the ink of the present invention is preferably 0.1 to 20 parts by mass. By setting the addition amount of the photopolymerization initiator within this range, good sensitivity and curability can be obtained. Moreover, as for the addition amount, when adding a sensitizer, 0.1-20 mass parts is preferable with respect to active energy ray hardening-type printing ink. By making the addition amount of a sensitizer into this range, the effect of a photoinitiator can be assisted.

  Moreover, it is preferable to add a polymerization inhibitor to the water-soluble ink. Specific examples of the polymerization inhibitor include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, p-t-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p- Methylphenol, chloranil, pyrogallol and the like can be mentioned. When adding a polymerization inhibitor, the addition amount thereof is preferably 0.001 to 5 parts by mass with respect to the active energy ray-curable printing ink. The storage stability of the ink can be obtained by setting the addition amount of the polymerization inhibitor in this range.

  Furthermore, the water-soluble ink preferably contains one or more selected from hydrocarbons, fluorocarbons, alkyl acrylates and alkyl methacrylates. These components are hereinafter referred to as "ink repellent components".

  The ink repellent component has the effect of reducing the ink adhesion to the ink repellent layer (B) of the waterless lithographic printing plate. The reason for reducing the adhesion is presumed as follows. That is, since the ink repulsion imparting component does not have good compatibility with other components contained in the ink, it diffuses from the ink upon contact with the plate surface and covers the silicone rubber surface in a thin film. It is presumed that the thin film thus formed prevents the adhesion of the ink and prevents the smearing.

  As a specific example of an ink repulsion imparting component, polyolefin oil, naphthenic oil, paraffin oil etc. are mentioned as hydrocarbon.

  As a fluorocarbon, 1,1,1,2,2-pentafluoroethane, 1,1,1,2,2,3,3,4,4-nonafluorobutane, 1,1,1,2,2,2,1. 3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7 1,8,8-heptadecafluorooctane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,3,3,4,4-octafluoro-2-tri Fluoromethylbutane, 1,1,1,2,3,3,4,4,5,5,6,6-dodecafluoro-2-trifluoromethylhexane, 1,1,2,2-tetrafluoroethane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,2,2,3,3,4,4,5,5,6,6-do Perfluoro hexane, and the like.

  Examples of the alkyl acrylate include nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, isooctadecyl acrylate and the like.

  Examples of the alkyl methacrylate include nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate and the like.

  The content of the ink repulsion imparting component in the water-soluble ink is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and further preferably 0.5% by weight or more, from the viewpoint of improving the ground stain resistance. More preferable. Moreover, 20 weight% or less is preferable, 15 weight% or less is preferable, 10 weight% or less is more preferable so as not to impair the long-term stability of the ink.

  When an active energy ray-curable water-soluble ink for lithographic printing is used as the lithographic printing ink, the water-soluble ink remaining on the ink roller 1, the lithographic printing plate 2 and the blanket 4 after printing is water, or It can be easily removed by an aqueous solution containing water as a main component (hereinafter referred to as washing water). The washing water may be impregnated into non-woven fabric, cotton wool, cloth, sponge etc. and the water-soluble ink may be wiped off, or the washing water may be spray applied directly to the water-soluble ink and then wiped with non-woven fabric, cotton wool, cloth, sponge etc. It is good. The water-soluble ink can also be removed by pouring washing water from the ink roller 1 and flowing the washing water from the planographic printing plate 2 to the blanket 4.

  The washing water is preferable because the wettability to the surfaces of the ink roller 1, the lithographic printing plate 2, the blanket 4 and the like can be improved by containing the surfactant, and as a result, the removal rate of the water-soluble ink can be improved. Any surfactant may be used as the surfactant, but from the viewpoints of safety, cost at the time of disposal, etc., commercially available household detergents and the like are preferably used. The content of the surfactant in the washing water is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and 1.0% by weight in view of lowering the surface energy of the washing water. It is particularly preferable to be the above. Further, it is preferably at most 30% by weight, at which affinity with a water-soluble ink can be obtained, more preferably at most 20% by weight, particularly preferably at most 10% by weight. Such washing water is highly safe and is preferable from the economical point of disposal cost and the like. Further, it is preferable that the pH of the washing water is 4 to 11, since the washing water hardly penetrates into the ink roller 1, the lithographic printing plate 2 and the blanket 4 and the problem of the penetration of the water-soluble ink hardly occurs.

  The method for producing a printed matter according to the present invention comprises the steps of depositing a lithographic printing ink and transferring the deposited ink directly to a printing material via a blanket, followed by irradiating active energy rays. Any active energy ray necessary for curing the water-soluble acrylic monomer contained in the ink may be used as long as it has excitation energy necessary for the curing reaction, but for example, ultraviolet rays and electron beams are preferable. Used. In the case of curing by electron beam, an electron beam apparatus having an energy beam of 100 to 500 eV is preferably used. In the case of curing by ultraviolet light, ultraviolet light irradiation devices such as high pressure mercury lamps, xenon lamps, metal halide lamps, and LEDs having a peak wavelength of 250 to 400 nm are preferably used. For example, when using a metal halide lamp, it is preferable from the viewpoint of productivity to be cured at a conveying speed of 50 to 150 m / min by a conveyor by a lamp having an illuminance of 80 to 150 W / cm.

  Furthermore, a photopolymerization initiator, a sensitizer for assisting the effect of the photopolymerization initiator, a polymerization inhibitor and the like may be included in order to improve the sensitivity to an active energy ray and storage stability of the aqueous ink.

  Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by these examples. In the following examples and comparative examples, evaluation was performed as follows.

Determination of crosslink density of silicone rubber
The crosslinking density of the addition type silicone rubber was quantified by solid ²⁹ Si-NMR analysis. The ink repellent layer is scraped from the lithographic printing plate, and the measurement nucleus: ²⁹ Si, spectrum width: 40 kHz, pulse width: 4.2 μsec, pulse repetition time: ACQTM 0 by DD / MAS method using AVANCE 400 (manufactured by Bruker) .02049 sec, PD 140 sec, observation point: 8192, Reference substance: hexamethyl cyclotrisiloxane (external standard: -9.66 ppm), temperature 22 ° C., sample rotation speed: measured at 4 kHz. The peak in the vicinity of the chemical shift of 22 ppm of the obtained ²⁹ Si DD / MAS NMR spectrum is assigned to the dimethylcyclohexane unit represented by the general formula (I), which is the base component of silicone rubber, and the peak in the vicinity of 7-8 ppm is It belonged to the siloxane unit represented by General formula (II) which is a crosslinking point. The peak area ratio of (II) / (I) (molar ratio of (II) / (I)) assigned by the above was calculated and used as the crosslink density.

<Surface roughness (Ra)>
The surface roughness (arithmetic mean roughness (Ra)) was measured in accordance with JIS B0601-1994. A laser microscope (VK-X210 manufactured by Keyence Corporation) was used.

<Inking property of ink>
After printing 10000 sheets of black ink on high quality paper continuously, the black density on the solid image print is measured using a reflection densitometer (SpectroEye, manufactured by GretagMacbeth), and the change rate from the 10th print and the 10000th black print The ink receptivity was evaluated according to the following criteria. It was judged that the ink receptivity was better as the black density change rate after 10000 sheets of continuous printing was smaller.
A: Change rate less than 5% B: Change rate 5% or more and less than 10% C: Change rate 10% or more and less than 30% D: Change rate 30% or more.

<Soil start temperature>
In continuous printing, the temperature of the ink roller was controlled using a chiller to change the plate surface temperature of the lithographic printing plate. The plate surface temperature was measured with a non-contact thermometer, and background dirt in the non-image area was confirmed every 0.1 ° C., and the temperature at which background dirt began to occur was taken as the background dirt start temperature. The ground stain start temperature is preferably 24.0 ° C. or higher, and more preferably 26.0 ° C. or higher. A lithographic printing plate having a high plate surface temperature and no background staining was judged to be a plate having good ink repulsion against the used ink, ie, resistance to background staining.

<Printing durability>
After the background dirt start temperature was measured, continuous printing was continued while maintaining the temperature, the background dirt state of the printed matter was confirmed every 5000 sheets, and the number of sheets until the visual deterioration made it possible was taken as the number of printed sheets. Specifically, the printing durability is good for 20000 or more, more preferably 50000 or more, and even more preferably 80000 or more.

<Image reproducibility>
Exposure and development processes were carried out by providing 10 μm and 6.4 μm thin lines and a belt-like solid image of 20 mm long × 650 mm wide at the center of a planographic printing plate precursor of 550 mm long × 650 mm wide. The thin lines of the obtained lithographic printing plate were observed with a loupe 100 times, the reproduced distance was measured, and the ratio to the total length was taken as the image reproduction rate. The image reproduction rate is good if it is 75% or more, and it is better if it is 90% or more.

<Surface tension of ink>
The surface tension of the active energy ray-curable water-soluble ink for lithographic printing used in the present invention was measured by the droplet method of an automatic contact angle meter (Drop Master DM-501, manufactured by Kyowa Interface Science Co., Ltd.) The contact angle was calculated using the known Fowkes model. Specifically, the surface of a glass substrate (5 cm glass plate (thickness 1 mm T × length 50 mm × width 50 mm), manufactured by Ishida Rika Co., Ltd.) is washed to remove impurities and then processed on glass. The ink was applied smooth and allowed to stand in the dark for 30 minutes. Then, using a syringe, droplets of pure water and ethylene glycol having known surface tension values were formed and deposited on the ink. The contact angle of pure water and ethylene glycol, which had been applied for 30 seconds after the deposition, was measured to calculate the surface tension of the ink.

<Method of exposing and developing a lithographic printing plate>
With respect to the lithographic printing plate precursor prepared by the method described in the examples, irradiation energy: 125 mJ / cm ² (drum rotation number: using a plate-type exposure apparatus “PlateRite” 8800E (Dainippon Screen Mfg. Co., Ltd.) for CTP. Exposure was performed under the conditions of 240 rpm. A thin line of 10 μm and 6.4 μm and a belt-like solid image of 20 mm long × 650 mm wide were provided at the center of a 550 mm long × 650 mm wide lithographic printing plate precursor. Using DP-1 (Toray Industries, Inc.) as a pretreatment solution and tap water as a developer, expose the exposed original plate through an automatic developing machine TWL-1160F (Toray Industries, Inc.) at a speed of 80 cm / min. The plate was exposed and developed.

<LED-UV printing>
A printing machine was prepared in which an irradiation device for emitting light having a wavelength of 300 to 450 nm, which incorporates a speed variable type conveyor, was connected to the paper discharge unit of the printing machine "Olivar 266EPZ" (manufactured by Sakurai Graphic Systems Co., Ltd.). The lithographic printing plate produced above was mounted on the printing press, and an LED-UV printing test was conducted at a speed of 5000 sheets / hour (sph) using the UV ink of each example. The ink was supplied to the lithographic printing plate by an ink roller, the lithographic printing plate was brought into contact with the blanket, and the ink was transferred from the lithographic printing plate to the blanket. Subsequently, the printing was performed by an offset printing method in which the ink on the blanket was transferred to a thin paper coated paper as a printing medium. The supply amount of the ink was controlled so that the reflection density of the solid printed portion was 1.7 (black), and the transferred coated paper was irradiated with active energy rays of a wavelength of 300 to 450 nm to obtain a printed matter.

Example 1
A lithographic printing plate precursor was produced by the following method.
After performing the following anodizing treatment on a degreased aluminum substrate (manufactured by Mitsubishi Aluminum Corporation) having a thickness of 0.24 mm, the heat-sensitive layer composition solution is applied and dried at 140 ° C. for 90 seconds. A 0 μm heat sensitive layer was provided. The heat sensitive layer composition solution was obtained by stirring and mixing the following components at room temperature.

<Anodizing treatment conditions>
(A) Electrolyte: 1% by weight nitric acid aqueous solution (containing 0.5% by weight of aluminum ion)
(B) Liquid temperature: 50 ° C
(C) AC voltage: 60 Hz
(D) AC power supply waveform: TP 0.8 msec, duty ratio 1: 1
(E) Electrode: carbon electrode, auxiliary anode: ferrite (f) Current density: 30 A / dm ² (For the auxiliary anode, 5% of the current flowing from the power supply is divided)
The amount of electricity in nitric acid electrolysis was 175 C / dm ² when the aluminum plate was an anode.

  The average film thickness of the anodized film of the obtained substrate was 0.8 μm as a result of measurement by the above method. The surface roughness was Ra = 0.30.

<Thermal layer composition solution>
(A) Infrared absorbing dye: “IR-813 p-toluenesulfonate” (manufactured by Tokyo Chemical Industry Co., Ltd.): 13.8 parts by weight (b) Dye: “LIONDGEW BLUE 6510” (manufactured by Toyo Color Co., Ltd.) ): 12.9 parts by weight (c) Melamine resin: “MW-30M” (manufactured by Nippon Carbide Co., Ltd.): 51.7 parts by weight (d) Curing catalyst: “p-toluenesulfonic acid” (Tokyo Chemical Industry Co., Ltd. Co., Ltd. product: 21.6 parts by weight (e) Tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.): 900 parts by weight In addition, the compounding quantity of each component of the heat-sensitive layer composition solution is the component (a) to (d) In parts by weight with respect to a total of 100 parts by weight of the compounding amount of The weight average molecular weight of the melamine resin after forming the heat sensitive layer was 50,000.

Next, the following ink repellent layer composition solution prepared immediately before application is coated on the heat sensitive layer, heated at 140 ° C. for 80 seconds, and provided with an ink repellent layer having an average film thickness of 2.0 μm. I got the original version. The ink repellent layer of the original plate was removed, and the peak intensity ratio of (II) Si ^{** to} the peak intensity / (I) Si ^* was calculated to be 0.0020. The ink repellent layer composition solution was obtained by stirring and mixing the following components at room temperature.

Ink Repellent Layer Composition Solution
(A) α, ω-divinylpolydimethylsiloxane: DMS-V35 (weight average molecular weight 49, 500, manufactured by GELEST Inc.): 86.7 parts by mass (b) methyl hydrogen siloxane: SH1107 (Toray Dow Corning (stock) )) 5.76 parts by mass (c) Vinyltris (methylethyl ketoximino) silane (Tokyo Chemical Industry Co., Ltd.): 1.32 parts by mass (d) Platinum catalyst SRX 212 (manufactured by Toray Dow Corning): 6 .22 parts by mass (e) "Isopar" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 900 parts by mass Furthermore, the blending amounts of the components (a) to (d) of the ink repellent layer composition solution are the respective components Parts by weight with respect to a total of 100 parts by weight.

  Next, the following active energy ray-curable water-soluble ink for lithographic printing was prepared, and the lithographic printing plate was placed in a printing machine on which the lithographic printing plate was set, and printing was performed.

<Active energy ray-curable water-soluble ink for lithographic printing>
20 parts by weight of carbon black (color index, PBK7) as a pigment, 18 parts by weight of a styrene / acrylic copolymer resin "YS-1274" (weight average molecular weight: 19,000, manufactured by Starlight PMC Co., Ltd.), reactive diluent 25 parts by weight of "I Miramer" (registered trademark) M340 (manufactured by MIWON Co., Ltd.), 25 parts by weight of reactive diluent II "Miramer" (registered trademark) M4004 (manufactured by MIWON Co., Ltd.), Photopolymerization initiator "IRGACURE""(Registered trademark) 907 (BASF Co., Ltd.) 5 parts by weight, sensitizer 4,4'-bis (diethylamino) benzophenone (Tokyo Chemical Industry Co., Ltd.) 6 parts by weight, polymerization inhibitor p-methoxyphenol 1 part by weight (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed, and a three-roll mill "EXAKT" (registered trademark) M-80S (manufactured by EXAKT) was manufactured. The ink was obtained by kneading the roller gap scale of the apparatus three times at a roller speed ratio of 3.3: 1.8: 1. As a result of measuring the surface tension of the ink, it was 57 mN / m.

  As a result of lithographic printing using the obtained ink, the ink receptivity was evaluated at a color density change rate of 2.0% A, background dirt start temperature 32.6 ° C., printing durability 100000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100%.

Examples 2 to 5 and Comparative Examples 1 and 2
The same operation as in Example 1 was performed except that the composition of the ink repellent layer B was changed as described in Table 1. The obtained evaluation results are shown in Tables 1 and 4.

The peak intensity ratio represented by the peak intensity of (II) Si ^** / peak intensity of (I) Si ^* of the ink repellent layer (B) of the printing plate precursor obtained in Example 2 is 0.0013 and the average film The thickness was 2.0 μm. The printing evaluation results are as follows: Evaluation A with a color density change rate of 2.6%, background dirt start temperature 27.8 ° C., printing durability 85000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 95% there were.

The peak intensity ratio represented by the peak intensity of (II) Si ^** / the peak intensity of (I) Si ^* of the ink repellent layer (B) of the printing plate precursor obtained in Example 3 is 0.0006, and the average film The thickness was 2.0 μm. The printing evaluation results are as follows: Evaluation A with color density change rate 4.5%, background dirt start temperature 24.3 ° C., printing durability 70000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 95% there were.

The peak intensity ratio represented by the peak intensity of (II) Si ^** / the peak intensity of (I) Si ^* of the ink repellent layer (B) of the printing plate precursor obtained in Example 4 is 0.0030, average film The thickness was 2.0 μm. The printing evaluation results are as follows: Evaluation A with color density change rate 1.9%, background dirt start temperature 28.7 ° C., printing durability 85000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 90% there were.

The peak intensity ratio represented by the peak intensity of (II) Si ^** / the peak intensity of (I) Si ^* of the ink repellent layer (B) of the printing plate precursor obtained in Example 5 is 0.0085, the average film The thickness was 2.0 μm. The printing evaluation results are as follows: Evaluation A, color contamination change rate 3.3%, background dirt start temperature 26.1 ° C., printing durability 50000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 90% there were.

The peak intensity ratio represented by the peak intensity of (II) Si ^** / the peak intensity of (I) Si ^* of the ink repellent layer (B) of the printing plate precursor obtained in Comparative Example 1 is 0.0003, the average film The thickness was 2.0 μm. The printing evaluation results are as follows: Evaluation D with color density change rate 50.1%, background dirt start temperature 21.5 ° C., printing durability 5000 sheets, image reproducibility 10 μm thin line: 30%, 6.4 μm thin line: 5% there were.

The peak intensity ratio represented by the peak intensity of (II) Si ^** / the peak intensity of (I) Si ^* of the ink repellent layer (B) of the printing plate precursor obtained in Comparative Example 2 is 0.0110, and the average film The thickness was 2.0 μm. The printing evaluation results are evaluated at a color density change rate of 37.7% D, background dirt start temperature 34.0 ° C., printing durability 5000 sheets, image reproducibility 10 μm thin line: 20%, 6.4 μm thin line: 0% there were.

Examples 6 to 11
The same operation as in Example 1 was performed except that among the composition of the active energy ray-curable water-soluble ink for lithographic printing, the addition amount of the resin, the reaction diluent and the reaction diluent was changed. The obtained evaluation results are shown in Table 1.

Example 6
The same operation as in Example 1 was performed except that 35 parts by weight of the reaction diluent I and 15 parts by weight of the reaction diluent II were used. The surface tension of the obtained active energy ray-curable water-soluble ink for lithographic printing was 53 mN / m. The printing evaluation results are as follows: Evaluation A with color density change rate 3.8%, background dirt start temperature 29.7 ° C., printing durability 95000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 7
The same operation as in Example 1 was performed except that 45 parts by weight of the reaction diluent I and 5 parts by weight of the reaction diluent II were changed. The surface tension of the obtained active energy ray-curable water-soluble ink for lithographic printing was 47 mN / m. The printing evaluation results are as follows: Evaluation A with a color density change rate of 4.7%, background dirt start temperature 25.5 ° C., printing durability 95000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 8
The same operation as in Example 1 was performed except that the resin was changed to acrylic resin "Alphon" (registered trademark) UC-3000 (Toa Gosei Co., Ltd.). The surface tension of the obtained active energy ray-curable water-soluble ink for lithographic printing was 62 mN / m. The printing evaluation results are as follows: Evaluation B: Color density change rate: 7.3%, background dirt start temperature: 30.3 ° C., printing durability: 95,000 sheets, image reproducibility: 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 9
The same operation as in Example 1 was performed except that the resin was changed to acrylic resin "Alfon" (registered trademark) UG-4035 (Toa Gosei Co., Ltd.). The surface tension of the obtained active energy ray-curable water-soluble ink for lithographic printing was 68 mN / m. The printing evaluation results are as follows: Evaluation B with color density change rate 8.5%, background dirt start temperature 30.5 ° C., printing durability 95000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 10
The same operation as in Example 1 was performed except that 50 parts by weight of the reaction diluent I was changed to the case where the reaction diluent II was not added. The surface tension of the obtained active energy ray-curable water-soluble ink for lithographic printing was 40 mN / m. The printing evaluation results were evaluated at a color density change rate of 37.8% D, background dirt start temperature 22.3 ° C., printing durability 95000 sheets, image reproducibility 10 μm thin line: 50%, 6.4 μm thin line: 20% there were.

Example 11
The same operation as in Example 1 was carried out except that the reaction diluent I was changed to 50 parts by weight without adding the reaction diluent I to the acrylic resin "Alphon" (registered trademark) UF-5022 (Toagosei Co., Ltd.) went. The surface tension of the obtained active energy ray-curable water-soluble ink for lithographic printing was 75 mN / m. The printing evaluation results were evaluated at a color density change rate of 42.2% D, background stain start temperature 35.1 ° C., printing durability 95000 sheets, image reproducibility 10 μm thin line: 70%, 6.4 μm thin line: 20% there were.

Examples 12 to 14
The same operation as in Example 1 was performed except that the conditions for the anodizing treatment of the lithographic printing plate precursor were changed. The evaluation results obtained are shown in Table 2.

Example 12
The same operation as in Example 1 was performed except that the anodizing treatment to the aluminum substrate was not performed. The print evaluation results are as follows: Color change rate 5.1%, B: background dirt start temperature 32.6 ° C., printing durability 30000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 13
Among the conditions of the anodizing treatment, the same operation as in Example 1 was performed except that the current density was changed to 10 A / dm ² . The printing evaluation results are as follows: Evaluation A with a color density change rate of 4.9%, background dirt start temperature 32.6 ° C., printing durability 70000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 95% there were.

Example 14
Among the conditions of the anodizing treatment, the same operation as in Example 1 was performed except that the aqueous solution was changed to 10 wt% nitric acid and the current density was 60 A / dm ² . The printing evaluation results are as follows: Evaluation A with a color density change rate of 1.7%, background dirt start temperature 32.6 ° C., printing durability 85000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 90% there were.

Example 15
Among the conditions of the anodizing treatment, the same operation as in Example 1 was performed except that a 40 wt% nitric acid aqueous solution, an AC voltage of 60 V, and a current density of 60 A / dm ² were changed. The printing evaluation results were evaluated at a color density change rate of 1.0% A, background dirt start temperature 32.6 ° C., printing durability 50000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 90% there were.

Examples 16 to 18
The same operation as in Example 1 was performed except that the type and amount of addition of the melamine resin added to the heat sensitive layer composition liquid, the curing catalyst, and the drying conditions were changed. The evaluation results obtained are shown in Table 2.

Example 16
The operation was performed in the same manner as in Example 1 except that the drying temperature was changed to 120 ° C. and the drying time was changed to 60 seconds. The print evaluation results are as follows: Evaluation A with a color density change rate of 4.8%, background dirt start temperature 32.6 ° C., printing durability 30000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 95% there were.

Example 17
The operation was performed in the same manner as in Example 1 except that the melamine resin was changed to 68.3 parts by weight of "MX-45" (manufactured by Nippon Carbide Co., Ltd.) and the amount of curing catalyst was changed to 5.0 parts by weight. The printing evaluation results are as follows: Evaluation A with color density change rate 1.5%, background dirt start temperature 32.6 ° C., printing durability 50000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 18
An operation was performed in the same manner as in Example 1 except that the melamine resin was changed to "MX-45" (manufactured by Nippon Carbide Co., Ltd.) and the drying time was changed to 180 seconds. The printing evaluation results are as follows: Evaluation A: Color density change rate: 1.3%, background dirt start temperature: 32.6 ° C., printing durability: 45,000 sheets, image reproducibility: 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Examples 19 to 22
A lithographic printing plate and an active energy ray-curable water-soluble ink for lithographic printing were obtained by the same operation as in Example 1 except that the film thickness of the heat-sensitive layer was changed. The obtained evaluation results are shown in Table 3.

Example 19
The operation was performed in the same manner as in Example 1 except that tetrahydrofuran in the heat sensitive layer composition solution was changed to 4500 parts by weight. The printing evaluation results are as follows: Evaluation A, color contamination change rate 2.0%, background dirt start temperature 32.6 ° C., printing durability 90000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 20
The procedure of Example 1 was repeated except that the tetrahydrofuran content of the heat sensitive layer composition solution was changed to 1440 parts by weight. The printing evaluation results are as follows: Evaluation A, color stain change rate 2.0%, background dirt start temperature 32.6 ° C., printing durability 85000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 21
The procedure of Example 1 was repeated except that the amount of tetrahydrofuran in the heat sensitive layer composition solution was changed to 300 parts by weight. The printing evaluation results are as follows: Evaluation A, color contamination change rate 2.0%, background dirt start temperature 32.6 ° C., printing durability 80000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 90% there were.

Example 22
The procedure of Example 1 was repeated except that the amount of tetrahydrofuran in the heat sensitive layer composition solution was changed to 112 parts by weight. The printing evaluation results are as follows: Evaluation A, color contamination change rate 2.0%, background dirt start temperature 32.6 ° C., printing durability 75000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 80% there were.

Examples 23 to 26
The same operation as in Example 1 was performed except that the film thickness of the ink repellent layer B was changed. The obtained evaluation results are shown in Table 3.

Example 23
The operation was performed in the same manner as in Example 1 except that the amount of Isopar E in the ink repellent layer composition solution was changed to 2970 parts by weight. The printing evaluation results are as follows: Evaluation A with a color density change rate of 2.0%, background dirt start temperature 25.7 ° C., printing durability 65000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 24
The operation was performed in the same manner as in Example 1 except that the Isopar E of the ink repellent layer composition solution was changed to 1130 parts by weight. The printing evaluation results are as follows: Evaluation A, color contamination change rate 2.0%, background dirt start temperature 30.1 ° C., printing durability 90000 sheets, image reproducibility 10 μm thin line: 100%, 6.4 μm thin line: 100% there were.

Example 25
The operation was performed in the same manner as in Example 1 except that the Isopar E of the ink repellent layer composition solution was changed to 563 parts by weight. The printing evaluation results are as follows: Evaluation A, color dirt change rate 2.0%, background dirt start temperature 33.7 ° C., printing durability 100000 sheets, image reproducibility 10 μm thin line: 90%, 6.4 μm thin line: 85% there were.

Example 26
The operation was performed in the same manner as in Example 1 except that the amount of Isopar E of the ink repellent layer composition solution was changed to 300 parts by weight. The printing evaluation results are as follows: Evaluation A, color dirt change rate 2.0%, background dirt start temperature 35.0 ° C., printing durability 110,000, image reproducibility 10 μm thin line: 80%, 6.4 μm thin line: 75% there were.

Comparative example 3
The procedure of Example 1 was repeated except that the resin of the heat sensitive layer was changed to phenol formaldehyde novolak resin: "Sumilight Resin" (registered trademark) PR53195 (manufactured by Sumitomo Bakelite Co., Ltd.). The printing evaluation results were as follows: Evaluation D with color density change rate 40%, background dirt start temperature 25.5 ° C., printing durability 5000 sheets, image reproducibility 10 μm thin line: 30%, 6.4 μm thin line: 30% . The results are shown in Table 4.

1 Ink roller 2 Lithographic printing plate 3 Plate cylinder 4 Blanket 5 Printing material 6 Support roller

Claims (16)

And a silicone rubber derived from the addition reaction of (A) a photothermal conversion substance and a melamine resin, and (B) (a) a hydrosilyl group-containing compound and (b) a vinyl group-containing polysiloxane on a substrate, The rubber contains a dimethylsiloxane unit represented by the following general formula (I) and a siloxane unit represented by (II), and is represented by the peak intensity of (II) Si ^** / the peak intensity of (I) Si ^* Ink repellent layer having a peak intensity ratio of 0.0005 or more and 0.0090 or less -Si ^* (CH ₃ ) ₂ -O- (I)
_{-Si (CH 3) 2 -CH 2} -CH 2 -Si ** (CH 3) 2 -O- (II)
A method for producing a printed matter, comprising the steps of: attaching a lithographic printing ink to a lithographic printing plate having the step of transferring the adhered ink directly or via a blanket onto a substrate.   The method according to claim 1, wherein the peak intensity ratio is 0.0010 or more and 0.0050 or less.   The method for producing a printed matter according to claim 1, wherein the peak intensity ratio is 0.0015 or more and 0.0023 or less.   The surface tension of the said ink for lithographic printing is the range of 45-70 mN / m, The manufacturing method of the printed matter in any one of Claims 1-3.   The method for producing a printed matter according to any one of claims 1 to 4, wherein the lithographic printing ink is an active energy ray-curable water-soluble ink for lithographic printing.   The method for producing a printed matter according to any one of claims 1 to 5, wherein the lithographic printing plate has a metal layer and / or a metal oxide layer between the substrate and the heat sensitive layer (A). The method according to claim 6, wherein the metal oxide layer is an aluminum oxide layer.   The method for producing a printed matter according to claim 7, wherein the arithmetic mean roughness (Ra) of the heat-sensitive layer side of the aluminum oxide layer is 0.01 μm or more and 1.0 μm or less.   The method for producing a printed matter according to any one of claims 6 to 8, wherein the metal layer is an aluminum layer.   The lithographic printing plate obtained by subjecting a lithographic printing plate precursor having a heat-sensitive layer (A) and an ink repellent layer (B) to imagewise exposure with a laser beam and then applying physical stimulation to the lithographic printing plate precursor. The manufacturing method of the printed matter in any one of 1-9.   In the presence of water or an aqueous solution obtained by adding a surfactant to water after imagewise exposing the lithographic printing plate precursor having a heat-sensitive layer (A) and an ink repellent layer (B) to a lithographic printing plate precursor The method for producing a printed matter according to any one of claims 1 to 10, which is a lithographic printing plate obtained by applying physical stimulation.   The lithographic printing plate precursor is imagewise exposed to laser light on a lithographic printing plate precursor having a heat-sensitive layer (A) and an ink repellent layer (B), and the plate is mounted on a printing machine to supply the lithographic printing ink. 12. The lithographic printing plate as claimed in claim 1, which is a lithographic printing plate obtained by the step of carrying out an on-press development process according to the method described above or the method of supplying the lithographic printing ink after image exposure after mounting on a printing machine. Method for producing the printed matter described.   The method for producing a printed matter according to any one of claims 1 to 12, wherein the printing material is selected from the group consisting of plastic films, plastic film-laminated paper, metals, metallized paper and metallized plastic films.   The method for producing a printed matter according to any one of claims 1 to 13, further comprising the step of irradiating an active energy ray after the transferring step according to claim 1.   The method for producing a printed matter according to claim 14, wherein the peak wavelength of the active energy ray is LED-UV in the range of 250 to 400 nm.   The method for producing a printed matter according to claim 14 or 15, wherein the active energy ray is an electron beam.

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