WO2017047817A1 - 平版印刷用インキ、平版インキ用ワニスおよびそれを用いた印刷物の製造方法 - Google Patents
平版印刷用インキ、平版インキ用ワニスおよびそれを用いた印刷物の製造方法 Download PDFInfo
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- WO2017047817A1 WO2017047817A1 PCT/JP2016/077750 JP2016077750W WO2017047817A1 WO 2017047817 A1 WO2017047817 A1 WO 2017047817A1 JP 2016077750 W JP2016077750 W JP 2016077750W WO 2017047817 A1 WO2017047817 A1 WO 2017047817A1
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- lithographic printing
- ink
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- printing ink
- resin
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/06—Lithographic printing
- B41M1/08—Dry printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5209—Coatings prepared by radiation-curing, e.g. using photopolymerisable compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0045—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by mechanical wave energy, e.g. ultrasonics, cured by electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams, or cured by magnetic or electric fields, e.g. electric discharge, plasma
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
Definitions
- the present invention relates to a lithographic printing ink, a lithographic ink varnish, and a printed matter, which have high sensitivity active energy ray curability and water washability, and are excellent in soil stain resistance during printing and water resistance of a cured film. It relates to the manufacturing method.
- VOCs Volatile Organic Compounds
- Lithographic printing is a printing method that is widely used as a system that supplies printed matter at high speed, in large quantities, and at low cost, and includes lithographic printing with water and lithographic printing without water.
- the fountain solution used in large quantities for image formation contains a large amount of volatile solvent, which is problematic in terms of work and environment.
- waterless lithographic printing uses silicone rubber or fluororesin for the non-image area and does not require dampening water.
- Patent Document 1 discloses a water-washable active energy ray-curable offset printing ink that can be printed using a waterless lithographic plate.
- Patent Document 2 discloses an alkali-soluble gravure ink composition for an ultraviolet curable resist.
- Patent Documents 1 and 2 With the conventional active energy ray-curable offset printing inks listed in Patent Documents 1 and 2, sufficient curing can be obtained at the printing speed in an actual UV printing machine and the exposure amount by power saving UV. Therefore, the water resistance of the cured film is insufficient. In addition, it may be necessary to add a thixotropic agent to impart the necessary printability to the ink (Patent Document 2). Even if the ink is sufficiently cured, the ink is cured with active energy rays immediately after the ink is applied to the substrate, resulting in unevenness due to insufficient leveling of the ink, and the gloss value of the printed material is higher than that of a normal printed material. There was a decline.
- the resin concentration in the lithographic printing ink is increased to increase the ink viscosity.
- the lithographic printing ink has a high viscosity, its fluidity decreases.
- the active energy ray curable printing in which the ink is instantly cured by the active energy rays, the ink is cured before leveling.
- irregularities are likely to occur on the surface of the lithographic printing ink film, and the gloss of the printed matter is inferior to that of the oil-based lithographic printing ink.
- the soil resistance during printing and the water resistance and glossiness of the cured film are also improved. It is an object of the present invention to provide an excellent lithographic printing ink, a lithographic ink varnish constituting the lithographic printing ink, and a method for producing a printed matter using the lithographic ink varnish.
- the lithographic printing ink of the present invention comprises (a) a pigment, and (b) a resin having an ethylenically unsaturated group and a hydrophilic group.
- a lithographic printing ink that is excellent in soil resistance during printing and water resistance of a cured film. By using it, a printed matter excellent in gloss can be obtained.
- the lithographic printing ink of the present invention comprises (a) a pigment and a varnish component.
- the varnish component includes (b) a resin having an ethylenically unsaturated group and a hydrophilic group. Further, as the varnish component, (c) a reactive diluent, (d) an ink adhesion inhibiting component, (e) a photopolymerization initiator, (f) an emulsifier, (g) a pigment dispersant, and the like can be optionally included.
- the varnish component may be referred to as “lithographic ink varnish”.
- the lithographic printing ink of the present invention has high sensitivity active energy ray curability.
- the active energy rays include ultraviolet rays (UV), electron beams (EB), visible rays, X-rays, and particle beams, but ultraviolet rays are preferable from the viewpoint of easy handling of the radiation source.
- the lithographic printing ink has a property of curing when irradiated with active energy rays, and its sensitivity is excellent.
- the lithographic printing ink of the present invention contains (a) a pigment.
- a pigment included in the present invention, at least one selected from inorganic pigments and organic pigments generally used in printing inks can be used. In particular, inorganic pigments and / or organic pigments used in lithographic printing inks can be used.
- the inorganic pigment used in the present invention include titanium dioxide, calcium carbonate, barium sulfate, bengara, cadmium red, yellow lead, zinc yellow, bitumen, ultramarine, organic bentonite, alumina white, iron oxide, carbon black, graphite, Aluminum etc. are mentioned.
- organic pigments examples include phthalocyanine pigments, soluble azo pigments, insoluble azo pigments, lake pigments, quinacridone pigments, isoindoline pigments, selenium pigments, metal complex pigments, and specific examples thereof include phthalocyanine.
- examples include blue, phthalocyanine green, azo red, monoazo red, monoazo yellow, disazo red, disazo yellow, quinacridone red, quinacridone magenta, and isoindoline yellow.
- Carbon black is preferably used for the (a) pigment of the present invention.
- carbon black having an acidic group is more preferably used because it has a high effect of improving the fluidity of the ink.
- the average particle size of the carbon black used in the present invention is preferably 10 nm or more, and more preferably 15 nm or more in order to suppress an increase in the viscosity of the ink composition. Moreover, in order to obtain the gloss of a printed material, 50 nm or less is preferable and 40 nm or less is more preferable.
- the average particle diameter here is an average value of particle diameters determined by the following method. From the two-dimensional image obtained by observing the particles with a scanning electron microscope (SEM), the one that maximizes the distance between the two intersections of the straight line that intersects the outer edge of the particles at two points is calculated as the particle diameter. It is defined as Furthermore, the same measurement is performed on arbitrary 20 different particles, and the average value of the obtained particle sizes is defined as the average particle size.
- SEM scanning electron microscope
- Dibutyl phthalate absorption of the carbon black of the present invention is in a range of carbon black per 100g 40 ⁇ 80 cm 3, it is preferable that is in the range of 40 ⁇ 80cm 3 / 100g.
- the method for measuring the amount of dibutyl phthalate absorbed by carbon black is shown in JIS K 6217-4: 2008 “Carbon black for rubber-Basic characteristics-Part 4: Determination of oil absorption (including compressed samples)”. From the absorption amount, the size of the secondary aggregate (structure) of carbon black can be estimated. It can be estimated that the larger the absorption amount, the larger the structure.
- dibutyl phthalate absorption of the carbon black is 40 cm 3/100 g or more, preferably it is possible to suppress the increase in viscosity of the ink composition that occurs when structure is too small. Further, when the dibutyl phthalate absorption of the carbon black is less than 80 cm 3/100 g, the phenomenon that the leveling of ink may be sufficient, print gloss by surface roughness of the printed matter becomes larger decreases occurred Is preferable.
- the carbon black having an acidic group which is preferably used in the present invention, usually has an oxidized surface and has an oxygen-containing group such as a carboxyl group, a quinone group, a lactone group or a hydroxyl group on the surface.
- an oxygen-containing group such as a carboxyl group, a quinone group, a lactone group or a hydroxyl group on the surface.
- those having a carboxyl group are preferably used because of their low cost.
- the pigment (a) of the present invention is preferably a water-insoluble salt in that it has a clear color tone and coloring and good solvent resistance.
- azo lake pigments are more preferably used because they have a clearer color tone and coloration and good solvent resistance despite being inexpensive.
- azo lake pigments examples include azo dyes obtained by coupling a diazonium salt of an aromatic amine having a water-soluble group and a coupler component with an alkaline earth metal salt, acetoacetanilide type, pyrazolone type. , ⁇ -naphthol, ⁇ -oxynaphthoic acid, ⁇ -oxynaphthoic acid anilide, etc. are known. Specific examples include tartrazine aluminum lake, lake red C, brilliant carmine 6B, brilliant scarlet G, lake Red D, Bordeaux 10B, Orange II, Carmine 3B, Permanent red, Resol red and the like can be mentioned.
- a metal complex pigment is also preferably used because of its clear color and high durability.
- copper phthalocyanine which is a copper complex of phthalocyanine, is more preferably used because it is excellent in color, is clear, has high light resistance, and is robust.
- metal complex pigments include phthalocyanine cobalt, which is a cobalt complex of phthalocyanine, and pigments, which are complexes of Schiff base and nickel. Yellow 150, pigment yellow 153, and the like. These pigments can be used alone or in admixture of two or more.
- the pigment concentration contained in the lithographic printing ink of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more in order to obtain the printing paper surface density. Moreover, in order to improve the fluidity
- the lithographic printing ink of the present invention contains (b) a resin having an ethylenically unsaturated group and a hydrophilic group.
- the (b) lithographic printing ink containing a varnish component made of a resin having an ethylenically unsaturated group and a hydrophilic group has both high-sensitivity active energy ray curability and water washability, as well as resistance to printing. Excellent soil resistance and water resistance of cured film.
- Solid stain here means that ink adheres to a non-image area of a lithographic printing plate to which ink does not adhere. As a result of ink adhering to the non-image area of the planographic printing plate, the ink is also transferred onto the printed matter.
- the resin (b) having an ethylenically unsaturated group and a hydrophilic group has an ethylenically unsaturated group in the side chain. It has curability by active energy rays. Further, (b) a resin having an ethylenically unsaturated group and a hydrophilic group preferably has a high molecular weight, and (b) the resin itself having an ethylenically unsaturated group and a hydrophilic group has curability by active energy rays.
- the ink is cured by a radical reaction between resins having a high molecular weight, the irradiation amount of the active energy ray necessary for curing is small, and as a result, it has a high sensitivity of the active energy ray curability.
- UV printing that instantly cures ink by irradiating ultraviolet rays as active energy rays
- sufficient ink curability can be obtained even with a small amount of ultraviolet irradiation, greatly improving productivity by improving printing speed.
- the cost can be reduced by applying a power-saving UV light source (for example, a metahalo lamp or LED).
- the resin (b) having an ethylenically unsaturated group and a hydrophilic group has a hydrophilic group in the side chain, so that it becomes soluble in an aqueous cleaning liquid containing water as a main component, and is a non-petroleum detergent. Applicable. Furthermore, since the hydrophilic group interacts with the surface functional group of the pigment in the ink, it can also have good dispersibility of the pigment.
- the resin (b) having an ethylenically unsaturated group and a hydrophilic group improves the viscosity property of the ink due to hydrogen bonding between the hydrophilic groups, so that the viscosity of the ink increases. If the ink has a high viscosity, the cohesive force of the ink under high shear during printing will increase, and the ink rebound on the non-image area will improve, that is, the adhesion of the ink to the silicone rubber will decrease. It also contributes to improved soil resistance during printing.
- Patent Document 1 In the prior art, it has been studied to realize an active energy ray-curable offset printing ink that can be washed with water by making the resin water-soluble (for example, Patent Document 1). For example, an exposure amount using power-saving UV in an actual UV printing machine may not provide sufficient film curing, resulting in insufficient water resistance of the cured film.
- the lithographic printing ink of the present invention (b) provides both an ethylenically unsaturated group and a hydrophilic group with a resin having an ethylenically unsaturated group and a hydrophilic group, and controls the content thereof.
- the sensitivity of curing of the film by active energy rays can be increased, and for example, good water resistance of the cured film can be realized even by exposure using power-saving UV.
- hydrophilic group of the resin (b) having an ethylenically unsaturated group and a hydrophilic group include a carboxyl group, a sulfo group, a phosphate group, and a hydroxyl group (hydroxyl group) from the viewpoint of solubility in water. And at least one functional group selected from amino groups.
- the hydrophilic group is preferably an acidic group, and a carboxyl group is more preferable from the viewpoint of good dispersibility of the pigment.
- the hydrophilic group particularly preferably contains a carboxyl group and a hydroxyl group.
- the acid value of the hydrophilic group in the resin having (b) the ethylenically unsaturated group and the hydrophilic group is preferably 30 mgKOH / g or more and 250 mgKOH / g or less.
- the acid value of the hydrophilic group is preferably 30 mgKOH / g or more, preferably 60 mgKOH / g or more in order to obtain good solubility of the resin in an aqueous cleaning solution, dispersibility of the pigment, and stain resistance. Is more preferably 75 mgKOH / g or more.
- it is preferably 250 mgKOH / g or less, more preferably 200 mgKOH / g or less, and further preferably 150 mgKOH / g or less.
- the acid value of the hydrophilic group is determined in accordance with JIS K 0070: 1992 “Testing Method for Acid Value, Saponification Value, Ester Value, Iodine Value, Hydroxyl Value, and Unsaponifiable Product of Chemical Products” “Section 3.1.
- the neutralization titration method can be obtained in accordance with
- the solubility of the resin (b) having an ethylenically unsaturated group and a hydrophilic group in the present invention in water is preferably 0.1 g / (100 g-H 2 O) or more. When the solubility is as described above, cleaning with an aqueous cleaning solution is facilitated.
- the water solubility of the resin having an ethylenically unsaturated group and a hydrophilic group is more preferably 0.3 g / (100 g-H 2 O) or more, and 0.5 g / (100 g-H 2 O). Or more). The higher the solubility in water, the better the water washability.
- the solubility of the resin to water is preferably from 100g / (100g-H 2 O ) or less, 50g / (100g-H 2 O) , more preferably less, more preferably 10g / (100g-H 2 O ) or less.
- the solubility is the solubility in water at 25 ° C.
- the iodine value in the ethylenically unsaturated group in the resin having (b) the ethylenically unsaturated group and the hydrophilic group is preferably 0.5 mol / kg or more and 3.0 mol / kg or less.
- the iodine value is preferably 0.5 mol / kg or more, and more preferably 1.0 mol / kg or more because good sensitivity to active energy rays can be obtained.
- it is preferably 3.0 mol / kg or less, more preferably 2.5 mol / kg or less, and further preferably 2.0 mol / kg or less. preferable.
- the iodine value of the ethylenically unsaturated group is JIS K 0070: 1992 “Testing Method for Acid Value, Saponification Value, Ester Value, Iodine Value, Hydroxyl Value and Unsaponified Product of Chemical Products” “Section 6.0 It can be determined by the method described in “Iodine value”.
- the base resin constituting the resin having an ethylenically unsaturated group and a hydrophilic group include acrylic resin, styrene acrylic resin, styrene maleic resin, rosin modified maleic resin, rosin modified acrylic resin, epoxy A resin, a polyester resin, a polyurethane resin, a phenol resin, and the like can be given, but there is no particular limitation.
- acrylic resin styrene acrylic resin, styrene are available from the viewpoints of availability of monomers, low cost, ease of synthesis, compatibility with other components contained in the ink, and dispersibility of pigments.
- Maleic acid resin is preferably used as the base of (b) a resin having an ethylenically unsaturated group and a hydrophilic group.
- the resin having an ethylenically unsaturated group and a hydrophilic group contains one or more kinds of resins selected from the group consisting of acrylic resins, styrene acrylic resins, and styrene maleic acid resins. Is preferred.
- a resin having an ethylenically unsaturated group and a hydrophilic group containing a resin selected from an acrylic resin, a styrene acrylic acid resin, and a styrene maleic acid resin can be produced by the following method.
- carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate or their acid anhydrides, hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, dimethylaminoethyl methacrylate Amino group-containing monomers such as 2- (mercaptoacetoxy) ethyl acrylate, mercapto group-containing monomers, acrylamide t-butyl sulfonic acid-containing monomers, 2-methacryloxyethyl acid phosphate-containing phosphate groups
- a compound selected from monomers, methacrylic acid esters, acrylic acid esters, styrene, acrylonitrile, vinyl acetate and the like is polymerized or copolymerized using a radical polymerization initiator, and then the active hydrogen content in the polymer is contained.
- Mercapto group is a group, the amino group, hydroxyl group or a carboxyl group, an ethylenically unsaturated compound, acrylic acid chloride having a glycidyl group and an isocyanate group, obtained by addition reaction of methacrylic acid chloride or allyl chloride. However, it is not limited to these methods.
- ethylenically unsaturated compound having a glycidyl group examples include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl crotonic acid, and glycidyl isocrotonic acid.
- ethylenically unsaturated compound having an isocyanate group examples include acryloyl isocyanate, methacryloyl isocyanate, acryloylethyl isocyanate, and methacryloylethyl isocyanate.
- the base resin constituting the resin having an ethylenically unsaturated group and a hydrophilic group include (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer , Styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid- (meth) acrylic acid copolymer And a styrene-maleic acid- (meth) acrylic acid ester copolymer.
- the weight average molecular weight of the resin (b) having an ethylenically unsaturated group and a hydrophilic group is preferably 5,000 or more, more preferably 15,000 or more in order to obtain water resistance of the cured film. 20,000 or more is more preferable, and 25,000 or more is particularly preferable. Moreover, in order to obtain water-solubility of the resin, it is preferably 100,000 or less, more preferably 75,000 or less, and further preferably 50,000 or less.
- the weight average molecular weight can be obtained by measuring in terms of polystyrene using gel permeation chromatography (GPC).
- the content of the resin (b) having an ethylenically unsaturated group and a hydrophilic group contained in the lithographic printing ink of the present invention is 5 mass for obtaining the viscosity of ink necessary for printing and the sensitivity necessary for curing. % Or more is preferable, and 10 mass% or more is more preferable. Moreover, in order to obtain the fluidity of the ink required for printing and the transferability between the rollers, the content is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.
- the lithographic printing ink of the present invention preferably contains (b) a resin having an ethylenically unsaturated group and a hydrophilic group, and (c) a reactive diluent as a varnish component.
- the reactive diluent may have a property of being cured by irradiation with active energy rays.
- C As a reactive diluent, the compound which has an ethylenically unsaturated group, what is called a monomer can be illustrated.
- resin which has a hydrophilic group resin which has a hydrophilic group and does not have an ethylenically unsaturated group other than (b) resin which has an ethylenically unsaturated group and a hydrophilic group can be included.
- a resin having an ethylenically unsaturated group and a hydrophilic group, and a resin having a hydrophilic group and not having an ethylenically unsaturated group may be referred to as a “resin having a hydrophilic group”.
- the lithographic ink varnish constituting the lithographic printing ink preferably contains a resin having a hydrophilic group and a reactive diluent.
- any compound having solubility in water, compatibility with a resin, and an ethylenically unsaturated group can be used.
- a reactive diluent having a hydrophilic skeleton such as ethylene oxide-modified, a hydrophilic group such as a carboxyl group, a hydroxyl group, and an amino group and having a weight average molecular weight of 100 to 1,000 has water solubility and resin And is preferably used.
- the reactive diluent preferably has 3 to 4 ethylenically unsaturated groups in one molecule, and a cured film having ink properties and sufficient water resistance necessary for lithographic printing can be obtained. it can. That is, as the (c) reactive diluent, a polyfunctional (meth) acrylate having hydrophilicity is preferably used. Of these, a polyfunctional (meth) acrylate having a hydroxyl group is more preferable.
- Preferred specific examples of the reactive diluent (c) include, but are not limited to, ethylene oxide modified products of trimethylolpropane triacrylate, pentaerythritol triacrylate, and ethylene oxide modified products of pentaerythritol tetraacrylate. It is not a thing.
- the amount of (c) reactive diluent added is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more because an ink viscosity suitable for lithographic printing can be obtained. preferable.
- the cured film which has favorable sensitivity and sufficient water resistance is obtained, 90 mass% or less is preferable, 80 mass% or less is more preferable, and 70 mass% or less is further more preferable.
- a polyfunctional (meth) acrylate having a hydroxyl group as the reactive diluent (c) because it can provide a varnish for a lithographic ink having high viscosity and excellent fluidity and pigment dispersibility. Further, a printed matter using a lithographic printing ink containing a lithographic ink varnish and a pigment is preferable because it exhibits high gloss.
- the lithographic ink varnish constituting the lithographic printing ink may contain the above-described polyfunctional (meth) acrylate having a hydroxyl group and a resin having a hydrophilic group.
- the polyfunctional (meth) acrylate having a hydroxyl group and the resin having a hydrophilic group have high compatibility, and the resulting lithographic ink varnish has a high viscosity. This is because the hydroxyl group and the hydrophilic group interact by hydrogen bonding or the like in the lithographic ink varnish.
- the lithographic printing ink of the present invention also has a high viscosity, increasing the cohesive strength of the ink under high shear during printing, and as a result improving the soil resistance.
- the lithographic ink varnish has good fluidity because it contains the polyfunctional (meth) acrylate having a hydroxyl group.
- the lithographic ink varnish is excellent in pigment dispersibility. Since the polar group contained in the lithographic ink varnish stabilizes the dispersion of the pigment, the lithographic printing ink containing the lithographic ink varnish has good fluidity.
- the content of the polyfunctional (meth) acrylate having a hydroxyl group in the lithographic ink varnish is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. preferable.
- the content is 20% by mass or more, the fluidity and pigment dispersibility of the varnish can be sufficiently obtained. Thereby, it is possible to prevent the pigment contained in the lithographic printing ink from forming an aggregate structure and lowering the fluidity of the ink. As a result, a highly glossy printed material can be obtained.
- the content of the polyfunctional (meth) acrylate having a hydroxyl group in the lithographic ink varnish in the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and 70% by mass or less. Further preferred. If the content is 90% by mass or less, in the varnish, the hydroxyl group in the polyfunctional (meth) acrylate having a hydroxyl group and the hydrophilic group in the resin having a hydrophilic group interact by hydrogen bonding or the like. It is sufficiently obtained and the viscosity of the varnish is improved. As a result of improving the viscosity of the varnish, the ink containing the lithographic ink varnish can maintain the cohesive strength of the ink even under high shear during printing, and can improve the stain resistance.
- the lithographic printing ink of the present invention preferably contains 20% by mass or more of the polyfunctional (meth) acrylate having a hydroxyl group, because the pigment dispersibility of the ink is improved. More preferably, it is 30 mass% or more, More preferably, it is 40 mass% or more. Moreover, since the fluidity
- the hydroxyl value of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 50 mgKOH / g or more and 200 mgKOH / g or less.
- the hydroxyl value is preferably 50 mgKOH / g or more, more preferably 75 mgKOH / g or more, and even more preferably 100 mgKOH / g or more.
- the hydroxyl value is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, and even more preferably 160 mgKOH / g or less.
- the molecular weight of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 100 or more and 1000 or less. Since the lithographic ink varnish has high viscosity, the molecular weight is preferably 100 or more, more preferably 200 or more, and even more preferably 250 or more. Since the fluidity of the lithographic ink varnish is good, the molecular weight is preferably 1000 or less, more preferably 700 or less, and even more preferably 500 or less.
- polyfunctional (meth) acrylate having a hydroxyl group include poly (meth) acrylates of polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, diglycerin, ditrimethylolpropane and dipentaerythritol, And these modified alkylene oxides.
- examples thereof include di- or tri (meth) acrylate, dipentaerythritol di-, tri-, tetra- or penta (meth) acrylate, ethylene oxide-modified products, propylene oxide-modified products, and tetraethylene oxide-modified products.
- the lithographic ink varnish is excellent in fluidity and pigment dispersibility, and the lithographic ink varnish has a high viscosity.
- pentaerythritol tri (meth) acrylate diglycerin tri (meth) acrylate, ditri Methylolpropane tri (meth) acrylate is particularly preferred and may contain at least one selected from these.
- the lithographic ink varnish can further contain a (meth) acrylate compound other than a polyfunctional (meth) acrylate having a hydroxyl group for the purpose of adjusting the viscosity.
- a (meth) acrylate compound other than a polyfunctional (meth) acrylate having a hydroxyl group for the purpose of adjusting the viscosity.
- the number of (meth) acrylate groups in the (meth) acrylate compound is high sensitivity, and is preferably bifunctional or more, and more preferably trifunctional or more.
- (meth) acrylate compounds monofunctional (meth) acrylates having 1 to 18 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate Octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, ethylene oxide modified products, propylene oxide modified products, and the like.
- benzyl (meth) acrylate isobornyl ( Examples include meth) acrylate, cyclohexyl (meth) acrylate, and tricyclodecane monomethylol (meth) acrylate.
- (meth) acrylate compounds made from dihydric alcohols and glycols can be used.
- a (meth) acrylate compound using tetrahydric alcohol and glycols as raw materials can be used. More specifically, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, diglycerin tetra (meta) ) Acrylate, these ethylene oxide modified products, and propylene oxide modified products.
- (meth) acrylate compounds made from pentavalent or higher alcohols and glycols can be used. More specifically, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified products, and propylene oxide-modified products. Is mentioned.
- low-viscosity and high-sensitivity trimethylolpropane tri (meth) acrylate modified with ethylene oxide low-viscosity and high-sensitivity trimethylolpropane tri (meth) acrylate modified with ethylene oxide, pentaerythritol tetra (meth) acrylate modified with ethylene oxide, diglycerin tetra (meth) acrylate modified with ethylene oxide, ditrile
- An ethylene oxide modified product of methylolpropane tetra (meth) acrylate is particularly preferred.
- the content of the (meth) acrylate compound is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more because the fluidity of the lithographic ink varnish is improved. Moreover, since the viscosity of the lithographic ink varnish does not decrease excessively, the content is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
- hydrophilic group of the resin having a hydrophilic group contained in the lithographic ink varnish examples include a polyethylene oxide group, a polypropylene oxide group, a hydroxyl group, a carboxyl group, a sulfo group, and a phosphoric acid group.
- a carboxyl group is particularly preferable because of good dispersibility of the pigment.
- the acid value of the resin having a hydrophilic group is preferably 30 mgKOH / g or more and 250 mgKOH / g or less. Since the pigment dispersibility of the lithographic ink varnish is good and the lithographic ink varnish has high viscosity, the acid value is preferably 30 mgKOH / g or more, more preferably 60 mgKOH / g or more, and 75 mgKOH / g or more. Further preferred. In view of good fluidity of the lithographic ink varnish, the acid value is preferably 250 mgKOH / g or less, more preferably 200 mgKOH / g or less, and even more preferably 150 mgKOH / g or less.
- the acid value of the resin having a hydrophilic group can be determined in accordance with the neutralization titration method of test method 3.1 of JIS K 0070: 1992.
- the weight average molecular weight of the resin having a hydrophilic group is preferably 5,000 or more and 100,000 or less. Since the lithographic ink varnish has high viscosity, the weight average molecular weight is preferably 5,000 or more, more preferably 15,000 or more, and further preferably 20,000 or more. Since the fluidity of the lithographic ink varnish is good, the weight average molecular weight is preferably 100,000 or less, more preferably 75,000 or less, and even more preferably 50,000 or less.
- the weight average molecular weight can be obtained by measuring in terms of polystyrene using gel permeation chromatography (GPC).
- the resin having a hydrophilic group examples include acrylic resin, styrene acrylic resin, styrene maleic acid resin, rosin modified maleic resin, rosin modified acrylic resin, epoxy resin, polyester resin, polyurethane resin, phenol resin, and the like. However, it is not particularly limited.
- acrylic resin styrene acrylic resin, styrene maleic acid resin from the viewpoints of availability of monomers, low cost, ease of synthesis, compatibility with other ink components, dispersibility of pigments, etc.
- it is preferably used as a resin having a hydrophilic group.
- acrylic resin, styrene acrylic acid resin, and styrene maleic acid resin can be prepared by the following method. That is, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate or their acid anhydrides, hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, dimethylaminoethyl methacrylate Amino group-containing monomers such as 2- (mercaptoacetoxy) ethyl acrylate, mercapto group-containing monomers, acrylamide t-butyl sulfonic acid-containing monomers, 2-methacryloxyethyl acid phosphate-containing phosphate groups It can be obtained by polymerizing or copolymerizing a compound selected from monomers, methacrylic acid esters, acrylic acid esters, styrene, acrylonitrile, vinyl a
- the resin having a hydrophilic group examples include (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid copolymer, styrene. -(Meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid- (meth) acrylic acid copolymer, styrene-maleic acid- (meth) acrylic acid ester A copolymer etc. are mentioned.
- the resin having a hydrophilic group preferably has an ethylenically unsaturated group since the curing sensitivity to active energy rays is improved. That is, the resin having a hydrophilic group is preferably the resin (b) having an ethylenically unsaturated group and a new aqueous group.
- the fluidity of the lithographic ink varnish is the ratio of the storage elastic modulus G ′ and loss elastic modulus G ′′ measured by the sinusoidal vibration method using a dynamic viscoelasticity measuring device at 25 ° C. and 1 rad / s.
- the value of the tangent loss tan ⁇ is preferably 1.5 or more, more preferably 2 or more, and further preferably 3 or more, because the varnish takes a viscous behavior and high fluidity is obtained.
- the value of tan ⁇ of the varnish is preferably 30 or less, more preferably 10 or less, and even more preferably 5 or less, because the viscosity of the varnish can be improved and the soil stain resistance of the ink having the varnish can be improved.
- the viscosity of the lithographic ink varnish is measured at 25 ° C. and 0.5 rpm using a B-type viscometer.
- the varnish viscosity is preferably 10 Pa ⁇ s or higher, more preferably 50 Pa ⁇ s or higher, and even more preferably 100 Pa ⁇ s or higher because the stencil resistance of the lithographic printing ink is improved.
- the varnish viscosity is preferably 400 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less, and even more preferably 250 Pa ⁇ s or less because the flowability of the lithographic printing ink is good.
- a method for producing a lithographic ink varnish is described below.
- a lithographic ink varnish is obtained by heating and dissolving a polyfunctional (meth) acrylate having a hydroxyl group, a resin having a hydrophilic group, and other components at 50 to 95 ° C., if necessary, and then cooling to room temperature. It is done.
- the lithographic printing ink of the present invention includes a lithographic ink varnish and a pigment.
- the lithographic printing ink is excellent in fluidity while having high viscosity. Since the lithographic ink has a high viscosity, it is excellent in soil resistance. Further, a printed matter using the lithographic ink exhibits high gloss.
- the lithographic ink varnish in the lithographic printing ink is contained in an amount of 50% by mass to 90% by mass. Since the lithographic printing ink has excellent pigment dispersibility and good background stain resistance during printing, the content is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. preferable. Since the fluidity of the lithographic printing ink is obtained, the content is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less.
- the lithographic printing ink of the present invention preferably contains (d) one or more components selected from the group consisting of a silicone liquid, an alkyl acrylate, a hydrocarbon solvent, and a fluorocarbon. Moreover, you may contain the fatty acid ester derived from vegetable oil or vegetable oil.
- the component (d) has the effect of reducing ink adhesion to the silicone rubber that is the non-image area of the waterless lithographic printing plate.
- the reason for reducing the ink adhesion to the silicone rubber is presumed as follows. That is, the component (d) contained in the ink diffuses from the ink by contact with the surface of the silicone rubber, and covers the surface of the silicone rubber in a thin film shape. It is presumed that the thin film formed in this manner prevents ink from adhering to the surface of the silicone rubber and prevents soiling on the silicone surface.
- alkyl acrylate is preferable because it cures when irradiated with active energy rays, and therefore improves the water resistance of the cured film of the ink and at the same time improves the sensitivity to the active energy rays.
- Silicone liquids include dimethyl silicone, methylphenyl silicone, alkyl modified silicone, polyether modified silicone, aralkyl modified silicone, fatty acid amide modified silicone, fatty acid ester modified silicone, fluoroalkyl modified silicone, methyl hydrogen silicone, silanol modified silicone, alcohol Examples include modified silicone, amino-modified silicone, epoxy-modified silicone, epoxy polyether-modified silicone, phenol-modified silicone, carboxy-modified silicone, and mercapto-modified silicone.
- alkyl acrylate examples 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.
- alkyl methacrylate examples include nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate and the like.
- hydrocarbon solvent examples include polyolefin oil, naphthene oil, paraffin oil and the like.
- Fluorocarbons include 1,1,1,2,2-pentafluoroethane, 1,1,1,2,2,3,4,4-nonafluorobutane, 1,1,1,2,2, 3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7 , 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- Decafluoro hexane, and the like.
- Examples of vegetable oils include soybean oil, linseed oil, safflower oil, tung oil, tall oil, and dehydrated castor oil.
- fatty acid esters derived from vegetable oils fatty acids having an alkyl main chain of about 15 to 20 carbon atoms such as stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, methyl, ethyl, Examples thereof include alkyl esters having about 1 to 10 carbon atoms such as propyl, isopropyl, butyl, isobutyl, tert-butyl and 2-ethylhexyl.
- the content of the component (d) with respect to the total amount of the lithographic printing ink is preferably 0.5% by mass or more since the soil resistance of the lithographic printing ink is good. More preferably, it is 1 mass% or more, More preferably, it is 2 mass% or more. Moreover, since the storage stability of the said lithographic printing ink is favorable, 10 mass% or less is preferable. More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less.
- the lithographic printing ink of the present invention preferably contains a surfactant.
- the surfactant takes in dampening water, which is a non-image area of lithographic printing with water, into the lithographic printing ink to form a W / O emulsion. That is, the surfactant means (f) an emulsifier.
- the lithographic printing ink increases the resilience of the non-image area to dampening water. Improves soil resistance. In addition, good fillability can be maintained even in the image area.
- the ratio of the hydrophilic group to the hydrophobic group of the surfactant, that is, (f) emulsifier is represented by an HLB value.
- the HLB value mentioned here is a value representing the degree of affinity of the surfactant, ie, (f) emulsifier, with water and oil.
- the HLB value ranges from 0 to 20, and the closer to 0, the more lipophilic. Higher and closer to 20 means higher hydrophilicity.
- the HLB value of the surfactant, that is, (f) the emulsifier is preferably 10 or more because it dissolves water. Moreover, since it melt
- surfactant that is, (f) emulsifier
- examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene palmitic Ether, polyoxypropylene alkyl ether, polyoxypropylene lauryl ether, polyoxypropylene oleyl ether, polyoxypropylene stearyl ether, polyoxypropylene cetyl ether, polyoxypropylene palmitic ether, polyoxyalkylene alkyl ether, polyoxyalkylene lauryl ether, Polyoxyalkylene oleyl ether, polyoxyalkylene stearyl ether, polyoxy Alkylene cetyl ether, polyoxyalkylene palmitic ether, sorbitan acid mono, di, trialkyl ether, sorbitan acid mono, di, trilauryl ether, sorbitan acid mono, di
- the lithographic printing ink of the present invention preferably contains 0.01% by mass or more of the surfactant, that is, (f) an emulsifier, since dampening water is taken in during printing and the emulsified state is stabilized. More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more. Further, the lithographic printing ink preferably contains 5% by mass or less in which dampening water is excessively taken in during printing and is not compatible with dampening water. More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.
- the lithographic printing ink of the present invention preferably contains (e) a photopolymerization initiator in order to improve ink curability. Further, (e) a sensitizer may be included to assist the effect of the photopolymerization initiator.
- a photopolymerization initiator such as single-molecule direct cleavage type, ion-pair electron transfer type, hydrogen abstraction type, and two-molecule complex system. Can do.
- the (e) photopolymerization initiator used in the present invention preferably generates an active radical species.
- an active radical species include benzophenone, methyl o-benzoylbenzoate, 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, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Dimethyldimethylketanol, benzylmeth
- the sensitizer examples 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) ) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone 1,3-carbon
- the amount of the (e) photopolymerization initiator added to the lithographic printing ink is preferably 0.1 to 20% by mass. (e) By making the addition amount of a photoinitiator into this range, favorable sensitivity and curability can be obtained. (e)
- the addition amount of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more because the lithographic printing ink can obtain good sensitivity. .
- the addition amount is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.
- the addition amount of the sensitizer is preferably 0.1 to 20% by mass with respect to the lithographic printing ink.
- the addition amount of the sensitizer is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more because the lithographic printing ink can obtain good sensitivity. Since the storage stability of the lithographic printing ink is improved, the addition amount is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.
- a polymerization inhibitor examples include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, and pyrogallol.
- the addition amount is preferably 0.001 to 5% by mass with respect to the lithographic printing ink. By setting the addition amount of the polymerization inhibitor within this range, the storage stability of the ink can be obtained.
- additives such as a pigment dispersant, a wax, an antifoaming agent, a transfer improver, and a leveling agent can be used as necessary.
- the lithographic printing ink of the present invention preferably further contains another surfactant.
- another surfactant By containing other surfactant, aggregation of the pigment can be suppressed and the fluidity of the ink can be improved. That is, the other surfactant means (g) a pigment dispersant.
- the (g) pigment dispersant of the present invention preferably contains an anion, that is, an acidic group.
- an acidic group a surfactant having a carboxyl group, a surfactant having a sulfo group, a surfactant having a phosphate group, and the like are more preferable, and a surfactant having a phosphate group. Is most preferably used.
- the azo lake pigment and metal complex pigment preferably used in the present invention contain cations such as Ca 2+ , Ba 2+ , Cu 2+ , and Co 2+ in the components, and these are (g) the acidity of the pigment dispersant.
- the pigment dispersant is adsorbed on the pigment surface.
- the acid value of the pigment dispersant is high, the amount of the acidic group of the (g) pigment dispersant increases in proportion to it, so that the pigment dispersant is more easily adsorbed on the pigment surface. As a result, it is considered that (g) the pigment dispersant covers the pigment surface, and thus aggregation of the pigment is suppressed.
- the pigment dispersant preferably has an acid value of 5 to 200 mgKOH / g.
- the acid value of the pigment dispersant is more preferably 50 mgKOH / g or more, and further preferably 100 mgKOH / g or more. Moreover, it is more preferable that it is 150 mgKOH / g or less.
- the acid value can be determined by “3.1 Neutralization Titration Method” in JIS K0070: 1992 “Testing Method of Acid Value, Saponification Value, Ester Value, Iodine Value, Hydroxyl Value and Unsaponified Product of Chemical Products”. it can.
- Examples of the surfactant having a carboxyl group suitable for the pigment dispersant include sodium octoate, sodium decanoate, sodium laurate, sodium myristate, sodium palmitate, sodium stearate, perfluorononanoic acid, N -Lauroyl sarcosine sodium, sodium cocoyl glutamate and the like.
- Examples of the surfactant having a sulfo group suitable for the pigment dispersant include sodium 1-hexanesulfonate, sodium 1-octanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, perfluoro Butane sulfonic acid, sodium linear alkylbenzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, sodium octyl benzene sulfonate, sodium naphthalene sulfonate, disodium naphthalene disulfonate, trisodium naphthalene trisulfonate, sodium butyl naphthalene sulfonate Etc.
- Examples of the surfactant having a phosphate group suitable for the pigment dispersant include polyoxyethylene alkyl ether phosphate ester, polyoxyethylene tridecyl ether phosphate ester, polyoxyethylene lauryl ether phosphate ester, And polyoxyethylene alkylphenyl ether phosphates.
- polyoxyethylene alkyl ether phosphate, polyoxyethylene tridecyl ether phosphate, and polyoxyethylene lauryl ether phosphate are preferably used.
- the (g) pigment dispersant preferably further has a basic group in addition to the acidic group. It is preferable to have a basic group because the effect of suppressing the aggregation of the pigment can be improved.
- Examples of the basic group of the (g) pigment dispersant include functional groups containing nitrogen elements such as amino groups, amide groups, azo groups, and cyano groups. Pigment dispersants having amino groups are particularly preferably used.
- the amine value of the (g) pigment dispersant is preferably 5 to 50 mgKOH / g.
- the pigment has an acidic group. Since it is easily adsorbed, the effect of suppressing the aggregation of the pigment can be improved.
- an increase in viscosity due to the interaction with the ethylenically unsaturated group-containing resin having an acidic group can be prevented.
- the amine value is in the above range, the aggregation of the pigment is suppressed, and the fluidity of the ink can be improved. As a result, the leveling property of the ink is improved, and the gloss of the printed matter printed using the ink can be improved.
- the amine value of the pigment dispersant (g) can be determined by the method described in “4.1 Potentiometric titration method” of JIS K 7237: 1995 “Testing method for total amine value of amine-based curing agent of epoxy resin”. .
- the content of the pigment dispersant (g) of the present invention is preferably 5 to 50% by mass with respect to 100% by mass of (a) pigment.
- the content of the pigment dispersant is preferably 5 to 50% by mass with respect to 100% by mass of (a) pigment.
- the content of the pigment dispersant is 5% by mass or more, it is preferable in terms of improving the pigment suppression effect, and if it is 50% by mass or less, a decrease in the pigment aggregation suppression effect can be prevented. ,preferable.
- the content of the pigment dispersant is within the above range, the pigment aggregation suppressing effect is enhanced.
- the lithographic printing ink of the present invention preferably contains water.
- the ink contains water, it becomes easy to adjust the viscosity of the ink, the amount of VOC discharged during printing is reduced, and a printed matter can be obtained without imposing a heavy load on the environment.
- the production cost of the lithographic printing ink of the present invention can be reduced.
- the content of water contained in the lithographic printing ink of the present invention is preferably 5% by mass or more. By allowing the water content to fall within such a numerical range, the ink exhibits good water washability and VOC emissions are reduced. More preferably, it is 10 mass% or more.
- the water content is preferably 60% by mass or less because the ink can obtain good sensitivity. More preferably, it is 50 mass% or less.
- the lithographic printing ink of the present invention preferably contains an amine compound.
- the amine compound By including the amine compound, the water solubility of the resin (b) having an ethylenically unsaturated group and a hydrophilic group is improved, and the detergency of the printing ink is improved.
- amine compound a monoamine compound or a polyamine compound having two or more functions can be used.
- a monoamine compound is preferably used because it does not cause a crosslinking reaction with the resin (b) having an ethylenically unsaturated group and a hydrophilic group and the viscosity of the ink is small.
- the molecular weight of the amine compound is preferably 100 or more so that the amine compound does not volatilize during printing.
- the molecular weight of the amine compound is preferably 200 or less in order to facilitate the removal of the amine compound in the drying step after printing.
- the content of the amine compound contained in the lithographic printing ink of the present invention is preferably 0.01% by mass or more, which improves the water solubility of the resin (b) having an ethylenically unsaturated group and a hydrophilic group. More preferably 1% by mass or more.
- the content of the amine compound is preferably 5% by mass or less, more preferably 1% by mass or less.
- amine compound examples include triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, triethanolamine, morpholine and the like.
- the lithographic printing ink of the present invention has a viscosity measured at 25 ° C. and a rotation speed of 0.5 rpm, preferably 10 Pa ⁇ s or more and 100 Pa ⁇ s or less. When the viscosity is within this range, the lithographic printing ink has good fluidity and good transferability.
- the viscosity region suitable for each printing method is preferably 10 Pa ⁇ s to 100 Pa ⁇ s for lithographic printing, and preferably 1 mPa ⁇ s to 50 mPa ⁇ s for inkjet printing, and gravure printing If it is, it will be 50 mPa * s or more and 1000 mPa * s or less, and if it is a flexographic printing use, 200 mPa * s or more and 3000 mPa * s or less are preferable.
- the viscosity is measured using a Brookfield type rotary viscometer, a cone plate type rotary viscometer, or the like.
- the method for producing the lithographic printing ink of the present invention comprises (a) a pigment, (b) a resin having an ethylenically unsaturated group and a hydrophilic group, and other components, which are heated and dissolved at 5 to 100 ° C. as necessary, and then kneadered. And a three-roll mill, a ball mill, a planetary ball mill, a bead mill, a roll mill, an attritor, a sand mill, a gate mixer, a paint shaker, a homogenizer, a self-revolving stirrer and the like. Defoaming is preferably carried out under vacuum or reduced pressure conditions after mixing or dispersing.
- the manufacturing method of the printed matter using the lithographic printing ink of the present invention is as follows. First, the lithographic printing ink of the present invention is applied onto a substrate and then irradiated with an active energy ray to be cured to obtain a printed matter having an ink cured film.
- the substrate include, but are not limited to, art paper, coated paper, cast paper, synthetic paper, newsprint paper, aluminum vapor-deposited paper, metal, polypropylene and polyethylene terephthalate films.
- plastic films such as polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, plastic film laminated paper in which the plastic film is laminated on paper, metal such as aluminum, zinc, copper, etc.
- the metal-deposited paper or metal-deposited plastic film in which the metal is deposited on paper or plastic does not absorb the ink, so the ink cannot be fixed on the substrate, so the ink is instantly cured by irradiating active energy rays.
- the lithographic printing ink of the present invention that can be fixed is preferably used.
- lithographic printing ink of the present invention As a method of applying the lithographic printing ink of the present invention onto a substrate, it is applied to the substrate by a known method such as offset printing (lithographic printing), flexographic printing, gravure printing, screen printing, bar coater, etc. Can do.
- lithographic printing is preferably used because a large amount of lithographic printing ink of the present invention can be printed at high speed and at low cost.
- planographic printing There are two types of planographic printing: a method using a waterless planographic printing plate and a method using a waterless planographic printing plate.
- the waterless lithographic printing plate contains a substrate and at least an ink repellent layer and a heat-sensitive layer provided on the substrate. Either the heat-sensitive layer or the ink repellent layer may be present near the substrate, but it is preferable that the substrate, the heat-sensitive layer, and the ink repellent layer be in this order.
- the substrate is not particularly limited, and known paper, metal, glass, film and the like which are conventionally dimensionally stable and used as a substrate for a printing plate can be used.
- an aluminum plate is particularly preferable because it is dimensionally stable and inexpensive.
- a polyethylene terephthalate film is particularly preferable as a flexible substrate for light printing.
- the heat-sensitive layer of a waterless lithographic printing plate has a function of efficiently absorbing laser light such as infrared rays used for image drawing and converting it into heat (photothermal conversion). It is preferable that the surface is decomposed, the solubility in the developer is increased, or the adhesive force with the ink repellent layer is decreased.
- a heat-sensitive layer can contain, for example, a composition containing a polymer having active hydrogen, an organic complex compound, and a photothermal conversion substance.
- the ink repellent layer desirably has hydrophobicity so as to repel the lithographic printing ink of the present invention and prevent it from adhering to the ink repellent layer.
- the hydrophobicity here means that the contact angle with water is 60 ° or more.
- the ink repellent layer preferably contains a hydrophobic substance.
- silicone rubber, fluorine resin, polyester resin, styrene butadiene rubber, nylon resin, nitrile rubber, polyvinyl acetate, urethane resin, ethylene vinyl acetate copolymer, polybutadiene, polyisoprene, polypropylene, polyethylene, etc. Is mentioned. Among these, it is particularly preferable to use silicone rubber.
- the lithographic printing plate with water includes a substrate, a photosensitive layer provided on the substrate, and a hydrophilic layer optionally provided between the substrate and the photosensitive layer.
- the substrate is not particularly limited, and a dimensionally stable hydrophilic substrate can be used.
- a dimensionally stable hydrophilic substrate can be used.
- an aluminum plate is particularly preferable because it is dimensionally stable and inexpensive.
- the aluminum plate is preferably subjected to surface treatment such as roughening treatment or anodizing treatment. Examples of the method for roughening the surface of the aluminum plate include known methods such as mechanical, electrochemical, and chemical roughening treatments.
- a photosensitive layer of a lithographic printing plate with water by absorbing laser light such as infrared rays used to draw an image, the exposed portion of the photosensitive layer is cured to form a hydrophobic region, and the unexposed portion is It preferably has a function of being removed from the substrate during printing or development.
- a photosensitive layer preferably contains an infrared absorber, a polymerization initiator, and a polymerizable compound having an ethylenically unsaturated group.
- the infrared absorber has a function of converting absorbed infrared rays into heat (photothermal conversion) and a function of generating radicals by being excited by infrared rays and transferring energy to a polymerization initiator.
- the polymerization initiator can generate radicals by light or heat. Further, the generated radical can promote curing of the polymerizable compound having an ethylenically unsaturated group.
- the thickness of the ink cured film on the printed material is preferably 0.1 to 50 ⁇ m.
- active energy rays can be used as long as it has excitation energy necessary for the curing reaction.
- ultraviolet rays or electron beams are preferably used.
- an electron beam apparatus having an energy beam of 100 to 500 eV is preferably used.
- an ultraviolet irradiation device such as a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or an LED is preferably used.
- Curing at a speed of 50 to 150 m / min is preferable from the viewpoint of productivity.
- the substrate easily expands and contracts due to heat generated by active energy rays. Therefore, an electron beam with less heat generation or an ultraviolet irradiation device using LEDs (LED-UV) ) Can be preferably used.
- LED-UV ultraviolet irradiation device using LEDs
- the method for producing a printed material using the lithographic printing ink of the present invention preferably includes a step of drying by heating after the lithographic printing ink of the present invention is applied on a substrate.
- the ink coating can be fixed on the substrate by heating the ink on the substrate and removing volatile components in the ink. Any heating drying method can be used as long as it generates heat energy.
- a hot air dryer or an IR dryer is preferably used, and drying at a temperature of 50 to 250 ° C. for 5 seconds to 30 minutes is preferable from the viewpoint of productivity.
- the method for producing a printed matter using the lithographic printing ink of the present invention includes a step in which the excess ink on the printing press is removed by washing water after the lithographic printing ink of the present invention is applied on a substrate. It is preferable to include. By removing the surplus ink with the washing water, the amount of VOC generated during the work is greatly reduced and the health damage of the worker can be reduced, so that safety is improved.
- the washing water preferably contains 90% by mass or more of the total weight of water. By containing 90% by mass or more of water, the health damage of the worker can be further reduced and the safety is further improved.
- the pH of the washing water is preferably 8 or more and 13 or less. Since the lithographic printing ink of the present invention is weakly acidic, the solubility of the lithographic printing ink in a basic aqueous solution is improved by bringing the pH within such a numerical range. When the pH of the washing water is 8 or more, the ink is easily dissolved and can be washed. More preferably, the pH of the washing water is 9 or more. In addition, it is preferable that the pH of the washing water is 13 or less because damage to printing equipment such as a printing press and a printing plate is reduced. More preferably, the pH of the washing water is 11 or less.
- Pigment I Seikacyanin blue (manufactured by Dainichi Seika Co., Ltd.).
- Resin I An addition reaction of 0.6 equivalent of glycidyl methacrylate (GMA) to a carboxyl group of a copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid, Resin I having an ethylenically unsaturated group and a hydrophilic group was obtained.
- the obtained resin I had a weight average molecular weight of 34,000, an acid value of 102 mgKOH / g, and an iodine value of 2.0 mol / kg.
- Resin II was obtained by addition reaction of 0.95 equivalents of glycidyl methacrylate to the carboxyl group of a copolymer consisting of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid. It was. The obtained resin II had a weight average molecular weight of 39,000, an acid value of 10 mgKOH / g, and an iodine value of 3.1 mol / kg.
- Resin III was obtained by addition reaction of 0.9 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer consisting of 25% by weight methyl methacrylate, 25% by weight styrene, and 50% by weight methacrylic acid. It was.
- the obtained resin III had a weight average molecular weight of 38,000, an acid value of 35 mgKOH / g, and an iodine value of 2.9 mol / kg.
- Resin IV was obtained by addition reaction of 0.8 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer composed of 25% by weight methyl methacrylate, 25% by weight styrene, and 50% by weight methacrylic acid. It was. The obtained resin IV had a weight average molecular weight of 37,000, an acid value of 62 mgKOH / g, and an iodine value of 2.5 mol / kg.
- Resin V was obtained by addition reaction of 0.4 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid. It was.
- the obtained resin V had a weight average molecular weight of 32,000, an acid value of 190 mgKOH / g, and an iodine value of 1.0 mol / kg.
- Resin VI was obtained by addition reaction of 0.2 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer consisting of 25% by weight methyl methacrylate, 25% by weight styrene, and 50% by weight methacrylic acid. It was.
- the obtained resin VI had a weight average molecular weight of 31,000, an acid value of 240 mgKOH / g, and an iodine value of 0.5 mol / kg.
- Resin VII was obtained by addition reaction of 0.1 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid. It was.
- the obtained resin VII had a weight average molecular weight of 30,000, an acid value of 259 mgKOH / g, and an iodine value of 0.25 mol / kg.
- Resin VIII A copolymer composed of 25% by mass of methyl acrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid was obtained.
- the obtained resin VIII had a weight average molecular weight of 29,000, an acid value of 282 mgKOH / g, and an iodine value of 0 mol / kg.
- Resin IX 1.0 equivalent of glycidyl methacrylate (GMA) was added to the carboxyl group of a copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid.
- the obtained resin IX had a weight average molecular weight of 40,000, an acid value of 0 mgKOH / g, and an iodine value of 3.2 mol / kg.
- Reactive diluent I “Miramer” (registered trademark) M340 (manufactured by MIWON)
- Reactive Diluent II “Miramer” (registered trademark) M4004 (manufactured by MIWON)
- Photoinitiator I “Irgacure” (registered trademark) 907 (manufactured by BASF)
- Sensitizer I Diethylaminobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Polymerization inhibitor I p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.)
- Additive I Lauryl acrylate (Wako Pure Chemical Industries, Ltd.)
- Amine compound I Diethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.).
- the weight average molecular weight of the resin is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase.
- the column was Shodex KF-803, and the weight average molecular weight was calculated in terms of polystyrene.
- ⁇ Lithographic printing aptitude test> A waterless lithographic printing plate (TAN-E, manufactured by Toray Industries, Inc.) was mounted on an offset printing machine (Oliver 266EPZ, manufactured by Sakurai Graphic System), and the compositions shown in Examples 1 to 8 and Comparative Examples 1 and 2 were used. Printing was performed on 10,000 coated papers using each ink, and printability and printed matter were evaluated.
- a photosensitive resin plate (“Trealeaf (registered trademark)" DWF95DIII, manufactured by Toray Industries, Inc.) is mounted on a flexographic printing tester (flexiproof 100, manufactured by PrintCoat Instruments), and the number of anilox rolls is 400. Then, using each of the inks of Examples 9 to 11 and Comparative Examples 3 to 4, a PET (polyethylene terephthalate) film (manufactured by Mitsubishi Chemical Corporation, “Novaclear (registered trademark)”, thickness: 100 ⁇ m) was printed. .
- the printed matter was irradiated with ultraviolet rays at a belt conveyor speed of 0 to 150 m / min using an ultraviolet irradiation device (120 W / cm, one ultra-high pressure meta-hara lamp) manufactured by USHIO Corporation.
- the belt conveyor speed was determined when the ink on the printed material was sufficiently cured and the cellophane adhesive tape (“Cellotape” (registered trademark) No. 405) was adhered and peeled, but could not be peeled off from the coated paper.
- the sensitivity was judged to be extremely good.
- Example 1 The ink composition shown in Table 1 was weighed and passed through gap 1 three times using a three-roll mill “EXAKT” (registered trademark) M-80S (manufactured by EXAKT) to obtain a lithographic printing ink.
- EXAKT registered trademark
- M-80S manufactured by EXAKT
- the obtained lithographic printing ink was subjected to a lithographic printing aptitude test as described above, and the sensitivity, water washability, water resistance of the film and soil resistance were evaluated. The results are shown in Table 1.
- the viscosity of the prepared lithographic printing ink was appropriate as 51 Pa ⁇ s.
- the sensitivity was 130 m / min at the belt conveyor speed and was very good.
- the water washability was that all the ink remaining on the roller could be washed with a single water wash.
- As for the water resistance of the film no elution of ink from the ink cured film was observed for up to 24 hours in water at 25 ° C.
- the ground stain resistance was very good with a reflection density of 0.2 at the non-image area.
- Example 2 to 7 Resins II to VII were blended in place of Resin I, and the same operations and sensitivities as in Example 1 except that the ethylenically unsaturated group concentration (iodine value) and hydrophilic group concentration (acid value) were as shown in Table 1.
- the water washability, the water resistance of the film and the soil resistance were evaluated. As the ethylenically unsaturated group concentration increases, the sensitivity and the water resistance of the membrane tend to improve, and as the hydrophilic group concentration increases, the viscosity increases and the water washability and soil resistance tend to improve. It was. More preferable results were obtained in Examples 3 to 6 and particularly preferable results in Examples 4 and 5 as lithographic printing inks having sensitivity, water washability, water resistance of the film, and stain resistance.
- Example 8 Except that lauryl acrylate was added as an additive, the same operation as in Example 1 was performed, and the sensitivity, water washability, water resistance of the film and soil resistance were evaluated.
- the viscosity of the produced lithographic printing ink was appropriate as 47 Pa ⁇ s.
- the sensitivity was 125 m / min at the belt conveyor speed, which was very good.
- the water washability was that all the ink remaining on the roller could be washed with a single water wash.
- As for the water resistance of the film no elution of ink from the ink cured film was observed for up to 24 hours in water at 25 ° C.
- the ground stain resistance was very good with a reflection density of 0.1 at the non-image area.
- Example 9 The ink compositions shown in Table 2-1 were weighed and mixed and dispersed using a paint conditioner to obtain a printing ink.
- the obtained ink was subjected to a flexographic printing aptitude test to evaluate sensitivity, water washability, and water resistance of the film.
- the results are shown in Table 2-1.
- the viscosity of the produced printing ink was appropriate at 1420 mPa ⁇ s.
- the sensitivity was 120 m / min at the belt conveyor speed, which was very good.
- the water washability was such that the ink on the printed material could be removed with a single wash.
- the water resistance of the film no elution of ink from the ink cured film was observed for up to 24 hours in water at 25 ° C.
- Examples 10 and 11 In the same manner as in Example 9, except that resin III or IV was added instead of resin I, and the ethylenically unsaturated group concentration (iodine value) and hydrophilic group concentration (acid value) were as shown in Table 2-1. Sensitivity, water washability, and water resistance of the membrane were evaluated. As the ethylenically unsaturated group concentration increases, the sensitivity and the water resistance of the membrane tend to improve, and as the hydrophilic group concentration increases, the water washability tends to improve.
- Example 12 An ink was prepared in the same manner as in Example 9 except that the ink composition shown in Table 2-1 was used and the flexo printability evaluation was changed to gravure printability evaluation, and the sensitivity, water washability, and water resistance of the film were evaluated. Went. The viscosity of the produced printing ink was appropriate at 570 mPa ⁇ s. The sensitivity was 120 m / min at the belt conveyor speed, which was very good. The water washability was such that the ink on the printed material could be removed with a single wash. As for the water resistance of the film, no elution of ink from the ink cured film was observed for up to 24 hours in water at 25 ° C.
- Examples 13 and 14 The ink was prepared in the same manner as in Example 12 except that the ink composition shown in Table 2-1 was used and the ethylenically unsaturated group concentration (iodine value) and hydrophilic group concentration (acid value) were as shown in Table 2-1.
- the ethylenically unsaturated group concentration iodine value
- hydrophilic group concentration acid value
- Example 6 The same operation and sensitivity as in Example 12 except that the ink composition shown in Table 2-2 was used, the resin weight average molecular weight was 40,000, the acid value was 0 mgKOH / g, and the iodine value was 3.2 mol / kg. And the water resistance of the membrane was evaluated. The viscosity of the prepared ink was as low as 41 mPa ⁇ s, which was inappropriate for gravure printing. The sensitivity was 140 m / min at the belt conveyor speed, which was very good. Further, regarding the water resistance of the film, no elution of ink from the ink cured film was observed for up to 24 hours in water at 25 ° C. However, with regard to water washability, ink residues were observed even after multiple washings.
- Example 15 An ink was prepared in the same manner as in Example 9 except that the ink composition shown in Table 2-1 was used and the flexo printing suitability evaluation was changed to inkjet printing suitability evaluation, and the sensitivity, water washability, and water resistance of the film were evaluated. Went. The sensitivity was 120 m / min at the belt conveyor speed, which was very good. The water washability was such that the ink on the printed material could be removed with a single wash. As for the water resistance of the film, no elution of ink from the ink cured film was observed for up to 24 hours in water at 25 ° C.
- Examples 16 and 17 The same operation ink as in Example 15 except that the ink composition shown in Table 2-1 was used, and the ethylenically unsaturated group concentration (iodine value) and hydrophilic group concentration (acid value) were as shown in Table 2-1. Prepared and evaluated for sensitivity, water washability, and water resistance of the membrane. As the ethylenically unsaturated group concentration increases, the sensitivity and the water resistance of the membrane tend to improve, and as the hydrophilic group concentration increases, the water washability tends to improve.
- Example 7 The same operation and sensitivity as in Example 15 except that the ink composition shown in Table 2-2 was used, the resin weight average molecular weight was 29,000, the acid value was 282 mgKOH / g, and the iodine value was 0 mol / kg.
- the water resistance of the film was evaluated.
- the viscosity of the ink thus prepared was as high as 235 mPa ⁇ s and was not suitable for ink jet printing.
- the water washability was such that the ink on the printed material could be removed with a single wash.
- the sensitivity was 40 m / min at the belt conveyor speed, which was insufficient.
- the water resistance of the film ink was eluted from the ink-cured film in water at 25 ° C. by 12 hours.
- Example 8 The same operation and sensitivity as in Example 15 except that the ink composition shown in Table 2-2 was used, and the weight average molecular weight of the resin was 40,000, the acid value was 0 mgKOH / g, and the iodine value was 3.2 mol / kg. And the water resistance of the membrane was evaluated. The viscosity of the prepared ink was as low as 0.7 mPa ⁇ s, which was inappropriate for ink jet printing. The sensitivity was 130 m / min at the belt conveyor speed and was very good. Further, regarding the water resistance of the film, no elution of ink from the ink cured film was observed for up to 24 hours in water at 25 ° C. However, with regard to water washability, ink residues were observed even after multiple washings. The composition of each component used in each example and each comparative example and the results of evaluation are shown in the table.
- Multifunctional (meth) acrylate 1 A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate “Miramer” (registered trademark) M340 (manufactured by MIWON) with hydroxyl group, hydroxyl value 115 mgKOH / g, molecular weight 298
- Polyfunctional (meth) acrylate 2 A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate “Aronix” (registered trademark) M-306 (manufactured by Toa Gosei Co., Ltd.) with hydroxyl group, hydroxyl value 171 mg KOH / g, molecular weight 298
- Polyfunctional (meth) acrylate 3 A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate “Aronix” (registered trademark) M-403 (manufactured by Toa Gosei Co., Ltd.) with hydroxyl group, hydroxyl value 53 mgKOH / g, molecular weight 524
- Multifunctional (meth) acrylate 4 Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate “Aronix” (registered trademark) M-402 (manufactured by Toa Gosei Co., Ltd.) with hydroxyl group, hydroxyl value 28 mgKOH / g, molecular weight 524
- Polyfunctional (meth) acrylate 5 glycerin dimethacrylate “NK ester” (registered trademark) 701 (manufactured by Shin-Nakamura Chemical Co., Ltd.) with hydroxyl group, hydroxyl value 240 mgKOH / g, molecular weight 228
- Polyfunctional (meth) acrylate 6 pentaerythritol tetraacrylate ethylene oxide modified product “Miramer” (registered trademark) M4004 (manufactured by MIWON) No hydroxyl group, molecular weight 571
- Resin 1 0.55 equivalents of glycidyl methacrylate was added to the carboxyl group of a copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid. A resin 1 having a saturated group and a hydrophilic group was obtained. The obtained resin 1 had a weight average molecular weight of 34,000, an acid value of 105 mgKOH / g, and an iodine value of 2.0 mol / kg.
- Resin 2 Addition reaction of 0.5 equivalents of glycidyl methacrylate to the carboxyl group of a copolymer consisting of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid A resin 2 having a saturated group and a hydrophilic group was obtained. The obtained resin 2 had a weight average molecular weight of 53,000, an acid value of 114 mgKOH / g, and an iodine value of 1.8 mol / kg.
- Resin 3 A resin 3 having a hydrophilic group composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid was obtained.
- the obtained resin 3 had a weight average molecular weight of 24,000 and an acid value of 210 mgKOH / g.
- Resin 4 VS-1057 (manufactured by Starlight PMC, acrylic resin, hydrophilic group, weight average molecular weight: 18000, acid value: 40 mgKOH / g)
- Resin 5 having a hydrophilic group composed of 25% by mass of methyl methacrylate, 20% by mass of styrene, and 55% by mass of methacrylic acid was obtained.
- the obtained resin 5 had a weight average molecular weight of 9,000 and an acid value of 262 mgKOH / g.
- Resin 6 Isodap (Daiso Chemicals, diallyl phthalate resin, no hydrophilic group, weight average molecular weight 30,000, acid value 0 mgKOH / g)
- Polymerization inhibitor 1 p-methoxyphenol (Wako Pure Chemical Industries, Ltd.)
- the weight average molecular weight of the resin is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase.
- the column was Shodex KF-803, and the weight average molecular weight was calculated in terms of polystyrene.
- Viscosity A cylinder spindle No. 4 was mounted on a Brookfield B-type viscometer DV-II manufactured by Brookfield, and the viscosity of the lithographic ink varnish at 25 ° C. and 0.5 rpm was measured.
- the viscosity is preferably from 10 to 400 Pa ⁇ s, more preferably from 50 to 300 Pa ⁇ s, and even more preferably from 100 to 250 Pa ⁇ s, since both the stain resistance and fluidity of the lithographic printing ink are improved.
- a waterless lithographic printing plate (TAN-E, manufactured by Toray Industries, Inc.) was mounted on an offset printing machine (Oliver 266EPZ, manufactured by Sakurai Graphic System), and Examples 18 to 26, Reference Examples 1 to 3 and Comparative Example 9 were used.
- Each evaluation method is as follows.
- a lithographic printing plate with water (XP-F, manufactured by Fuji Film Co., Ltd.) is mounted on an offset printing machine (Oliver 266EPZ, manufactured by Sakurai Graphic System), and an etchant (SOLAIA-505, T & K TOKA) in dampening water.
- Oliver 266EPZ manufactured by Sakurai Graphic System
- SOLAIA-505, T & K TOKA an etchant
- Using a device 120 W / cm, one ultra-high pressure meta-hara lamp), ultraviolet rays were applied at a belt conveyor speed of 80 m / min to cure the ink and obtain a printed matter.
- varnishes 2-5 the same operation as varnish 1 was performed except that the type of polyfunctional (meth) acrylate having a hydroxyl group was changed to polyfunctional (meth) acrylate 2-5 as shown in Table 3. Created with.
- Varnishes 6 to 8 were prepared by performing the same operation as varnish 1 except that the content of polyfunctional (meth) acrylate 1 having a hydroxyl group was changed as shown in Table 3. The higher the content of the polyfunctional (meth) acrylate having a hydroxyl group, the higher the varnish viscosity and the lower the tan ⁇ value.
- Varnishes 9 to 13 were prepared by performing the same operation as varnish 1 except that the resin type was changed to resins 2 to 6 as shown in Table 3.
- the varnish viscosity was less than 10 Pa ⁇ s.
- Example 18 ⁇ Preparation of waterless lithographic printing ink>
- varnish 1, pigment 1, photopolymerization initiators 1 and 2, sensitizer 1, additive 1 and wax 1 were weighed, and a three-roll mill “EXAKT” (registered trademark) M-80S ( Using EXAKT), a lithographic printing ink was obtained by passing the roller gap 1 twice at a speed of 500 rpm. About the obtained ink, the waterless printing test was done and the performance was evaluated. The results are shown in Table 4.
- the prepared lithographic printing ink had a viscosity of 58 Pa ⁇ s at 0.5 rpm.
- the reflection density at the non-image area was 0.04, and the soil resistance was very good.
- the obtained printed matter had a solid portion with a gloss value of 38 and was very good.
- Example 19 to 22 ⁇ Types of polyfunctional (meth) acrylate having a hydroxyl group> Lithographic printing inks of Examples 19 to 22 were prepared in the same manner as in Example 18 except that varnish 1 was changed to varnishes 2 to 5 with the composition shown in Table 4. The higher the hydroxyl value and molecular weight of the polyfunctional (meth) acrylate having a hydroxyl group constituting the varnishes 2 to 5, the higher the viscosity of the ink, and the tendency to improve the stain resistance. On the other hand, the gloss value in the solid portion of the printed matter tended to decrease.
- Examples 23 to 25 ⁇ Content of polyfunctional (meth) acrylate having a hydroxyl group> Lithographic printing inks of Examples 23 to 25 were prepared in the same manner as in Example 18 except that the varnish 1 was changed to varnishes 6 to 8 with the composition shown in Table 4. The prepared lithographic printing ink tends to increase in viscosity as the content of the polyfunctional (meth) acrylate having a hydroxyl group constituting the varnishes 6 to 8 increases, and the soil resistance tends to improve. It was. On the other hand, the gloss value in the solid portion of the printed matter tended to decrease.
- Example 26 Reference Examples 1 to 3, and Comparative Example 9
- ⁇ Types of resins having hydrophilic groups> With the composition shown in Table 4, the same operations as in Example 18 were performed except that varnish 1 was changed to varnishes 9 to 13, and lithographic printing inks of Example 26, Reference Examples 1 to 3 and Comparative Example 9 were prepared. did.
- the prepared lithographic printing ink has a tendency to increase in viscosity and to improve the soil resistance as the acid value and molecular weight of the resin constituting the varnishes 9 to 13 increase.
- the gloss in the solid portion of the printed matter obtained tends to decrease.
- the viscosity of the ink was low and the soil resistance was insufficient.
- Example 27 ⁇ Preparation of lithographic printing ink with water> A lithographic printing ink of Example 27 was prepared in the same manner as in Example 18 except that the composition shown in Table 5 was used and that emulsifier 1 was added.
- the prepared lithographic printing ink had a viscosity of 66 Pa ⁇ s at 0.5 rpm.
- the reflection density at the non-image area was 0.02, and the soil resistance was very good.
- the obtained printed matter had a solid portion gloss value of 36 and was very good.
- Examples 28 to 29, Reference Example 4 and Comparative Example 10 ⁇ Preparation of water-based lithographic printing ink with varnish change>
- the lithographic printing inks of Examples 28 to 29, Reference Example 4 and Comparative Example 10 were prepared in the same manner as in Example 27 except that the varnish was changed with the composition shown in Table 5.
- the prepared lithographic printing ink was less likely to take up fountain solution as the acid value of the resin constituting the varnish increased, and the soil resistance was liable to decrease (Reference Example 4).
- the soil resistance was improved because the hydroxyl value of the polyfunctional (meth) acrylate having a hydroxyl group composing the varnish was decreased and the ink became suitable hydrophobicity (Examples 28 and 29).
- the ink had a low viscosity, and the soil resistance was insufficient.
- Pigment A (Azo lake pigment) “Lake Red” (registered trademark) C # 405 (F) (manufactured by Dainichi Seika Kogyo Co., Ltd.)
- Pigment B (Azo lake pigment) “Seika First” (registered trademark) Carmine 1476T-7 (manufactured by Dainichi Seika Kogyo Co., Ltd.)
- Pigment C (Azo lake pigment) 430 Brilliant Bordeaux 10B (manufactured by Dainichi Seika Kogyo Co., Ltd.)
- Pigment D (Azo lake pigment) “LIONOL” (registered trademark) RED TT-4801G (manufactured by Toyo Ink Co., Ltd.)
- Pigment E (phthalocyanine copper complex) “Chromofine” (registered trademark) ⁇ -type blue PB-15: 3 (manufactured by Dainichi Seika Kogyo Co., Ltd.
- Pigment dispersant A “DISPERBYK” (registered trademark) -111 Acid value: 129 mg KOH / g Phosphoric acid group-containing anionic surfactant (manufactured by Big Chemie Japan Co., Ltd.)
- Pigment dispersant B “Plisurf” (registered trademark) A212C Acid value: 110 mg KOH / g Anionic surfactant containing phosphoric acid group (Daiichi Kogyo Seiyaku Co., Ltd.)
- Pigment dispersant C “Disparon” (registered trademark) 1850 Acid value: 73 mg KOH / g Phosphoric acid group-containing anionic surfactant (manufactured by Kashiwagi Kasei Co., Ltd.)
- Pigment dispersant D “Plisurf” (registered trademark) A208N Acid value: 145 mg KOH / g Phosphoric acid group-containing anionic surfactant (Daiichi Ko
- Resin A (containing ethylenically unsaturated group and hydrophilic group (acidic group)): 0 with respect to the carboxyl group of the copolymer of 25% by mass of methyl methacrylate, 25% by mass of styrene and 50% by mass of methacrylic acid .6 addition equivalent of glycidyl methacrylate.
- a solution of methyl methacrylate, styrene, methacrylic acid, and azoisobutyronitrile dissolved in a solvent kept at 75 ° C. is slowly dropped. After 5 hours of reaction, glycidyl methacrylate, tetrabutylammonium chloride, and p-methoxyphenol are dissolved. It is obtained by slowly dropping and reacting for 3 hours.
- Resin B (containing ethylenically unsaturated groups and hydrophilic (acidic group) groups): with respect to the carboxyl group of the copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid
- Resin C (containing ethylenically unsaturated groups and hydrophilic groups (acidic groups)): 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid based on the carboxyl group of the copolymer
- Resin D (containing ethylenically unsaturated group, hydrophilic group (acidic group)): with respect to a carboxyl group of a copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid
- An addition reaction of 0.8 equivalent of glycidyl methacrylate Weight average molecular weight 37,000, acid value 62 mgKOH / g, iodine value 2.5 mol / kg.
- Resin E (containing ethylenically unsaturated group, hydrophilic group (acidic group)): with respect to the carboxyl group of the copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid
- Resin F (containing ethylenically unsaturated group, hydrophilic group (acidic group)): with respect to the carboxyl group of the copolymer composed of 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid
- Resin G (containing ethylenically unsaturated groups and hydrophilic groups (acidic groups)): 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid based on the carboxyl group of the copolymer
- Resin H (containing only hydrophilic groups (acidic groups): a copolymer comprising 25% by mass of methyl acrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid. Weight average molecular weight 29,000, acid value 282 mgKOH / g, iodine value 0 mol / kg.
- Resin I (containing only ethylenically unsaturated groups): 1.0 equivalent of glycidyl methacrylate with respect to the carboxyl group of a copolymer consisting of 25% by weight methyl methacrylate, 25% by weight styrene, and 50% by weight methacrylic acid Is an addition reaction.
- Reactive diluent A (containing ethylenically unsaturated groups and hydrophilic groups): “Miramer” (registered trademark) M340 pentaerythritol triacrylate (manufactured by MIWON)
- Reactive diluent B (containing only ethylenically unsaturated groups): “Miramer” (registered trademark) M280 polyethylene glycol diacrylate (manufactured by MIWON)
- Reactive diluent C (containing only ethylenically unsaturated groups): “Miramer” (registered trademark) M300 trimethylolpropane triacrylate (manufactured by MIWON)
- Photoinitiator A “Irgacure” (registered trademark) 907 (manufactured by BASF)
- Sensitizer A Diethylaminobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)
- the elastic modulus (elasticity) was measured, and the value of the loss tangent tan ⁇ represented by the ratio of the loss elastic modulus to the storage elastic modulus was calculated.
- tan ⁇ is 1 or more, it has fluidity, when it is 2.0 or more, fluidity is good, and when it is 3.0 or more, fluidity is extremely good.
- ⁇ Printing test> A waterless lithographic printing plate (TAN-E, manufactured by Toray Industries, Inc.) is mounted on an offset printing machine (Oliver 266EPZ, manufactured by Sakurai Graphic System) and coated with each ink having the composition shown in Tables 6-14. Printing was performed on 10,000 sheets of paper, and printability and printed matter were evaluated. Each evaluation method is as follows.
- the printed matter was irradiated with ultraviolet rays at a belt conveyor speed of 0 to 150 m / min using an ultraviolet irradiation device (120 W / cm, one ultra-high pressure meta-hara lamp) manufactured by USHIO Corporation.
- the belt conveyor speed was determined when the ink on the printed material was sufficiently cured and the cellophane pressure-sensitive adhesive tape (“Cellotape” (registered trademark) No. 405) was adhered and peeled, but could not be peeled off from the coated paper.
- the sensitivity was judged to be extremely good.
- the gloss value of the ink cured film on the printed material was measured at a measurement angle of 60 degrees using a precision gloss meter GM-26D (manufactured by Murakami Color Research Laboratory Co., Ltd.). A gloss value of less than 30 is poor, a gloss value of 30 or more is good, and a gloss value of 35 or more is very good.
- Example 30 The ink composition shown in Table 6 was weighed and lithographic printing ink was obtained by using a three-roll mill “EXAKT” (registered trademark) M-80S (manufactured by EXAKT) three times with a gap of 10 ⁇ m.
- EXAKT registered trademark
- M-80S manufactured by EXAKT
- the obtained lithographic printing ink was subjected to a fluidity test and a printing test as described above to evaluate ink fluidity, sensitivity, water washability, glossiness, and soil resistance. The results are shown in Table 6.
- the fluidity of the produced lithographic printing ink was very good with a loss tangent tan ⁇ of 3.67.
- the sensitivity was 130 m / min at the belt conveyor speed and was very good.
- the water washability was that all the ink remaining on the roller could be washed with a single water wash. As for water resistance, no elution of ink was observed until 24 hours.
- the gloss value was very good at 40.
- the ground stain resistance was very good with a reflection density of 0.05 at the non-image area.
- Examples 31 to 36 ⁇ Types of pigments> The same operation as in Example 30 was performed except that the types of pigments were as shown in Table 6, and the fluidity test, sensitivity, water washability, glossiness, and soil resistance were evaluated. In any of the lithographic printing inks of Examples 31 to 36, the flowability test, sensitivity, water washability, water resistance, glossiness, and soil resistance were very good.
- Example 37 to 42 ⁇ Types of pigment dispersant> The same operation as in Example 30 was performed except that the type of the pigment dispersant was changed as shown in Table 7, and the fluidity test, sensitivity, water washability, glossiness, and soil resistance were evaluated. In any of the lithographic printing inks of Examples 37 to 42, the fluidity test, sensitivity, water washability, water resistance, glossiness, and background stain resistance were generally good. For Examples 37 and 39 having acid values of 110 mgKOH / g and 145 mgKOH / g, the results of ink fluidity and gloss were very good, and the acid values of the pigment dispersants were 10 mgKOH / g and 180 mgKOH / g, respectively. In Examples 41 and 42, the fluidity of the ink was relatively lowered, and the glossiness was good.
- Example 43 to 47 ⁇ Content of pigment dispersant> The same operation as in Example 30 was performed except that the content of the pigment dispersant was as shown in Table 8, and the fluidity test, sensitivity, water washability, water resistance, glossiness, and soil resistance were evaluated. . In any of the lithographic printing inks of Examples 43 to 47, the fluidity test, the sensitivity, the water washability, the water resistance, the glossiness, and the stain resistance were generally good.
- Example 45 in which the content is 30% with respect to the pigment, the fluidity test and gloss results are very good, and the content of the pigment dispersant is 3% and 60% with respect to the pigment, respectively. For 46 and 471, the fluidity of the ink was relatively lowered, and the glossiness was good.
- Example 48 The same operation as in Example 30 was performed except that the type of resin was as shown in Table 9, and the fluidity test, sensitivity, water washability, water resistance, glossiness, and soil resistance were evaluated.
- the acid value of the resin was 10 mg KOH / g
- the fluidity of the ink was relatively lowered, resulting in good glossiness.
- the water washability was B.
- the soil dirt resistance was slightly poor.
- Example 53 in which the iodine value of the resin was 0.25 mol / kg, the ink was low in curing, the sensitivity was good, and the water resistance was B.
- the flowability test, sensitivity, water washability, water resistance, glossiness, and stain resistance were generally very good.
- Example 54 The same operation as in Example 30 was performed except that the type of the pigment dispersant was changed as shown in Table 10, and the fluidity test, sensitivity, water washability, water resistance, glossiness, and soil resistance were evaluated. As a result of measuring the fluidity of the produced ink, the loss tangent tan ⁇ was 0.95, and the fluidity was lowered. The sensitivity, water washability, water resistance, and soil resistance were very good, but the gloss value was greatly reduced to 24, and the glossiness was poor.
- Example 55 The same operation as in Example 30 was performed except that the content of the pigment dispersant was as shown in Table 10, and the fluidity test, sensitivity, water washability, water resistance, glossiness, and soil resistance were evaluated. .
- the loss tangent tan ⁇ was 0.88, and the fluidity was lowered. Sensitivity, water washability, water resistance, and dirt resistance were good, but the gloss value was greatly reduced to 21 and the glossiness was poor.
- Example 11 The same operation as in Example 30 was conducted except that the type of the resin / reactive diluent and the content of the pigment dispersant were as shown in Table 10, and the fluidity test, sensitivity, water washability, water resistance, glossiness and The soil resistance was evaluated.
- the prepared ink had good water washability and stain resistance, but as a result of measuring the fluidity, the loss tangent tan ⁇ was 0.84 and the fluidity was lowered.
- As a result of measuring the sensitivity it was 75 m / min at the belt conveyor speed, and the sensitivity was insufficient.
- the water resistance elution of ink was observed in 6 hours, and the water resistance was C. Further, the gloss value was greatly reduced to 19, and the glossiness was poor.
- Example 12 The same operation as in Example 30 was carried out except that the types of the resin / reactive diluent were as shown in Table 10, and evaluation of fluidity test, sensitivity, water washability, water resistance, glossiness, and soil resistance was performed. Went. As a result of measuring the fluidity of the produced ink, the loss tangent tan ⁇ was 1.24, and the fluidity was lowered. The sensitivity was good, but the water washability was C, with ink residue remaining even after three water washes. Regarding glossiness, the gloss value was 27, which was poor. The soil stain resistance was poor with a reflection density of 0.75 at the non-image area.
- Example 56 The ink composition shown in Table 11 was weighed, and lithographic printing ink was obtained by using a three roll mill “EXAKT” (registered trademark) M-80S (manufactured by EXAKT) three times with a gap of 10 ⁇ m.
- EXAKT registered trademark
- M-80S manufactured by EXAKT
- the obtained lithographic printing ink was subjected to a fluidity test and a printing test as described above, and the ink fluidity, sensitivity, water washability, water resistance, glossiness and background stain resistance were evaluated. The results are shown in Table 11.
- the fluidity of the prepared lithographic printing ink was very good with a loss tangent tan ⁇ of 3.27.
- the sensitivity was 130 m / min at the belt conveyor speed and was very good.
- the water washability was that all the ink remaining on the roller could be washed with a single water wash.
- As for water resistance no elution of ink was observed until 24 hours.
- the gloss value was 42, which was very good.
- the ground stain resistance was very good with a reflection density of 0.05 at the non-image area.
- Example 57 to 61 ⁇ Types of pigment> The same operation as in Example 56 was carried out except that the types of pigments were as shown in Table 11, and the fluidity test, sensitivity, water washability, water resistance, glossiness and stain resistance were evaluated. In Examples 60 and 61 in which the carbon black dibutyl phthalate absorption amount was 100 and 93, the surface roughness of the printed matter was relatively large, and thus the glossiness was good. In Examples 57 to 59, the flow test, sensitivity, water washability, water resistance, glossiness, and soil resistance were very good in any of the lithographic printing inks.
- Example 62 to 67 ⁇ Type of resin> The same operation as in Example 56 was performed except that the type of resin was as shown in Table 12, and the fluidity test, sensitivity, water washability, water resistance, glossiness, and soil resistance were evaluated.
- the acid value of the resin B is 10 mgKOH / g
- the fluidity of the ink was relatively lowered, resulting in good glossiness.
- the acid value of the resin was low, the water washability was low. It became B, and soil dirt resistance was also somewhat poor.
- Example 67 in which the iodine value of the resin G was 0.25 mol / kg, the ink was low in curing, the sensitivity was good, and the water resistance was B.
- the results were generally very good in terms of fluidity test, sensitivity, water washability, water resistance, glossiness, and soil resistance.
- Example 68 to 72 ⁇ Types of pigment dispersant> The same operation as in Example 56 was conducted except that the type of the pigment dispersant was changed as shown in Table 13, and the fluidity test, sensitivity, water washability, water resistance, glossiness, and soil resistance were evaluated. In Examples 71 and 72 in which the pigment dispersant had an amine value of 61 mgKOH / g and 4 mgKOH / g, the fluidity of the ink was relatively lowered, and thus the glossiness was good. In Examples 68 to 70, in all the lithographic printing inks, the fluidity test, the sensitivity, the water washability, the water resistance, the glossiness, and the stain resistance were generally good.
- Example 73 The same operation as in Example 56 was carried out except that the types of pigments were as shown in Table 14, and the fluidity test, sensitivity, water washability, water resistance, glossiness and soil resistance were evaluated. As a result of measuring the fluidity of the produced ink, the loss tangent tan ⁇ was 0.95, and the fluidity was lowered. The sensitivity, water washability, water resistance, and soil resistance were very good, but the gloss value was greatly reduced to 24, and the glossiness was poor.
- Example 13 The same operation as in Example 56 was carried out except that the type of resin was as shown in Table 14, and the fluidity test, sensitivity, water washability, water resistance, glossiness and soil resistance were evaluated. The fluidity test, water washability, and soil resistance of the ink prepared were good. However, as a result of measuring the sensitivity, the belt conveyor speed was 75 m / min, and the sensitivity was insufficient. As a result of measuring the water resistance, elution of ink was observed in 6 hours, and the water resistance was C.
- Example 14 The same operation as in Example 56 was carried out except that the type of resin was as shown in Table 14, and the fluidity test, sensitivity, water washability, water resistance, glossiness and soil resistance were evaluated.
- the loss tangent tan ⁇ was 1.24, and the fluidity was lowered.
- the sensitivity and water resistance were good, but the water washability was C, with ink residue remaining even after three water washes.
- the gloss value was 27, which was poor.
- the soil stain resistance was poor with a reflection density of 0.75 at the non-image area.
- Example 74 Using the lithographic printing ink having the same composition as in Example 1 shown in Table 1, the following lithographic printing suitability test and curing test were conducted to evaluate sensitivity, water resistance of the film, and warpage of the substrate.
- a waterless lithographic printing plate (TAN-E, manufactured by Toray Industries, Inc.) is mounted on an offset printing machine (Oliver 266EPZ, manufactured by Sakurai Graphic System), and a polyethylene terephthalate film using ink having the composition shown in Example 1 is used. Printing was performed on 10,000 sheets.
- the printed matter was irradiated with ultraviolet rays at a belt conveyor speed of 0 to 150 m / min using an ultraviolet irradiation device (120 W / cm, one ultra-high pressure meta-hara lamp) manufactured by USHIO Co., Ltd.
- the belt conveyor speed was determined when the ink on the printed material was sufficiently cured and the cellophane adhesive tape ("Cellotape" (registered trademark) No. 405) was adhered and peeled, but could not be peeled off from the polyethylene terephthalate film. .
- the sensitivity was insufficient when the belt conveyor speed was less than 100 m / min, the sensitivity was good when it was 100 m / min or more and less than 120 m / min, and the sensitivity was judged to be very good when it was 120 m / min or more.
- the sensitivity was 130 m / min at the belt conveyor speed and was very good. Furthermore, the water resistance of the film was such that no ink was eluted from the ink cured film in water at 25 ° C. for up to 24 hours. However, warping due to thermal expansion and contraction was visually observed in the polyethylene terephthalate film after ultraviolet irradiation.
- Example 75 Except that USHIO Co., Ltd. ultraviolet irradiation device (120 W / cm, one ultra-high pressure meta-hara lamp) was changed to Panasonic Device Sunx Co., Ltd. ultraviolet irradiation device (5 W / cm 2 , LED-UV), In the same manner as in Example 74, a lithographic printing suitability test and a curing test were conducted to evaluate sensitivity, water resistance of the film, and warpage of the substrate.
- the sensitivity was 120 m / min at the belt conveyor speed, which was very good. Furthermore, the water resistance of the film was such that no ink was eluted from the ink cured film in water at 25 ° C. for up to 24 hours. Further, no warp due to thermal expansion or contraction was observed in the polyethylene terephthalate film after LED-UV irradiation.
- Example 76 The polyethylene terephthalate film was changed to aluminum vapor-deposited paper, and the ultraviolet irradiation device (120 W / cm, one ultra-high pressure meta-hara lamp) manufactured by USHIO Co., Ltd. was used as the electron beam irradiation device “Min-EB” (100 eV) manufactured by USHIO Co., Ltd.
- the lithographic printing suitability test and the curing test were carried out in the same manner as in Example 74 except that the change was made to), and the sensitivity, water resistance of the film, and warpage of the substrate were evaluated.
- the sensitivity was 130 m / min at the belt conveyor speed and was very good. Furthermore, the water resistance of the film was such that no ink was eluted from the ink cured film in water at 25 ° C. for up to 24 hours. Further, no warp due to thermal expansion or contraction was observed in the aluminum vapor-deposited paper after electron beam irradiation.
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Abstract
Description
本発明の平版印刷用インキは、(a)顔料、およびワニス成分からなる。ワニス成分は、(b)エチレン性不飽和基および親水性基を有する樹脂を含む。またワニス成分として、任意に(c)反応性希釈剤、(d)インキ付着抑制成分、(e)光重合開始剤、(f)乳化剤、(g)顔料分散剤、等を含むことができる。本明細書において、上記ワニス成分を「平版インキ用ワニス」と言うことがある。
これらの顔料は、単独又は2種以上を混合して使用することができる。
平版インキ用ワニスは、ヒドロキシル基を有する多官能(メタ)アクリレートと親水性基を有する樹脂、その他成分を、必要に応じて50~95℃で加温溶解した後、室温に冷却することで得られる。
シリコーン液体としては、ジメチルシリコーン、メチルフェニルシリコーン、アルキル変性シリコーン、ポリエーテル変性シリコーン、アラルキル変性シリコーン、脂肪酸アミド変性シリコーン、脂肪酸エステル変性シリコーン、フルオロアルキル変性シリコーン、メチルハイドロジェンシリコーン、シラノール変性シリコーン、アルコール変性シリコーン、アミノ変性シリコーン、エポキシ変性シリコーン、エポキシポリエーテル変性シリコーン、フェノール変性シリコーン、カルボキシ変性シリコーン、メルカプト変性シリコーン等が挙げられる。
本発明において、(e)光重合開始剤や増感剤は1種または2種以上使用することができる。
顔料I:セイカシアニンブルー(大日精化(株)社製)。
樹脂I:25質量%のメタクリル酸メチル、25質量%のスチレン、50質量%のメタクリル酸からなる共重合体のカルボキシル基に対して0.6当量のグリシジルメタクリレート(GMA)を付加反応させて、エチレン性不飽和基と親水性基を有する樹脂Iを得た。得られた樹脂Iは重量平均分子量34,000、酸価102mgKOH/g、ヨウ素価2.0mol/kgであった。
反応性希釈剤II:“Miramer”(登録商標)M4004(MIWON社製)
光重合開始剤I:“イルガキュア”(登録商標)907(BASF社製)
増感剤I:ジエチルアミノベンゾフェノン(東京化成(株)社製)
重合禁止剤I:p-メトキシフェノール(和光純薬工業(株)社製)
添加剤I:ラウリルアクリレート(和光純薬工業(株)社製)
アミン化合物I:ジエタノールアミン(東京化成(株)社製)。
樹脂の重量平均分子量はテトラヒドロフランを移動相としたゲル浸透クロマトグラフィー(GPC)により測定した値である。カラムはShodex KF-803を用い、重量平均分子量はポリスチレン換算により計算した。
水なし平版印刷版(TAN-E、東レ(株)社製)をオフセット印刷機(オリバー266EPZ、桜井グラフィックシステム社製)に装着し、実施例1~8および比較例1~2に示す組成の各インキを用いて、コート紙10000枚に印刷を行い、印刷適性および印刷物を評価した。
感光性樹脂版(“トレリーフ(登録商標)” DWF95DIII、東レ(株)社製)をフレキソ印刷試験機(フレキシプルーフ100、PrintCoat Instruments社製)に装着し、アニロックスロールの線数は400線を使用し、実施例9~11および比較例3~4の各インキを用いて、PET(ポリエチレンテレフタレート)フィルム(三菱化学(株)社製、“ノバクリアー(登録商標)”、厚み:100μm)に印刷した。
実施例12~14、比較例5~6の印刷用インキを、ヘリオ彫刻版(175線/インチ)を備えたグラビア印刷試験機GP-10(クラボウ社製)を用いて、PETフィルム(三菱化学(株)社製、“ノバクリアー(登録商標)”、厚み:100μm)に印刷し、ドライヤーで乾燥させた。
実施例15~17、比較例7~8の印刷用インキを、インクジェットプリンター(キャノン(株)社製)を改造したものを使用して、PETフィルム(三菱化学(株)社製、“ノバクリアー(登録商標)”、厚み:100μm)に印刷した。
各評価方法は以下の通りである。
前記印刷物を、USHIO(株)社製紫外線照射装置(120W/cm、超高圧メタハラランプ1灯)を用いて、ベルトコンベアースピードを0~150m/minの条件で紫外線を照射した。印刷物上のインキが十分に硬化して、セロハン粘着テープ(“セロテープ”(登録商標)No.405)を接着させて剥離しても、コート紙上から剥がれなくなるときのベルトコンベアースピードを求めた。ここで、ベルトコンベアースピードが速いほど少ない露光量で硬化できることから高感度である。ベルトコンベアースピードが100m/min未満であると感度が不十分であり、100m/min以上120m/min未満であると感度が良好であり、120m/min以上であると省電力UV印刷機にも対応できるため、感度が極めて良好と判断した。
洗浄方法A:実施例1~8および比較例1~2に示す組成の各インキを用いた平版印刷適正試験終了後の印刷機で、ローラー上に残ったインキを水洗浄し、インキの水洗浄性の可否について3段階で評価した。
3:一度の水洗浄ですべてのインキが洗い流せた。
2:二度の水洗浄ですべてのインキが洗い流せた。
1:三度の水洗浄でインキ残渣が残った。
3:一回の拭き取りですべてのインキが洗い流せた。
2:二回の拭き取りですべてのインキが洗い流せた。
1:三回以上拭き取りを行ってもインキ残渣が残った。
印刷物上のインキ硬化膜を、25℃の水中に保持したときに、印刷物の耐水性を3段階で評価した。水中へのインキの溶出は、目視により確認した。
3:24時間までインキの溶出が見られなかった。
2:12時間までインキの溶出が見られなかったが、24時間ではインキの一部溶出が見られる。
1:12時間までにインキの溶出が見られた。
印刷物のベタ部藍色濃度が2.0であるときの、非画線部における藍色濃度を反射濃度計(GretagMacbeth社製、SpectroEye)を用いて評価した。反射濃度が0.5以下であると耐地汚れ性が良好であり、0.3以下であると耐地汚れ性が極めて良好である。
アントン・パール(Anton Paar)社製レオメーターMCR301にコーンプレート(コーン角1°、φ=40mm)を装着し、0.15mlのインキの25℃、5rpmにおける粘度を測定した。
表1に示すインキ組成を秤量し、三本ロールミル“EXAKT”(登録商標)M-80S(EXAKT社製)を用いて、ギャップ1で3回通すことで平版印刷用インキを得た。
樹脂Iの代わりに樹脂II~VIIを配合しエチレン性不飽和基濃度(ヨウ素価)と親水性基濃度(酸価)を表1のとおりにする以外は実施例1と同様の操作ならびに感度、水洗浄性、膜の耐水性および耐地汚れ性の評価を行った。エチレン性不飽和基濃度が大きくなるほど感度と膜の耐水性が良化する傾向にあり、親水性基濃度が大きくなるほど粘度が増大し、水洗浄性と耐地汚れ性が良化する傾向にあった。感度、水洗浄性、膜の耐水性、および耐地汚れ性を備えた平版印刷用インキとして、実施例3~6においてより好ましい結果を、実施例4および5において特に好ましい結果を得られた。
添加剤としてラウリルアクリレートを添加したこと以外は実施例1と同様の操作を行い、感度、水洗浄性、膜の耐水性および耐地汚れ性の評価を行った。作製した平版印刷用インキの粘度は、47Pa・sと適切であった。感度は、ベルトコンベアースピードで125m/minであり、極めて良好であった。水洗浄性は、一度の水洗浄でローラー上に残ったすべてのインキが洗浄可能であった。膜の耐水性は、25℃の水中でも24時間までインキ硬化膜からインキの溶出が見られなかった。耐地汚れ性は、非画線部における反射濃度が0.1であり、極めて良好であった。
樹脂Iの代わりに樹脂VIIIを配合し、樹脂の重量平均分子量29,000、酸価282mgKOH/g、ヨウ素価0mol/kgとする以外は実施例1と同様の操作ならびに感度、水洗浄性、膜の耐水性および耐地汚れ性の評価を行った。作製した印刷用インキの粘度は、114Pa・sと高粘度で、平版印刷に不適当であった。水洗浄性は、一度の水洗浄でローラー上に残ったすべてのインキが洗浄可能であった。さらに耐地汚れ性は、非画線部における反射濃度が0.2であり、極めて良好であった。しかしながら感度は、ベルトコンベアースピードで75m/minであり、不十分であった。また、膜の耐水性についても、25℃の水中で12時間までにインキ硬化膜からインキの溶出が見られた。
樹脂Iの代わりに樹脂IXを配合し、樹脂の重量平均分子量40,000、酸価0mgKOH/g、ヨウ素価3.2mol/kgとする以外は実施例1と同様の操作ならびに感度、水洗浄性、膜の耐水性および耐地汚れ性の評価を行った。作製した印刷用インキの粘度は、9Pa・sと低粘度で、平版印刷に不適当であった。感度は、ベルトコンベアースピードで150m/minであり、極めて良好であった。さらに膜の耐水性は、25℃の水中でも24時間までインキ硬化膜からインキの溶出が見られなかった。しかしながら水洗浄性は、三度の水洗浄でもローラー上にインキ残渣が残った。また耐地汚れ性は、非画線部における反射濃度が0.8であり、不十分であった。
表2-1に示すインキ組成を秤量し、ペイントコンディショナーを用いて混合分散し、印刷用インキを得た。
樹脂Iの代わりに樹脂IIIまたはIVを配合しエチレン性不飽和基濃度(ヨウ素価)と親水性基濃度(酸価)を表2-1のとおりにする以外は実施例9と同様の操作ならびに感度、水洗浄性、および膜の耐水性の評価を行った。エチレン性不飽和基濃度が大きくなるほど感度と膜の耐水性が良化する傾向にあり、親水性基濃度が大きくなるほど水洗浄性が良化する傾向にあった。
樹脂Iの代わりに樹脂VIIIを配合し、樹脂の重量平均分子量29,000、酸価282mgKOH/g、ヨウ素価0mol/kgとする以外は実施例9と同様の操作ならびに感度、水洗浄性、および膜の耐水性の評価を行った。作成したインキの粘度は4090mPa・sと高粘度で、フレキソ印刷に不適当であった。水洗浄性は、一度の洗浄で印刷物上のインキが除去可能であった。しかしながら感度は、ベルトコンベアースピードで40m/minであり、不十分であった。膜の耐水性は、25℃の水中で12時間までにインキ硬化膜からインキの溶出が見られた。
樹脂Iの代わりに樹脂IXを配合し、樹脂の重量平均分子量40,000、酸価0mgKOH/g、ヨウ素価3.2mol/kgとする以外は実施例9と同様の操作ならびに感度、水洗浄性、および膜の耐水性の評価を行った。作成したインキの粘度は170mPa・sと低粘度で、フレキソ印刷に不適当であった。感度は、ベルトコンベアースピードで140m/minであり、極めて良好であった。さらに膜の耐水性は、25℃の水中でも24時間までインキ硬化膜からインキの溶出が見られなかった。しかしながら水洗浄性は、複数回の洗浄を行ってもインキ残渣が見られた。
表2-1に示したインキ組成とし、フレキソ印刷適性評価をグラビア印刷適性評価にする以外は実施例9と同様の操作でインキを作成し、感度、水洗浄性、および膜の耐水性の評価を行った。作製した印刷用インキの粘度は570mPa・sと適切であった。感度は、ベルトコンベアースピードで120m/minであり、非常に良好であった。水洗浄性は、一度の洗浄で印刷物上のインキが除去可能であった。膜の耐水性は、25℃の水中でも24時間までインキ硬化膜からインキの溶出が見られなかった。
表2-1に示したインキ組成とし、エチレン性不飽和基濃度(ヨウ素価)と親水性基濃度(酸価)を表2-1のとおりにする以外は実施例12と同様の操作でインキを作成し、感度、水洗浄性、および膜の耐水性の評価を行った。エチレン性不飽和基濃度が大きくなるほど感度と膜の耐水性が良化する傾向にあり、親水性基濃度が大きくなるほど水洗浄性が良化する傾向にあった。
表2-2に示したインキ組成とし、樹脂の重量平均分子量29,000、酸価282mgKOH/g、ヨウ素価0mol/kgとする以外は実施例12と同様の操作ならびに感度、水洗浄性、および膜の耐水性の評価を行った。作成したインキの粘度は1280mPa・sと高粘度で、グラビア印刷に不適当であった。水洗浄性は、一度の洗浄で印刷物上のインキが除去可能であった。しかしながら感度は、ベルトコンベアースピードで50m/minであり、不十分であった。膜の耐水性は、25℃の水中で12時間までにインキ硬化膜からインキの溶出が見られた。
表2-2に示したインキ組成とし、樹脂の重量平均分子量40,000、酸価0mgKOH/g、ヨウ素価3.2mol/kgとする以外は実施例12と同様の操作ならびに感度、水洗浄性、および膜の耐水性の評価を行った。作成したインキの粘度は41mPa・sと低粘度で、グラビア印刷に不適当であった。感度は、ベルトコンベアースピードで140m/minであり、極めて良好であった。さらに膜の耐水性は、25℃の水中でも24時間までインキ硬化膜からインキの溶出が見られなかった。しかしながら水洗浄性は、複数回の洗浄を行ってもインキ残渣が見られた。
表2-1に示したインキ組成とし、フレキソ印刷適性評価をインクジェット印刷適性評価にする以外は実施例9と同様の操作でインキを作成し、感度、水洗浄性、および膜の耐水性の評価を行った。感度は、ベルトコンベアースピードで120m/minであり、非常に良好であった。水洗浄性は、一度の洗浄で印刷物上のインキが除去可能であった。膜の耐水性は、25℃の水中でも24時間までインキ硬化膜からインキの溶出が見られなかった。
表2-1に示したインキ組成とし、エチレン性不飽和基濃度(ヨウ素価)と親水性基濃度(酸価)を表2-1のとおりにする以外は実施例15と同様の操作インキを作成し、感度、水洗浄性、および膜の耐水性の評価を行った。エチレン性不飽和基濃度が大きくなるほど感度と膜の耐水性が良化する傾向にあり、親水性基濃度が大きくなるほど水洗浄性が良化する傾向にあった。
表2-2に示したインキ組成とし、樹脂の重量平均分子量29,000、酸価282mgKOH/g、ヨウ素価0mol/kgとする以外は実施例15と同様の操作ならびに感度、水洗浄性、および膜の耐水性の評価を行った。作成したインキの粘度は235mPa・sと高粘度で、インクジェット印刷に不適当であった。水洗浄性は、一度の洗浄で印刷物上のインキが除去可能であった。しかしながら感度は、ベルトコンベアースピードで40m/minであり、不十分であった。膜の耐水性は、25℃の水中で12時間までにインキ硬化膜からインキの溶出が見られた。
表2-2に示したインキ組成とし、樹脂の重量平均分子量40,000、酸価0mgKOH/g、ヨウ素価3.2mol/kgとする以外は実施例15と同様の操作ならびに感度、水洗浄性、および膜の耐水性の評価を行った。作成したインキの粘度は0.7mPa・sと低粘度で、インクジェット印刷に不適当あった。感度は、ベルトコンベアースピードで130m/minであり、極めて良好であった。さらに膜の耐水性は、25℃の水中でも24時間までインキ硬化膜からインキの溶出が見られなかった。しかしながら水洗浄性は、複数回の洗浄を行ってもインキ残渣が見られた。
各実施例および各比較例において用いられた各成分の組成と評価の結果を表に示す。
多官能(メタ)アクリレート1:ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物“Miramer”(登録商標)M340(MIWON社製)ヒドロキシル基あり、水酸基価115mgKOH/g、分子量298
重合禁止剤1:p-メトキシフェノール(和光純薬工業(株)社製)
樹脂の重量平均分子量はテトラヒドロフランを移動相としたゲル浸透クロマトグラフィー(GPC)により測定した値である。カラムはShodex KF-803を用い、重量平均分子量はポリスチレン換算により計算した。
(1)流動性
アントン・パール(Anton Paar)社製レオメーターMCR301にパラレルプレート(ギャップ0.1mm、φ=25mm)を装着し、インキピペットで秤量した0.05mlの平版インキ用ワニスの、25℃、ひずみ1%、角速度1rad/sにおける正接損失tanδを測定した。tanδの値が3~5で流動性が良好であり、5~10で流動性がより良好であり、10以上で流動性が極めて良好である。
ブルックフィールド(BROOKFIELD)社製B型粘度計DV-IIにシリンダースピンドルNo4を装着し、平版インキ用ワニスの25℃、0.5rpmにおける粘度を測定した。前記粘度は、平版印刷用インキの耐地汚れ性と流動性の両方が良好となる、10~400Pa・sが好ましく、50~300Pa・sがより好ましく、100~250Pa・sがさらに好ましい。
顔料1:セイカシアニンブルー4920(大日精化(株)社製)
光重合開始剤1:“イルガキュア”(登録商標)907(BASF社製)
光重合開始剤2“イルガキュア”(登録商標)TPO-L(BASF社製)
増感剤1:ジエチルアミノベンゾフェノン(東京化成(株)社製)
添加剤1:ラウリルアクリレート(和光純薬工業(株)社製)
乳化剤1:“レオドール”(登録商標)スーパーTW-L120(花王(株)社製)HLB値16.7
ワックス1:PTFEワックス、KTL-4N(喜多村(株)社製)
水なし平版印刷版(TAN-E、東レ(株)社製)をオフセット印刷機(オリバー266EPZ、桜井グラフィックシステム社製)に装着し、実施例18~26、参照例1~3および比較例9~11に示す組成の各インキを用いて、コート紙5000枚に印刷、USHIO(株)社製紫外線照射装置(120W/cm、超高圧メタハラランプ1灯)を用いて、ベルトコンベアースピードを80m/minにて紫外線を照射し、インキを硬化させ、印刷物を得た。各評価方法は以下の通りである。
水あり平版印刷版(XP-F、富士フィルム(株)社製)をオフセット印刷機(オリバー266EPZ、桜井グラフィックシステム社製)に装着し、湿し水にエッチ液(SOLAIA-505、T&K TOKA社製)を3重量%混合した水道水を用い、実施例27~29、参照例4および比較例12,13の各インキを用いて、コート紙5000枚に印刷、USHIO(株)社製紫外線照射装置(120W/cm、超高圧メタハラランプ1灯)を用いて、ベルトコンベアースピードを80m/minにて紫外線を照射し、インキを硬化させ、印刷物を得た。
(1)粘度
アントン・パール(Anton Paar)社製レオメーターMCR301にコーンプレート(コーン角1°、φ=40mm)を装着し、インキピペットで秤量した0.15mlのインキの25℃、0.5rpmを測定した。
印刷物のベタ部藍色濃度が2.0であるときの、印刷物の非画線部における藍色濃度を反射濃度計(GretagMacbeth製、SpectroEye)を用いて評価した。反射濃度が0.15を超えると耐地汚れ性が不良であり、0.10以下であると耐地汚れ性が良好、0.05以下であると耐地汚れ性が極めて良好である。
印刷物上のインキ硬化膜を、精密光沢計GM-26D((株)村上色彩技術研究所社製)を用いて光沢値を測定した。光沢値は30以上あれば良好であり、35以上あれば極めて良好である。
樹脂1、多官能(メタ)アクリレート1、重合禁止剤1を表3に示す割合で秤量し、樹脂1、及び重合禁止剤1を多官能(メタ)アクリレート1に90℃で加え、撹拌溶解後室温に冷却することで、平版インキ用ワニス1を得た。
表4に示す組成で、ワニス1、顔料1、光重合開始剤1及び2、増感剤1、添加剤1ならびにワックス1を秤量し、三本ロールミル“EXAKT”(登録商標)M-80S(EXAKT社製)を用いて、ローラーギャップ1で2度500rpmの速度で通すことで平版印刷用インキを得た。
得られたインキについて、水なし印刷試験を行い、性能を評価した。結果を表4に示す。
表4に示す組成で、ワニス1をワニス2~5に変更する以外は実施例18と同様の操作を行い、実施例19~22の平版印刷用インキを作成した。ワニス2~5を組成するヒドロキシル基を有する多官能(メタ)アクリレートの水酸基価、分子量が高いほどインキは高粘度化し、耐地汚れ性が向上する傾向にあった。一方で、印刷物のベタ部分における光沢値は低下する傾向にあった。
表4に示す組成で、ワニス1をワニス6~8に変更する以外は実施例18と同様の操作を行い、実施例23~25の平版印刷用インキを作成した。作成した平版印刷用インキは、ワニス6~8を組成するヒドロキシル基を有する多官能(メタ)アクリレートの含有量が高いほど、高粘度化する傾向にあり、耐地汚れ性は向上する傾向にあった。一方で、印刷物のベタ部分における光沢値は低下する傾向にあった。
表4に示す組成で、ワニス1をワニス9~13に変更する以外は実施例18と同様の操作を行い、実施例26、参照例1~3、および比較例9の平版印刷用インキを作成した。作成した平版印刷用インキは、ワニス9~13を組成する樹脂の酸価、分子量が大きいほど、高粘度化する傾向にあり、耐地汚れ性も向上する傾向にあった。しかしながら、得られる印刷物のベタ部分における光沢は低下する傾向にあった。特に比較例9の酸性基を持たない樹脂では、インキの粘度が低く、耐地汚れ性が不十分であった。
表5に示す組成とし、乳化剤1を添加すること以外は実施例18と同様の操作を行い、実施例27の平版印刷用インキを作成した。作成した平版印刷用インキは、0.5rpmにおける粘度が66Pa・sであった。非画線部における反射濃度が0.02であり、耐地汚れ性は極めて良好であった。得られた印刷物はベタ部分の光沢値が36であり、極めて良好であった。
表5に示す組成で、ワニスを変更する以外は実施例27と同様の操作を行い、実施例28~29、参照例4、および比較例10の平版印刷用インキを作成した。作成した平版印刷用インキは、ワニスを組成する樹脂の酸価が増大すると湿し水を取り込みにくくなり、耐地汚れ性が低下する傾向にあった(参照例4)。また、ワニスを組成するヒドロキシル基を有する多官能(メタ)アクリレートの水酸基価が減少し、インキが適度な疎水性となることで、耐地汚れ性が向上した(実施例28、29)。比較例10にインキは粘度が低く、耐地汚れ性が不十分であった。
顔料A:(アゾレーキ顔料)“レーキレッド”(登録商標) C #405(F)(大日精化工業(株)社製)
顔料B:(アゾレーキ顔料)“セイカファースト”(登録商標) カーミン 1476T-7 (大日精化工業(株)社製)
顔料C:(アゾレーキ顔料)430 ブリリアントボルドー 10B(大日精化工業(株)社製)
顔料D:(アゾレーキ顔料)“LIONOL”(登録商標) RED TT-4801G(東洋インキ(株)社製)
顔料E:(フタロシアニン銅錯体)“クロモファイン”(登録商標) β型ブルー PB-15:3(大日精化工業(株)社製)
顔料F:(フタロシアニン銅錯体)“クロモファイン”(登録商標) グリーン PG-7(大日精化工業(株)社製)
顔料G:(フタロシアニンコバルト錯体)“クロモファイン”(登録商標) コバルトフタロシアニンブルー PB-75(大日精化工業(株)社製)
顔料H:カーボンブラックMA8(三菱化学(株)社製) 粒子径24nm、ジブチルフタレート吸収量57cm3/100g、酸性基(カルボキシル基)を有する
顔料I:“カーボンブラックMA77(三菱化学(株)社製) 粒子径23nm、ジブチルフタレート吸収量68cm3/100g、酸性基(カルボキシル基)を有する
顔料J:カーボンブラックMA11(三菱化学(株)社製) 粒子径29nm、ジブチルフタレート吸収量64cm3/100g、酸性基(カルボキシル基)を有する
顔料K:カーボンブラックMA14(三菱化学(株)社製) 粒子径40nm、ジブチルフタレート吸収量73cm3/100g、酸性基(カルボキシル基)を有する
顔料L:“カーボンブラックMA100(三菱化学(株)社製) 粒子径24nm、ジブチルフタレート吸収量100cm3/100g、酸性基(カルボキシル基)を有する
顔料M:カーボンブラックMA220(三菱化学(株)社製) 粒子径55nm、ジブチルフタレート吸収量93cm3/100g、酸性基(カルボキシル基)を有する
顔料N:カーボンブラック#45(三菱化学(株)社製) 粒子径24nm、ジブチルフタレート吸収量53cm3/100g、酸性基を有しない
顔料分散剤B:“プライサーフ”(登録商標)A212C 酸価:110mgKOH/g リン酸基含有アニオン性界面活性剤 (第一工業製薬(株)社製)
顔料分散剤C:“ディスパロン”(登録商標)1850 酸価:73mgKOH/g リン酸基含有アニオン性界面活性剤 (楠木化成(株)社製)
顔料分散剤D:“プライサーフ”(登録商標)A208N 酸価:145mgKOH/g リン酸基含有アニオン性界面活性剤 (第一工業製薬(株)社製)
顔料分散剤E:“プライサーフ”(登録商標)A219B 酸価:51mgKOH/g リン酸基含有アニオン性界面活性剤 (第一工業製薬(株)社製)
顔料分散剤F:“DISPERBYK”(登録商標)-2015 酸価:10mgKOH/g (ビックケミージャパン(株)社製)
顔料分散剤G:“プライサーフ”(登録商標)A208F 酸価:180mgKOH/g リン酸基含有アニオン性界面活性剤 (第一工業製薬(株)社製)
顔料分散剤H:“DISPERBYK”(登録商標)-2155 酸価:0mgKOH/g (ビックケミージャパン(株)社製)
顔料分散剤I:“ディスパロン”(登録商標)DA-325 アミン価:20mgKOH/g (楠木化成(株)社製)
顔料分散剤J:“BYK”(登録商標)-9076 アミン価:44mgKOH/g (ビックケミージャパン(株)社製)
顔料分散剤K:“DISPERBYK”(登録商標)-191 アミン価:20mgKOH/g (ビックケミージャパン(株)社製)
顔料分散剤L:“DISPERBYK”(登録商標)-2155 アミン価:48mgKOH/g (ビックケミージャパン(株)社製)
顔料分散剤M:“DISPERBYK”(登録商標)-2022 アミン価:61mgKOH/g (ビックケミージャパン(株)社製)
顔料分散剤N:“DISPERBYK”(登録商標)-2000 アミン価:4mgKOH/g (ビックケミージャパン(株)社製)
反応性希釈剤B(エチレン性不飽和基のみ含有):“Miramer”(登録商標)M280 ポリエチレングリコールジアクリレート(MIWON社製)
反応性希釈剤C(エチレン性不飽和基のみ含有):“Miramer”(登録商標)M300 トリメチロールプロパントリアクリレート(MIWON社製)
光重合開始剤A:“イルガキュア”(登録商標)907(BASF社製)
増感剤A:ジエチルアミノベンゾフェノン(東京化成(株)社製)
重合禁止剤A:ヒドロキノンモノメチルエーテル(東京化成(株)社製)
添加剤A:ラウリルアクリレート(和光純薬工業(株)社製)
アントン・パール(Anton Paar)社製レオメーターMCR301にパラレルプレート(φ=25、ギャップ0.1mm)を装着し、25℃、角速度100rad/s、ひずみ1%以下における損失弾性率(粘性)と貯蔵弾性率(弾性)を測定し、損失弾性率と貯蔵弾性率の比で表される損失正接tanδの値を計算した。tanδが1以上で流動性があり、2.0以上で流動性が良好で、3.0以上で流動性が極めて良好である。
水なし平版印刷版(TAN-E、東レ(株)社製)をオフセット印刷機(オリバー266EPZ、桜井グラフィックシステム社製)に装着し、表6~14に示す組成の各インキを用いて、コート紙10000枚に印刷を行い、印刷適性および印刷物を評価した。各評価方法は以下の通りである。
前記印刷物を、USHIO(株)社製紫外線照射装置(120W/cm、超高圧メタハラランプ1灯)を用いて、ベルトコンベアースピードを0~150m/minの条件で紫外線を照射した。印刷物上のインキが十分に硬化して、セロハン粘着テープ(“セロテープ” (登録商標)No.405)を接着させて剥離しても、コート紙上から剥がれなくなるときのベルトコンベアースピードを求めた。ここで、ベルトコンベアースピードが速いほど少ない露光量で硬化できることから高感度である。ベルトコンベアースピードが100m/min未満であると感度が不十分であり、100m/min以上120m/min未満であると感度が良好であり、120m/min以上であると省電力UV印刷機にも対応できるため、感度が極めて良好と判断した。
印刷終了後の印刷機で、1Lの水を印刷機に流水することでローラー上に残ったインキを水洗浄し、インキの水洗浄性の可否について3段階で評価した。
A:一度の水洗浄ですべてのインキが洗い流せた。
B:二度の水洗浄ですべてのインキが洗い流せた。
C:三度の水洗浄でもインキ残渣が残った。
印刷物上のインキ硬化膜を、25℃の水中に保持したときに、印刷物の耐水性を3段階で評価した。水中へのインキの溶出は、目視により確認した。
A:24時間までインキの溶出が見られなかった。
B:12時間までインキの溶出が見られなかったが、24時間ではインキの一部溶出が見られる。
C:12時間までにインキの溶出が見られた。
印刷物上のインキ硬化膜を、精密光沢計GM-26D((株)村上色彩技術研究所社製)を用いて測定角度60度で光沢値を測定した。光沢値は30未満では不良であり、光沢値は30以上あれば良好であり、35以上あれば極めて良好である。
印刷物のベタ部紅色濃度が2.0であるときの、印刷物の非画線部における紅色濃度を反射濃度計(GretagMacbeth製、SpectroEye)を用いて評価した。反射濃度が0.5を超えると耐地汚れ性が不良であり、0.3を超えると耐地汚れ性がやや不良であり、0.3以下であると耐地汚れ性が良好であり、0.1以下であると耐地汚れ性が極めて良好である。
表6に示すインキ組成を秤量し、三本ロールミル“EXAKT” (登録商標)M-80S(EXAKT社製)を用いて、10μmのギャップで3回通すことで平版印刷用インキを得た。
顔料の種類を表6のとおりにする以外は実施例30と同様の操作を行い、流動性試験、感度、水洗浄性、光沢性および耐地汚れ性の評価を行った。実施例31~36のいずれの平版印刷用インキにおいても、流動性試験、感度、水洗浄性、耐水性、光沢性、および耐地汚れ性について極めて良好な結果であった。
顔料分散剤の種類を表7のとおりにする以外は実施例30と同様の操作を行い、流動性試験、感度、水洗浄性、光沢性および耐地汚れ性の評価を行った。実施例37~42のいずれの平版印刷用インキにおいても、流動性試験、感度、水洗浄性、耐水性、光沢性、および耐地汚れ性について総じて良好な結果であったが、顔料分散剤の酸価が110mgKOH/g,145mgKOH/gである実施例37および39については、インキの流動性や光沢性の結果が極めて良好であり、顔料分散剤の酸価がそれぞれ10mgKOH/g、180mgKOH/gである実施例41および42については、比較的インキの流動性が低下したため、光沢性は良好という結果だった。
顔料分散剤の含有量を表8のとおりにする以外は実施例30と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。実施例43~47のいずれの平版印刷用インキにおいても、流動性試験、感度、水洗浄性、耐水性、光沢性、および耐地汚れ性について総じて良好な結果であったが、顔料分散剤の含有量が顔料に対して30%である実施例45の流動性試験、光沢性の結果が極めて良好であり、顔料分散剤の含有量がそれぞれ顔料に対して3%および60%である実施例46および471については、比較的インキの流動性が低下したため、光沢性は良好という結果だった。
樹脂の種類を表9のとおりにする以外は実施例30と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。樹脂の酸価が10mgKOH/gである実施例48においては、比較的インキの流動性が低下したため、光沢性は良好という結果であり、さらに樹脂の酸価が低いために、水洗浄性がBとなり、耐地汚れ性もやや不良だった。樹脂のヨウ素価が0.25mol/kgである実施例53においては、インキの硬化が低く、感度は良好という結果にとどまり、耐水性もBであった。実施例49~52については、流動性試験、感度、水洗浄性、耐水性、光沢性、および耐地汚れ性について総じて極めて良好な結果であった。
顔料分散剤の種類を表10のとおりにする以外は実施例30と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。作製したインキの流動性を測定した結果、損失正接tanδは0.95となり、流動性が低下した。感度、水洗浄性、耐水性、耐地汚れ性は極めて良好だったが、光沢値が24と大きく低下し、光沢性は不良だった。
顔料分散剤の含有量を表10のとおりにする以外は実施例30と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。作製したインキの流動性を測定した結果、損失正接tanδは0.88となり、流動性が低下した。感度、水洗浄性、耐水性、耐地汚れ性は良好だったが、光沢値が21と大きく低下し、光沢性は不良だった。
樹脂・反応性希釈剤の種類、顔料分散剤の含有量を表10のとおりにする以外は実施例30と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。作製したインキの水洗浄性、耐地汚れ性は良好だったが、流動性を測定した結果、損失正接tanδは0.84となり、流動性が低下した。また感度を測定した結果、ベルトコンベアースピードで75m/minであり、感度は不十分だった。また耐水性を測定した結果、6時間でインキの溶出が見られ、耐水性はCだった。さらに、光沢値が19と大きく低下し、光沢性は不良だった。
樹脂・反応性希釈剤の種類を、表10のとおりにする以外は実施例30と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。作製したインキの流動性を測定した結果、損失正接tanδは1.24となり、流動性が低下した。感度は良好だったが、水洗浄性については、3度の水洗浄でもインキ残渣が残り、Cだった。光沢性については、光沢値は27となり、不良だった。耐地汚れ性は非画線部における反射濃度が0.75となり、不良だった。
表11に示すインキ組成を秤量し、三本ロールミル“EXAKT”(登録商標)M-80S(EXAKT社製)を用いて、10μmのギャップで3回通すことで平版印刷用インキを得た。
顔料の種類を表11のとおりにする以外は実施例56と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。カーボンブラックのジブチルフタレート吸収量が100、93である実施例60,61については、比較的印刷物の表面粗さが大きくなったために、光沢性は良好という結果だった。実施例57~59については、いずれの平版印刷用インキにおいても、流動性試験、感度、水洗浄性、耐水性、光沢性、および耐地汚れ性について極めて良好な結果であった。
樹脂の種類を表12のとおりにする以外は実施例56と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。樹脂Bの酸価が10mgKOH/gである実施例62においては、比較的インキの流動性が低下したため、光沢性は良好という結果であり、さらに樹脂の酸価が低いために、水洗浄性がBとなり、耐地汚れ性もやや不良だった。樹脂Gのヨウ素価が0.25mol/kgである実施例67においては、インキの硬化が低く、感度は良好という結果にとどまり、耐水性もBであった。実施例63~66については、流動性試験、感度、水洗浄性、耐水性、光沢性、および耐地汚れ性について総じて極めて良好な結果であった。
顔料分散剤の種類を表13のとおりにする以外は実施例56と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。顔料分散剤のアミン価が61mgKOH/g,4mgKOH/gである実施例71,72については、比較的インキの流動性が低下したため、光沢性は良好という結果だった。実施例68~70については、いずれの平版印刷用インキにおいても、流動性試験、感度、水洗浄性、耐水性、光沢性、および耐地汚れ性について総じて良好な結果であった。
顔料の種類を表14のとおりにする以外は実施例56と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。作製したインキの流動性を測定した結果、損失正接tanδは0.95となり、流動性が低下した。感度、水洗浄性、耐水性、耐地汚れ性は極めて良好だったが、光沢値が24と大きく低下し、光沢性は不良だった。
樹脂の種類を表14のとおりにする以外は実施例56と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。作製したインキの流動性試験、水洗浄性、耐地汚れ性は良好だったが、感度を測定した結果、ベルトコンベアースピードで75m/minであり、感度は不十分だった。また耐水性を測定した結果、6時間でインキの溶出が見られ、耐水性はCだった。
樹脂の種類を表14のとおりにする以外は実施例56と同様の操作を行い、流動性試験、感度、水洗浄性、耐水性、光沢性および耐地汚れ性の評価を行った。作製したインキの流動性を測定した結果、損失正接tanδは1.24となり、流動性が低下した。感度、耐水性は良好だったが、水洗浄性については、3度の水洗浄でもインキ残渣が残り、Cだった。光沢性については、光沢値は27となり、不良だった。耐地汚れ性は非画線部における反射濃度が0.75となり、不良だった。
表1に示す実施例1と同じ組成の平版印刷用インキを用いて、以下の平版印刷適性試験、並びに硬化試験を実施し、感度、膜の耐水性、ならびに基材の反りを評価した。
水なし平版印刷版(TAN-E、東レ(株)社製)をオフセット印刷機(オリバー266EPZ、桜井グラフィックシステム社製)に装着し、実施例1に示す組成のインキを用いて、ポリエチレンテレフタレートフィルム10000枚に印刷を行った。
前記印刷物を、USHIO(株)社製紫外線照射装置(120W/cm、超高圧メタハラランプ1灯)を用いて、ベルトコンベアースピードを0~150m/minの条件で紫外線を照射した。印刷物上のインキが十分に硬化して、セロハン粘着テープ(“セロテープ”(登録商標)No.405)を接着させて剥離しても、ポリエチレンテレフタレートフィルム上から剥がれなくなるときのベルトコンベアースピードを求めた。ここで、ベルトコンベアースピードが速いほど少ない露光量で硬化できることから高感度である。ベルトコンベアースピードが100m/min未満であると感度が不十分であり、100m/min以上120m/min未満であると感度が良好であり、120m/min以上であると感度が極めて良好と判断した。
USHIO(株)社製紫外線照射装置(120W/cm、超高圧メタハラランプ1灯)をパナソニックデバイスSUNX(株)社製紫外線照射装置(5W/cm2、LED-UV)に変更したこと以外は、実施例74と同様にして平版印刷適性試験、並びに硬化試験を実施し、感度、膜の耐水性、ならびに基材の反りを評価した。
ポリエチレンテレフタレートフィルムをアルミ蒸着紙に変更し、USHIO(株)社製紫外線照射装置(120W/cm、超高圧メタハラランプ1灯)をUSHIO(株)社製電子線照射装置“Min-EB”(100eV)に変更したこと以外は、実施例74と同様にして平版印刷適性試験、並びに硬化試験を実施し、感度、膜の耐水性、ならびに基材の反りを評価した。
Claims (43)
- (a)顔料、並びに(b)エチレン性不飽和基および親水性基を有する樹脂、を含むことを特徴とする平版印刷用インキ。
- 活性エネルギー線硬化性を有する、請求項1に記載の平版印刷用インキ。
- 前記(b)エチレン性不飽和基および親水性基を有する樹脂の親水性基が、カルボキシル基、スルホ基、リン酸基、水酸基、およびアミノ基から選ばれる少なくとも1つの官能基を含む、請求項1または2に記載の平版印刷用インキ。
- 前記(b)エチレン性不飽和基および親水性基を有する樹脂の親水性基が、カルボキシル基を含む、請求項1または2に記載の平版印刷用インキ。
- 前記(b)エチレン性不飽和基および親水性基を有する樹脂の親水性基が、カルボキシル基、および水酸基を含む、請求項1または2に記載の平版印刷用インキ。
- 前記(b)エチレン性不飽和基および親水性基を有する樹脂の親水性基の酸価が、30mgKOH/g以上250mgKOH/g以下である、請求項1~5のいずれかに記載の平版印刷用インキ。
- 前記(b)エチレン性不飽和基および親水性基を有する樹脂のヨウ素価が、0.5mol/kg以上3.0mol/kg以下である、請求項1~6のいずれかに記載の平版印刷用インキ。
- 前記(b)エチレン性不飽和基および親水性基を有する樹脂が、アクリル樹脂、スチレンアクリル樹脂、およびスチレンマレイン酸樹脂から選ばれる少なくとも1つの樹脂を含む、請求項1~7のいずれかに記載の平版印刷用インキ。
- 前記(b)エチレン性不飽和基および親水性基を有する樹脂の重量平均分子量が、20,000以上100,000以下である、請求項1~8のいずれかに記載の平版印刷用インキ。
- さらに、(c)反応性希釈剤を含む、請求項1~9のいずれかに記載の平版印刷用インキ。
- 前記(c)反応性希釈剤が、親水性の多官能(メタ)アクリレートである、請求項10に記載の平版印刷用インキ。
- 前記(c)反応性希釈剤が、ヒドロキシル基を有する多官能(メタ)アクリレートである請求項10または11に記載の平版印刷用インキ。
- 前記ヒドロキシル基を有する多官能(メタ)アクリレートの水酸基価が、50mgKOH/g以上200mgKOH/g以下である、請求項12に記載の平版印刷用インキ。
- 前記ヒドロキシル基を有する多官能(メタ)アクリレートの分子量が、100以上1000以下である、請求項12または13に記載の平版印刷用インキ。
- 前記ヒドロキシル基を有する多官能(メタ)アクリレートが、ペンタエリスリトールトリ(メタ)アクリレート、ジグリセリントリ(メタ)アクリレート、ジトリメチロールプロパントリ(メタ)アクリレートから選ばれる少なくとも1つを含む、請求項12~14のいずれかに記載の平版印刷用インキ。
- さらに、(e)光重合開始剤を含む、請求項1~15のいずれかに記載の平版印刷用インキ。
- さらに、(g)顔料分散剤を含む、請求項1~16のいずれかに記載の平版印刷用インキ。
- 前記(g)顔料分散剤が酸性基を有する、請求項17に記載の平版印刷用インキ。
- 前記(g)顔料分散剤が、カルボキシル基、スルホ基、リン酸基の少なくとも1つの官能基を有する、請求項17または18に記載の平版印刷用インキ。
- 前記(g)顔料分散剤の酸価が5~200mgKOH/gである、請求項18または19に記載の平版印刷用インキ。
- 前記(g)顔料分散剤が、さらに塩基性基を有する、請求項18~20のいずれかに記載の平版印刷用インキ。
- 前記(g)顔料分散剤がアミノ基を有する、請求項18~21のいずれかに記載の平版印刷用インキ。
- 前記(g)顔料分散剤のアミン価が5~50mgKOH/gである、請求項21または22に記載の平版印刷用インキ。
- 前記(g)顔料分散剤の含有量が、前記(a)顔料100質量%に対して5~50質量%である、請求項17~23のいずれかに記載の平版印刷用インキ。
- 前記(a)顔料が水不溶性の塩である、請求項1~24のいずれかに記載の平版印刷用インキ。
- 前記(a)顔料がアゾレーキ顔料である、請求項1~25のいずれかに記載の平版印刷用インキ。
- 前記(a)顔料が金属錯体である、請求項1~25のいずれかに記載の平版印刷用インキ。
- 前記(a)顔料がカーボンブラックである、請求項1~24のいずれかに記載の平版印刷用インキ。
- 前記カーボンブラックが酸性基を有する、請求項28に記載の平版印刷用インキ。
- 前記カーボンブラックの平均粒子径が10~50nmである、請求項28または29に記載の平版印刷用インキ。
- 前記カーボンブラック100gあたりのジブチルフタレート吸収量が、40~80cm3/100gである、請求項28~30のいずれかに記載の平版印刷用インキ。
- さらに、(f)乳化剤を含む、請求項1~31のいずれかに記載の平版印刷用インキ。
- 前記(f)乳化剤のHLB値が、10以上18以下である、請求項32に記載の平版印刷用インキ。
- さらに、(d)シリコーン液体、アルキルアクリレート、炭化水素系溶媒、およびフルオロカーボンから選ばれる1種類以上の化合物を含む、請求項1~33のいずれかに記載の平版印刷用インキ。
- 請求項1~34の何れかに記載の平版印刷用インキを構成する平版インキ用ワニスであって、ヒドロキシル基を有する多官能(メタ)アクリレート、および親水性基を有する樹脂を含む、平版インキ用ワニス。
- 前記平版インキ用ワニス中のヒドロキシル基を有する多官能(メタ)アクリレートの含有量が40質量%以上90質量%以下である請求項35に記載の平版インキ用ワニス。
- 請求項1~34のいずれかに記載の平版印刷用インキを用いる印刷物の製造方法。
- 請求項1~34のいずれかに記載の平版印刷用インキを基材上に塗布し、活性エネルギー線を照射する工程を含む、印刷物の製造方法。
- 請求項1~34のいずれかに記載の平版印刷用インキを、水なし平版印刷版を用いて基材に印刷する工程を含む印刷物の製造方法。
- 請求項1~34のいずれかに記載の平版印刷用インキを、水あり平版印刷版を用いて基材に印刷する工程を含む印刷物の製造方法。
- さらに、活性エネルギー線を照射する工程を含む、請求項39または40に記載の印刷物の製造方法。
- 前記基材がプラスチックフィルム、プラスチックフィルムラミネート紙、金属、金属蒸着紙、金属蒸着プラスチックフィルムから選ばれる少なくとも1つを含む請求項38~41のいずれかに記載の印刷物の製造方法。
- 前記活性エネルギー線が、電子線、またはLED-UVである請求項38,41または42に記載の印刷物の製造方法。
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JP2016573144A JP6652508B2 (ja) | 2015-09-17 | 2016-09-20 | 平版印刷用インキ、平版インキ用ワニスおよびそれを用いた印刷物の製造方法 |
SG11201802107XA SG11201802107XA (en) | 2015-09-17 | 2016-09-20 | Lithographic printing ink, varnish for lithographic inks, and method for producing printed matter using said ink |
US15/755,816 US20180327617A1 (en) | 2015-09-17 | 2016-09-20 | Lithographic printing ink, varnish for lithographic inks, and method for producing printed matter using said ink |
CN201680053606.9A CN108026399A (zh) | 2015-09-17 | 2016-09-20 | 平版印刷用墨水、平版墨水用清漆和使用其的印刷物的制造方法 |
KR1020187001656A KR102278863B1 (ko) | 2015-09-17 | 2016-09-20 | 평판 인쇄용 잉크, 평판 잉크용 바니시, 및 그것을 사용한 인쇄물의 제조 방법 |
EP16846688.6A EP3351602A4 (en) | 2015-09-17 | 2016-09-20 | LITHOGRAPHIC PRINTING INK, LACK FOR LITHOGRAPHIC PRINTING INKS, AND METHOD FOR PRODUCING PRINTED SIZES USING THIS INK |
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JP2015-229339 | 2015-11-25 | ||
JP2015229338 | 2015-11-25 | ||
JP2016-038606 | 2016-03-01 | ||
JP2016038606 | 2016-03-01 | ||
JP2016-104087 | 2016-05-25 | ||
JP2016104087 | 2016-05-25 | ||
JP2016104089 | 2016-05-25 | ||
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US (1) | US20180327617A1 (ja) |
EP (1) | EP3351602A4 (ja) |
JP (2) | JP6652508B2 (ja) |
KR (1) | KR102278863B1 (ja) |
CN (1) | CN108026399A (ja) |
SG (1) | SG11201802107XA (ja) |
TW (1) | TW201720881A (ja) |
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WO2019203263A1 (ja) | 2018-04-19 | 2019-10-24 | 東レ株式会社 | 印刷版、印刷版の製造方法、およびそれを用いた印刷物の製造方法 |
JP2020059822A (ja) * | 2018-10-11 | 2020-04-16 | サカタインクス株式会社 | 表刷りフィルム用水性印刷インキ組成物 |
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CN113321966A (zh) * | 2021-06-01 | 2021-08-31 | 安徽德瑞新材料科技有限公司 | 一种uv光固化纳米金属导电油墨专用炭黑材料 |
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WO2021044838A1 (ja) | 2019-09-03 | 2021-03-11 | 東レ株式会社 | 印刷物の製造方法 |
CN113321966A (zh) * | 2021-06-01 | 2021-08-31 | 安徽德瑞新材料科技有限公司 | 一种uv光固化纳米金属导电油墨专用炭黑材料 |
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JP2018188671A (ja) | 2018-11-29 |
KR102278863B1 (ko) | 2021-07-19 |
KR20180055795A (ko) | 2018-05-25 |
SG11201802107XA (en) | 2018-04-27 |
TW201720881A (zh) | 2017-06-16 |
CN108026399A (zh) | 2018-05-11 |
JPWO2017047817A1 (ja) | 2018-03-29 |
JP6870668B2 (ja) | 2021-05-12 |
US20180327617A1 (en) | 2018-11-15 |
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EP3351602A4 (en) | 2019-05-22 |
EP3351602A1 (en) | 2018-07-25 |
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