WO2018062108A1 - 平版印刷用インキを用いた印刷物の製造方法、および平版印刷用インキセット - Google Patents
平版印刷用インキを用いた印刷物の製造方法、および平版印刷用インキセット Download PDFInfo
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- WO2018062108A1 WO2018062108A1 PCT/JP2017/034564 JP2017034564W WO2018062108A1 WO 2018062108 A1 WO2018062108 A1 WO 2018062108A1 JP 2017034564 W JP2017034564 W JP 2017034564W WO 2018062108 A1 WO2018062108 A1 WO 2018062108A1
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- ink
- lithographic printing
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- acrylate
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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
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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
- B41M1/14—Multicolour printing
- B41M1/18—Printing one ink over another
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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
- B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
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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
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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
- 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 method for producing a printed material using a lithographic printing ink and a lithographic printing ink set.
- 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.
- lithographic printing inks in order to cope with environmental problems.
- active energy ray curable lithographic printing ink use of a lithographic printing ink that does not contain a volatile component and instantaneously cures upon irradiation with an active energy ray (hereinafter referred to as “active energy ray curable lithographic printing ink”) has been promoted.
- active energy ray curable lithographic printing ink further shortens the drying process and further increases the productivity of lithographic printing.
- a material repelling ink is patterned as a non-image area to form an image.
- Water-containing lithographic printing using fountain solution as a material repelling ink and water-free lithographic printing using silicone rubber can be mentioned.
- the ink cohesion is insufficient under high shear during printing, the ink adheres to the non-image area where ink is not originally attached without repelling. The adhered ink is transferred to an unintended place on the substrate. This phenomenon is called scumming and is a kind of printing failure.
- Patent Document 1 In order to increase the cohesive strength of ink, there is a proposal of a lithographic printing ink that increases the resin concentration in the ink and suppresses background stains (for example, Patent Document 1).
- the ink in the uppermost layer of the printed part is one or more selected from a phthalate ester, adipic acid ester, and sebacic acid ester as a gloss improver
- a phthalate ester for example, adipic acid ester
- sebacic acid ester for example, a phthalate ester, adipic acid ester, and sebacic acid ester
- low molecular weight compounds such as phthalic acid esters, adipic acid esters, and sebacic acid esters evaporate little by little under high shear during printing.
- print defects such as deterioration in transferability due to thickening of the ink and changes in the quality of printed matter between the early and late stages of printing occur.
- the problem to be solved by the present invention is to provide a production method for obtaining a printed material having a high gloss in a printing portion where multiple colors overlap in lithographic printing, and an ink set for lithographic printing. Also provided are a production method and a lithographic printing ink set for suitably obtaining a printed matter that guarantees ground stain resistance and has a single-color portion having high gloss.
- the method for producing a printed material according to the present invention includes a step of applying at least a black ink for lithographic printing, a cyan ink for lithographic printing, a magenta ink for lithographic printing, and a yellow ink for lithographic printing on the substrate.
- the difference in the surface tension of the ink applied to the ink is 3.5 mN / m or less.
- the lithographic printing ink set of the present invention is a lithographic printing ink set containing at least a black ink, a cyan ink, a magenta ink, and a yellow ink, and a difference in surface tension between the inks contained in the lithographic printing ink set. Is within 3.5 mN / m.
- the method for producing a printed matter and the lithographic printing ink set of the present invention in lithographic printing, it is possible to obtain a printed matter having a high gloss printing portion where multiple colors overlap. Further, it is possible to suitably obtain a printed matter having no background stain and having a single color portion having high gloss.
- the color of a printed material is expressed using black ink, cyan ink, magenta ink, and yellow ink.
- the method for producing a printed matter according to the present invention includes a step of applying at least a black ink for lithographic printing, a cyan ink for lithographic printing, a magenta ink for lithographic printing, and a yellow ink for lithographic printing on a substrate. .
- the surface tension of the lithographic printing ink of the present invention is calculated from the contact angle measured by the droplet method of an automatic contact angle meter.
- an ink is applied smoothly on a glass substrate. If the ink surface is not smooth, an angle smaller than the true contact angle is measured, causing an error.
- the ink surface smoother after applying the ink on the glass substrate, the ink is allowed to stand for 30 minutes in a dark place, and then the contact angle is measured.
- pure water having a known surface tension value and ethylene glycol are used as the solution to be deposited on the ink.
- a droplet of the solution is prepared using a syringe, and the droplet is brought into contact with the ink applied to the glass substrate to be deposited.
- the surface tension of the ink is calculated using the contact angle when 30 seconds have passed since the ink was deposited. In general, the closer the surface tension, the better the wettability.
- the surface tension is decomposed into a nonpolar dispersion force component ⁇ d and a polar hydrogen bonding dispersion force component ⁇ h (see the following formula (1)).
- the Young equation is established for the substances A and B (the surface tension of the substance A is ⁇ A , the surface tension of the solution B is ⁇ B , and the substance A and the solution the surface tension between the B gamma a-B, referred to as theta a-B and the contact angle of the substance a and the solution B) (following formula (2) refer).
- the extended Fowkes model is proposed about the surface tension between the substance A and the solution B (refer following numerical formula (3)).
- ink is used as the substance A
- pure water and ethylene glycol are used as the solution B
- formulas (4) and (5) are derived from the formulas (1), (2), and (3).
- the surface tension is calculated.
- the surface tension ⁇ of pure water is 72.8 mN / m
- the nonpolar dispersive force component ⁇ d is 21.8 mN / m
- the polar hydrogen bonding dispersive force component ⁇ h is 51.0 mN / m
- ethylene glycol Has a surface tension ⁇ of 48.8 mN / m
- a non-polar dispersion force component ⁇ d of 32.8 mN / m
- a polar hydrogen bonding dispersion force component ⁇ h of 16.0 mN / m.
- the ink supplied to the ink fountain is transferred in the order of a metal roll, a lithographic plate, and a blanket, and is finally transferred from the blanket to the base material to obtain a printed matter.
- the blanket material has a great influence on the quality of the printed matter.
- the blanket material is ethylene / propylene / diene rubber or acrylonitrile / butadiene rubber.
- ethylene / propylene / diene rubber which is hard to penetrate the monomer in the ink, is widely used.
- the surface tension of ethylene / propylene / diene rubber is 25.4 mN / m
- the surface tension of acrylonitrile / butadiene rubber is 38.0 mN / m.
- the method for producing a printed material according to the present invention is characterized in that the difference in surface tension of the ink applied on the substrate is within 3.5 mN / m. This means that the difference between the maximum surface tension and the minimum surface tension is 3.5 mN / m or less with respect to the surface tension of each of the plurality of lithographic printing inks applied on the substrate.
- the difference in surface tension is within 3.5 mN / m, the wetness of the upper layer ink with respect to the lower layer ink is improved in the printing area where multiple colors overlap, the upper layer ink tends to be smooth, and the gloss of the printed matter is improved. To do.
- the difference in the surface tension of the ink is more preferably within 3.0 mN / m, and even more preferably within 2.5 mN / m.
- the surface tension of each ink can be adjusted by at least one kind and / or content selected from a resin, a polyfunctional (meth) acrylate, and a surfactant that are formed in the ink. Therefore, the difference in the surface tension of the ink applied on the base material can be caused by changing the types of resin, polyfunctional (meth) acrylate and / or surfactant composing each ink, and increasing or decreasing their contents. Can be adjusted.
- the surface tension of the lithographic printing ink applied on the substrate is preferably 45 mN / m or more and 60 mN / m or less. This means that the surface tension of each of the plurality of lithographic printing inks applied on the substrate is 45 mN / m or more and 60 mN / m or less.
- the surface tension of the lithographic printing ink is 45 mN / m or more, the ink is easily peeled off when it is transferred from the blanket to the base material, and the surface of the ink transferred to the base material becomes smooth so that the gloss of the printed matter Will improve.
- the transfer property of the ink to the blanket is improved. More preferably, it is 58 mN / m or less, More preferably, it is 56 mN / m or less.
- a printed matter is obtained by transferring ink onto a substrate in order, and the gloss of the printed matter changes depending on the order of transferring the ink.
- the ink may be transferred onto the substrate in the order of lithographic black ink, lithographic cyan ink, lithographic magenta ink, and lithographic yellow ink.
- the tack value of the lithographic printing ink of the present invention is measured at an rpm of 400 rpm and 38 ° C. using 1.31 ml of ink weighed with an ink pipette. The measured value 1 minute after the start of measurement is taken as the tack value in the present invention.
- the tack value is an index representing the tackiness of the ink, and the higher the tack value, the higher the tackiness of the ink.
- the tack value (1 minute value) of the black ink for lithographic printing applied on the substrate is 5.0 or more and 8.0 or less.
- the phenomenon in which the lower layer ink previously transferred to the substrate is peeled off by the post-printing ink is called reverse trapping.
- reverse trapping occurs, a print with the desired pattern cannot be obtained and an unclear print is formed, or the preprinted ink is mixed with the post-printing ink, and the color of the print changes at the start and end of printing. Defects occur.
- a method for reducing the tack value it is known to reduce the resin concentration in the ink or to add a silicone liquid.
- the resin concentration in the ink is lowered, the cohesive strength of the ink will be reduced and the ink stain resistance will be lowered.
- silicone liquid is added, the silicone liquid will form a film on the ink surface and the transferability between the ink rollers will be reduced. Print defects such as lowering occur.
- the tack value of the lithographic black ink is more preferably 5.5 or more, and still more preferably 6.0 or more.
- the tack value of the ink is high, irregularities are likely to occur on the surface of the ink transferred to the substrate, and the gloss of the printed matter is lowered.
- the tack value of the black ink for lithographic printing is more preferably 7.5 or less, and further preferably 7.0 or less.
- the tack value (1 minute value) of the lithographic printing cyan ink, lithographic printing magenta ink, and lithographic yellow ink applied on the substrate is 5.0 or more and 8.0 as in the lithographic black ink. The following is preferable, and the more preferable range is the same. In order to prevent reverse trapping, it is preferable to lower the tack of the ink according to the printing order. When printing in the order of black ink, cyan ink, magenta ink, and yellow ink, the tack value of each ink is black in order of increasing tack value. The ink, cyan ink, magenta ink, and yellow ink should be adjusted.
- the ink coating on the printed matter can be instantly cured by irradiating the active energy ray.
- the manufacturing method of the printed matter of this invention includes the process of irradiating and hardening
- Any active energy ray can be used as long as it has excitation energy necessary for the curing reaction, and for example, ultraviolet rays or electron beams are preferably used.
- an electron beam apparatus having an energy beam of 100 eV or more and 500 eV or less 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.
- a metal halide lamp a lamp having an illuminance of 80 W / cm or more and 150 W / cm or less When the conveyance speed by the conveyor is 50 m / min or more and 150 m / min or less, the ink is easily cured, and this is preferable from the viewpoint of productivity.
- the illuminance of the lamp is preferably 90 W / cm or more, and more preferably 100 W / cm or more because the ink is easily cured.
- 140 W / cm or less is more preferable for power consumption reduction, and 130 W / cm or less is further more preferable.
- About the conveyance speed of a conveyor 60 m / min or more is more preferable for production tact improvement, and 70 m / min or more is still more preferable.
- 130 m / min or less is more preferable, and 110 m / min or less. Is more preferable.
- the ink is not sufficiently smoothed because the ink is cured by irradiating active energy rays shortly after the ink is transferred to the substrate. As a result, there was a problem in that unevenness was generated on the surface and the gloss of the printed matter was lowered.
- the quality of the printed matter can be further improved by adjusting the viscosity of the lithographic printing ink as follows.
- the viscosity of lithographic printing ink is measured at 25 ° C. using 0.15 ml of ink weighed with an ink pipette using a cone-plate rotary viscometer.
- the viscosity (A) of the lithographic printing ink applied on the substrate at a rotation speed of 0.5 rpm is preferably 5 Pa ⁇ s or more and 200 Pa ⁇ s or less.
- the viscosity (A) is 5 Pa ⁇ s or more, transferability between ink rollers is increased. More preferably, it is 10 Pa.s or more, More preferably, it is 20 Pa.s or more.
- the viscosity (A) is 200 Pa ⁇ s or less, the fluidity of the ink is improved, the ink transferred to the substrate is easily smoothed, and the gloss of the printed matter is improved. More preferably, it is 150 Pa * s or less, More preferably, it is 100 Pa * s or less.
- the viscosity (B) at a rotational speed of 20 rpm (corresponding to a shear speed of 120 s ⁇ 1 ) and the viscosity (C) at a rotational speed of 50 rpm of the lithographic printing ink applied on the substrate are: Both are preferably 5 Pa ⁇ s or more and 200 Pa ⁇ s or less. When the viscosity (B) and the viscosity (C) are both 5 Pa ⁇ s or more, the cohesive force of the ink is increased, and the stain resistance of the ink can be improved. More preferably, it is 10 Pa ⁇ s or more, and further preferably 15 Pa ⁇ s or more.
- the ink is satisfactorily attached to the lithographic printing plate. More preferably, it is 40 Pa * s or less, More preferably, it is 20 Pa * s or less.
- the viscosity ratio (C) / (B) which is the ratio of the viscosity (B) to the viscosity (C) of the lithographic printing ink applied on the substrate, is 0.75. It is preferable that it is above 1.00.
- the viscosity ratio (C) / (B) is within the above range, the ink cohesion is sufficiently maintained even at high speed and high shear during printing, improving the ink stain resistance. It can be made. More preferably, it is 0.80 or more and 1.00 or less, More preferably, it is 0.90 or more and 1.00 or less.
- the lithographic printing ink to be applied onto the substrate is a resin having a hydrophilic group and a polyfunctional (meth) acrylate having a hydroxyl group in order to adjust the viscosity ratio (C) / (B) described above. It is preferable to contain.
- the hydrophilic group and hydroxyl group improve the pigment dispersibility in the ink, so that the structural viscosity of the ink (the pigment forms a cohesive structure and increases the viscosity) is reduced, and the ink has a low viscosity under low shear. It is thought that. It is considered that the printed matter using the lithographic printing ink exhibits high gloss due to the low ink viscosity under low shear.
- the resin having the hydrophilic group is dissolved in the polyfunctional (meth) acrylate having the hydroxyl group, and the viscosity is increased by an interaction such as a hydrogen bond between the hydrophilic group and the hydroxyl group.
- the lysate is a Newtonian fluid and maintains a constant viscosity regardless of shear strength.
- the viscosity of the melt as the medium is dominant, so that the decrease in viscosity due to shearing is small and high. Maintain high viscosity under shear.
- the ink cohesive force is high and the ink resilience to the non-image area is improved under high shear as in printing, thereby improving the background stain resistance.
- the lithographic printing ink applied on the substrate can contain a resin having a hydrophilic group, a polyfunctional (meth) acrylate, a pigment, and a surfactant.
- the hydrophilic group of the resin having the hydrophilic group is considered to improve the fluidity of the ink because the pigment in the ink is dispersed and stabilized. By improving the fluidity of the ink, the ink transferred to the substrate tends to be smooth, and the gloss of the printed matter is improved. Further, the hydrophilic group enhances the cohesive strength of the ink under high shear during printing due to interaction such as hydrogen bonding. When the cohesive strength of the ink is increased, the ink resilience with respect to the non-image area is improved, and as a result, the soil resistance is improved.
- the lithographic printing ink to be applied on the base material contains a resin having a hydrophilic group, so that it becomes soluble in an aqueous cleaning liquid containing water as a main component, and is non-petroleum-based cleaning.
- the agent can be applied.
- the surface tension of the lithographic printing ink is increased / decreased by adjusting the type and / or content of the resin having a hydrophilic group, and the difference in the surface tension of the lithographic printing ink applied on the substrate is 3.5 mN / It contributes to adjustment within m.
- hydrophilic group of the resin having a hydrophilic group examples include a hydroxyl group, an amino group, a mercapto 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 because good solubility of the resin in an aqueous cleaning solution, pigment dispersibility, and soil resistance can be obtained. More preferably, it is 60 mgKOH / g or more, More preferably, it is 75 mgKOH / g or more. Further, it is preferable that the acid value is 200 mgKOH / g or less because interaction such as hydrogen bonding can be suppressed and the fluidity of the lithographic printing ink of the present invention can be maintained, so that tack (adhesiveness) can be reduced.
- the acid value can be determined according to the neutralization titration method of the test method 3.1 of JIS K 0070: 1992.
- the solubility of the resin having a hydrophilic group in water is preferably 0.1 g / (100 g-H 2 O) or more. When the solubility is within the above range, cleaning with an aqueous cleaning solution is facilitated.
- the solubility of the resin having a hydrophilic group in water is more preferably 0.3 g / (100 g-H 2 O) or more, and further preferably 0.5 g / (100 g-H 2 O) or more. .
- so the solubility of the resin having a hydrophilic group in water is 100 g / (100 g-H 2 O) or less is preferable, 50 g / (100 g-H 2 O) or less is more preferable, and 10 g / (100 g-H 2 O) or less is more preferable.
- the solubility is the mass (g) of resin dissolved in 100 g of water at 25 ° C.
- the resin having a hydrophilic group has a weight average molecular weight of 5,000 or more because the soil resistance of the lithographic printing ink is improved. More preferably, it is 15,000 or more, More preferably, it is 20,000 or more.
- the weight average molecular weight is preferably 100,000 or less because the fluidity of the lithographic printing ink is maintained and tack (adhesiveness) can be reduced. More preferably, it is 75,000 or less, More preferably, it is 50,000 or less.
- the weight average molecular weight of the resin can be obtained by measuring in terms of polystyrene using gel permeation chromatography (GPC).
- the resin having a hydrophilic group examples include an acrylic resin, a styrene acrylic resin, a styrene maleic acid resin, a rosin modified maleic resin, a rosin modified acrylic resin, an epoxy resin, a polyester resin, a polyurethane resin, and a phenol resin. It is not particularly limited. Among the resins listed above, acrylic resins, styrene acrylic resins, styrene malees are available from the viewpoints of availability of monomers, low cost, ease of synthesis, compatibility with other components in the ink, and dispersibility of pigments. An acid resin is preferably used as the resin having the hydrophilic group.
- acrylic resin, styrene acrylic 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 Such as amino group-containing monomers such as 2- (mercaptoacetoxy) ethyl acrylate, mercapto group-containing monomers such as acrylamide t-butylsulfonic acid, phosphoric acid such as 2-methacryloxyethyl acid phosphate, etc.
- carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate or their acid anhydrides
- 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 because it is easily cured by active energy rays.
- the iodine value of the ethylenically unsaturated group in the resin having a hydrophilic group and an ethylenically unsaturated group is preferably 0.5 mol / kg or more and 3.0 mol / kg or less. When the iodine value is within the above range, the ink is easily cured by active energy rays, and the acid value of the resin having the hydrophilic group and the ethylenically unsaturated group is easily adjusted to a suitable range.
- the iodine value of the ethylenically unsaturated group is preferably 1.0 mol / kg or more, and more preferably 1.5 mol / kg or more in order to promote the curing of the ink. Further, in order to easily adjust the acid value of the resin having a hydrophilic group and an ethylenically unsaturated group to a suitable range, it is more preferably 2.7 mol / kg or less, and further preferably 2.4 mol / kg or less.
- the iodine value of the ethylenically unsaturated group can be determined by the method described in JIS K 0070: 1992, test method section 6.0.
- the resin having the hydrophilic group and the ethylenically unsaturated group can be prepared by the following method. That is, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, an acrylic acid chloride, or a methacrylic acid chloride with respect to a mercapto group, amino group, hydroxyl group or carboxyl group which is an active hydrogen-containing group in a resin having a hydrophilic group Alternatively, a resin having a hydrophilic group and an ethylenically unsaturated group can be obtained by addition reaction of 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 lithographic printing ink applied on the substrate has a pigment dispersibility of the ink and a ground resistance of 5% by mass or more when the content of the resin having the hydrophilic group is 5% by mass or more.
- This is preferable because the dirtiness is improved. More preferably, it is 8 mass% or more, More preferably, it is 11.5 mass% or more.
- content of the resin which has the said hydrophilic group is 30 mass% or less, since the fluidity
- the lithographic printing ink applied on the substrate may contain a polyfunctional (meth) acrylate. Since the polyfunctional (meth) acrylate has a double bond group, the ink is easily cured by active energy rays. Also, the surface tension of the lithographic printing ink is increased or decreased by adjusting the type and / or content of the polyfunctional (meth) acrylate, and the difference in the surface tension of the lithographic printing ink applied on the substrate is 3.5 mN / It contributes to adjustment within m.
- the polyfunctional (meth) acrylate is not particularly limited as long as it is a compound having two or more (meth) acrylate groups.
- the number of (meth) acrylate groups (hereinafter sometimes referred to as “functional group number”) is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
- the number of functional groups of the polyfunctional (meth) acrylate is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
- the polyfunctional (meth) acrylate preferably has a polar group.
- the polar group include a hydroxyl group and a carboxy group, and among these, a hydroxyl group is preferable.
- the polar group such as the hydroxyl group is considered to improve the fluidity of the ink in order to stabilize the dispersion of the pigment. By improving the fluidity of the ink, the ink transferred to the substrate tends to be smooth, and the gloss of the printed matter is improved.
- the polar group such as the hydroxyl group enhances the cohesive strength of the ink under high shear during printing due to interaction such as hydrogen bonding. When the cohesive strength of the ink is increased, the ink resilience with respect to the non-image area is improved, and as a result, the soil resistance is improved.
- the hydroxyl value of the polyfunctional (meth) acrylate is preferably 50 mgKOH / g or more because the pigment dispersibility and the stain resistance of the ink are improved. More preferably, it is 75 mgKOH / g or more, More preferably, it is 100 mgKOH / g or more. Moreover, since the hydroxyl value is 200 mgKOH / g or less, interaction such as hydrogen bonding can be suppressed, and the fluidity of the ink can be kept good, so that the tack (adhesiveness) can be reduced. . More preferably, it is 180 mgKOH / g or less, More preferably, it is 160 mgKOH / g or less.
- the hydroxyl value of the polyfunctional (meth) acrylate can be determined by the method described in test method section 7.1 of JIS K 0070: 1992.
- the molecular weight of the polyfunctional (meth) acrylate is 100 or more because the soil stain resistance of the ink is improved. More preferably, it is 200 or more, More preferably, it is 250 or more.
- the molecular weight is preferably 1,000 or less because the fluidity of the ink can be kept good and tack (adhesiveness) can be reduced. More preferably, it is 700 or less, More preferably, it is 500 or less.
- polyfunctional (meth) acrylate examples include bifunctional ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, 1,3 butylene glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc.
- sid adduct examples include tetraerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, diglycerin tetra (meth) acrylate, and ethylene oxide adducts and propylene oxide adducts.
- dipentaerythritol hexa (meth) acrylate these ethylene oxide adducts, and propylene oxide adducts can be mentioned.
- Preferred specific examples of the polyfunctional (meth) acrylate having a hydroxyl group include poly (meta) of polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, diglycerin, ditrimethylolpropane, isocyanuric acid, and dipentaerythritol. ) Acrylates, and their alkylene oxide adducts.
- trimethylolpropane di (meth) acrylate trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di or tri (meth) acrylate, diglycerin di or tri (meth) acrylate, ditrimethylolpropane
- di- or tri (meth) acrylate dipentaerythritol di-, tri-, tetra- or penta (meth) acrylate, and ethylene oxide adducts, propylene oxide adducts, tetraethylene oxide adducts, and the like.
- the lithographic printing ink of the present invention has excellent fluidity and pigment dispersibility, and has improved soil stain resistance, so pentaerythritol tri (meth) acrylate, diglycerin tri (meth) acrylate, and ditrimethylol.
- pentaerythritol tri (meth) acrylate diglycerin tri (meth) acrylate, and ditrimethylol.
- Propane tri (meth) acrylate is particularly preferred.
- the lithographic printing ink applied on the substrate contains 20% by mass or more of the polyfunctional (meth) acrylate, the pigment dispersibility and the stain resistance of the ink are improved. Therefore, it is preferable. More preferably, it is 30 mass% or more, More preferably, it is 40 mass% or more. Moreover, since the fluidity
- the surface tension of the ink basically, the surface tension increases as the amount of polar groups in the ink increases, and the surface tension decreases as the amount of polar groups in the ink decreases.
- the content of the resin having the hydrophilic group and the polyfunctional (meth) acrylate having a hydroxyl group By adjusting the content of the resin having the hydrophilic group and the polyfunctional (meth) acrylate having a hydroxyl group, the amount of polar group in the ink is changed, and the difference in the surface tension of the ink applied on the substrate Can be easily adjusted within 3.5 mN / m.
- the difference in the surface tension of the ink applied on the substrate may be adjusted depending on the type and / or content of the resin having a hydrophilic group and the polyfunctional (meth) acrylate, and in addition to these, or independently.
- the difference in the surface tension of the ink applied on the substrate may be adjusted according to the type and / or content of the surfactant, pigment and diluent.
- the acid value of the resin having a hydrophilic group is preferably 60 mgKOH / g to 200 mgKOH / g
- the content of the resin having a hydrophilic group is 11.5% to 14% by mass
- the hydroxyl value of the polyfunctional (meth) acrylate having a hydroxyl group is 50 mgKOH / g to 200 mgKOH / g.
- the content of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 20% by mass or more and 30% by mass or less.
- the acid value of the resin having a hydrophilic group is preferably 60 mgKOH / g in order to easily adjust the tack value to 5.0 or more and 8.0 or less while ensuring the soil resistance.
- 200 mgKOH / g or less the weight average molecular weight of the resin having a hydrophilic group is 15,000 or more and 50,000 or less, the content of the resin having a hydrophilic group is 11.5% by mass or more and 14% by mass or less, a hydroxyl group
- the polyfunctional (meth) acrylate having a hydroxyl value of 50 mgKOH / g to 200 mgKOH / g and the content of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 20% by mass to 30% by mass.
- the lithographic printing ink applied on the substrate may contain a surfactant.
- the surfactant content adjusts the difference between the surface tension of the lithographic printing ink applied on the substrate and the surface tension of the lithographic printing ink, in addition to improving the fluidity of the lithographic printing ink. Therefore, it is preferably 5% by mass or more and 50% by mass or less with respect to the pigment.
- surfactant examples include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)”, “Disperbyk-101” manufactured by BYK Chemie.
- the lithographic printing ink applied on the substrate may contain a pigment.
- the pigment one or more selected from inorganic pigments and organic pigments generally used in lithographic printing ink compositions can be used.
- inorganic pigments 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 and the like. It is done.
- 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.
- the pigment concentration 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 to be applied on the substrate is a component selected from a silicone liquid, an alkyl (meth) acrylate, a hydrocarbon solvent, a vegetable oil, a fatty acid ester derived from a vegetable oil, and a fluorocarbon. It is preferable to include one or more types.
- the component has the effect of reducing the ink adhesion to the silicone rubber that is the non-image area of the waterless lithographic printing plate, and as a result, a printed product without background stains can be obtained.
- the reason for reducing the ink adhesion to the silicone rubber is presumed as follows. That is, the component contained in the ink diffuses out of the ink by contact with the silicone rubber surface and covers the silicone rubber surface in a thin film. 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 (meth) acrylate is preferable because it cures when irradiated with active energy rays, and thus improves the physical properties of the cured film of the ink and at the same time the sensitivity to the active energy rays.
- Specific compounds of the above components are as follows.
- 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 (meth) acrylate nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate
- Examples include hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and isooctadecyl (meth) acrylate.
- hydrocarbon solvent examples include polyolefin oil, naphthene oil, paraffin oil 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.
- 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.
- the lithographic printing ink applied on the substrate is a component selected from the silicone liquid, alkyl (meth) acrylate, hydrocarbon solvent, vegetable oil, fatty acid ester derived from vegetable oil, and fluorocarbon. It is preferable to contain 0.5% by mass or more of one or more of the above in order to improve the soil resistance. More preferably, it is 1 mass% or more, More preferably, it is 2 mass% or more. Moreover, since the storage stability of lithographic printing ink can be improved, it is preferable to contain 10 mass% or less. More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less.
- the lithographic printing ink applied on the substrate contains an oil-soluble surfactant (emulsifier).
- emulsifier here refers to a surfactant that dissolves in oil (an organic compound insoluble in water) and takes in water to form a W / O emulsion.
- an appropriate amount generally said to be 10 to 20% by mass of the total amount of ink
- dampening water is taken in and emulsified, so that the non-image area can be repelled with dampening water.
- the ink stain resistance is improved.
- the ratio between the hydrophilic group and the hydrophobic group of the emulsifier is represented by the HLB value.
- the HLB value mentioned here is a value representing the degree of affinity of the surfactant with water and oil.
- the HLB value takes a value from 0 to 20, and the closer to 0, the higher the lipophilicity and the closer to 20, Means high hydrophilicity.
- the HLB value of the emulsifier is preferably 10 or more because it dissolves water well. More preferably, it is 11 or more. Further, it is preferably 18 or less because it dissolves well in the lithographic printing ink. More preferably, it is 17 or less.
- the emulsifier 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, polyoxy Alkylene stearyl ether, polyoxyalkylene cetyl ether Polyoxyalkylene palmitic ether, sorbitan acid mono, di, trialkyl ether, sorbitan acid mono, di, trilauryl ether, sorbitan acid mono, di, trioleyl ether, sorbitan acid mono, di, di
- the lithographic printing ink applied on the substrate preferably contains 0.01% by mass or more of an emulsifier because 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 0.10 mass% or more. Further, since the lithographic printing ink does not take in dampening water excessively during printing and is incompatible with dampening water, the emulsifier is preferably 5.00% by mass or less. More preferably, it is 3.00 mass% or less, More preferably, it is 1.00 mass% or less.
- the lithographic printing ink applied on the substrate preferably contains a photopolymerization initiator and has ultraviolet curability.
- the lithographic printing ink preferably contains a sensitizer in addition to the photopolymerization initiator.
- the photopolymerization initiator preferably generates active radical species.
- active radical species include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone (also known as Michler's ketone), 4, 4-bis (diethylamino) benzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, 1-hydroxycyclohexyl-phenyl ketone, 4-phenylbenzophenone, hydroxybenzophenone, dibenzyl ketone, fluorenone, 2, 2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy)- Phenyl] -2-hydr Roxy-2-methyl-1-propan-1-one, pt-butyldichloroacetophenone,
- the sensitizer examples include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,3-bis (4-diethylaminobenzal) Cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, 4,4-bis (dimethylamino) -benzophenone ( Alias: Michler's ketone), 4,4-bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethyl Aminobenzyliden
- one or more of these photopolymerization initiators and sensitizers can be used for the lithographic printing ink applied on the substrate.
- the lithographic printing ink preferably contains 0.1% by mass or more of the photopolymerization initiator because good sensitivity can be obtained. More preferably, it is contained in an amount of 1.0% by mass or more, and more preferably 3.0% by mass or more. Further, it is preferable that the photopolymerization initiator is contained in an amount of 20.0% by mass or less because the storage stability of the ink is improved. 15.0 mass% or less is more preferable, and 10.0 mass% or less is further more preferable.
- the content thereof is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, based on the fact that the ink can obtain good sensitivity. More preferably, the content is 0.0% by mass or more. From the viewpoint of improving the storage stability of the ink, the content is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and still more preferably 10.0% by mass or less based on the ink.
- a polymerization inhibitor to the lithographic printing ink applied on the substrate in order to improve the stability during storage.
- the polymerization inhibitor include hydroquinone, monoetherified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, and pyrogallol.
- the addition amount of the polymerization inhibitor is preferably 0.01% by mass or more and 5.00% by mass or less based on the ink because good storage stability can be obtained.
- the lithographic printing ink to be applied on the substrate can use additives such as a wax, an antifoaming agent, and a transferability improving agent as necessary.
- a coating material in which a white pigment such as clay or calcium carbonate and an adhesive such as starch are mixed is applied to the surface of fine paper or medium paper, It is preferable to use glossy coated paper having a smooth surface.
- glossy coated paper include, but are not limited to, art paper, coated paper, cast paper, and the like.
- the glossy coated paper is preferably a coated paper having a 75 ° specular gloss of 20% or more as described in JIS P 8142: 2005.
- a method of applying onto a substrate it can be applied onto the substrate by lithographic printing.
- lithographic printing There are water and no water as a lithographic printing method, but either method can be used.
- the thickness of the ink coating on the printed material is preferably 0.1 to 50.0 ⁇ m.
- the ink cost can be reduced while maintaining good print quality.
- the lithographic printing ink set of the present invention is a lithographic printing ink set containing at least a black ink, a cyan ink, a magenta ink, and a yellow ink, and there is a difference in surface tension between the inks contained in the lithographic printing ink set. It is within 3.5 mN / m. This is because the difference between the maximum surface tension and the minimum surface tension of the black ink, cyan ink, magenta ink, and yellow ink constituting the lithographic printing ink set is 3.5 mN / m or less. Means.
- the difference in the surface tension of the ink is more preferably within 3.0 mN / m, and even more preferably within 2.5 mN / m.
- the surface tension of each ink can be adjusted by at least one kind and / or content selected from a resin, a polyfunctional (meth) acrylate, and a surfactant that are composed in each ink. Therefore, the difference in the surface tension of the ink can be adjusted by changing the type of resin, polyfunctional (meth) acrylate and / or surfactant constituting each ink, or by increasing or decreasing the content thereof. .
- the surface tension of the ink contained in the lithographic printing ink set of the present invention is preferably 45 mN / m or more and 60 mN / m or less. This means that the surface tension of each of the black ink, cyan ink, magenta ink, and yellow ink constituting the lithographic printing ink set is 45 mN / m or more and 60 mN / m or less.
- the surface tension of the lithographic printing ink is 45 mN / m or more, the ink is easily peeled off when transferred from the blanket to the substrate, and transferred to the substrate. The gloss of the printed matter is improved by the smoothed ink surface.
- the transfer property of the ink to the blanket is improved. More preferably, it is 58 mN / m or less, More preferably, it is 56 mN / m or less.
- lithographic printing a printed matter is obtained by transferring ink onto a substrate in order, and the gloss of the printed matter changes depending on the order of transferring the ink.
- the tack value (1 minute value) of the black ink contained in the lithographic printing ink set of the present invention at 38 ° C. and 400 rpm measured with an incometer is preferably 5.0 or more and 8.0 or less.
- the tack value of the black ink is more preferably 5.5 or more, and even more preferably 6.0. That's it.
- irregularities are likely to occur on the surface of the ink transferred to the substrate, and the gloss of the printed matter is lowered.
- the tack value of the black ink is more preferably 7.5 or less, and even more preferably 7.0 or less.
- the tack value (1 minute value) of the lithographic printing cyan ink, lithographic printing magenta ink, and lithographic yellow ink applied on the substrate is 5.0 or more and 8.0 as in the lithographic black ink. The following is preferable, and the more preferable range is the same. In order to prevent reverse trapping, it is preferable to lower the tack of the ink according to the printing order. When printing in the order of black ink, cyan ink, magenta ink, and yellow ink, the tack value of each ink is black in order of increasing tack value. The ink, cyan ink, magenta ink, and yellow ink should be adjusted.
- the viscosity (A) of the ink contained in the lithographic printing ink set of the present invention at a rotation speed of 0.5 rpm is preferably 5 Pa ⁇ s or more and 200 Pa ⁇ s or less.
- the viscosity (A) is 5 Pa ⁇ s or more, transferability between ink rollers is increased. More preferably, it is 10 Pa.s or more, More preferably, it is 20 Pa.s or more.
- the viscosity (A) is 200 Pa ⁇ s or less, the fluidity of the ink is improved, the ink transferred to the substrate is easily smoothed, and the gloss of the printed matter is improved. More preferably, it is 150 Pa * s or less, More preferably, it is 100 Pa * s or less.
- the viscosity (B) at a rotational speed of 20 rpm (corresponding to a shear speed of 120 s ⁇ 1 ) and the viscosity (C) at a rotational speed of 50 rpm of the ink contained in the lithographic printing ink set of the present invention are both 5 Pa ⁇ s or more and 200 Pa ⁇ It is preferable that it is s or less.
- the viscosity (B) and the viscosity (C) are both 5 Pa ⁇ s or more, the cohesive force of the ink is increased, and the stain resistance of the ink can be improved. More preferably, it is 10 Pa ⁇ s or more, and further preferably 15 Pa ⁇ s or more.
- the ink is satisfactorily attached to the lithographic printing plate. More preferably, it is 40 Pa * s or less, More preferably, it is 20 Pa * s or less.
- the viscosity ratio (C) / (B), which is the ratio of the viscosity (B) and the viscosity (C), of the ink contained in the lithographic printing ink set of the present invention is 0.75 or more and 1.00 or less. Preferably there is.
- the viscosity ratio (C) / (B) is within the above range, the ink cohesion is sufficiently maintained even at high speed and high shear during printing, improving the ink stain resistance. It can be made. More preferably, it is 0.80 or more and 1.00 or less, More preferably, it is 0.90 or more and 1.00 or less.
- the ink contained in the lithographic printing ink set of the present invention contains a resin having a hydrophilic group and a polyfunctional (meta) having a hydroxyl group in order to bring the viscosity ratio (C) / (B) into the desired range. ) It is preferable to contain an acrylate.
- the hydrophilic group and hydroxyl group improve the pigment dispersibility in the ink, so that the structural viscosity of the ink (the pigment forms a cohesive structure and increases the viscosity) is reduced, and the ink has a low viscosity under low shear. It is thought that.
- the printed matter using the ink contained in the lithographic printing ink set of the present invention exhibits high glossiness due to the low ink viscosity under low shear.
- the resin having the hydrophilic group is dissolved in the polyfunctional (meth) acrylate having the hydroxyl group, and the viscosity is increased by an interaction such as a hydrogen bond between the hydrophilic group and the hydroxyl group.
- the lysate is a Newtonian fluid and maintains a constant viscosity regardless of shear strength.
- the viscosity of the dissolved material that is the medium becomes dominant. Maintain high viscosity.
- the ink cohesive force is high and the ink resilience to the non-image area is improved under high shear as in printing, thereby improving the background stain resistance.
- the ink contained in the lithographic printing ink set of the present invention can contain a resin having a hydrophilic group, a polyfunctional (meth) acrylate, a pigment, and a surfactant.
- the hydrophilic group of the resin having the hydrophilic group is considered to improve the fluidity of the ink because the pigment in the ink is dispersed and stabilized. By improving the fluidity of the ink, the ink transferred to the substrate tends to be smooth, and the gloss of the printed matter is improved. Further, the hydrophilic group enhances the cohesive strength of the ink under high shear during printing due to interaction such as hydrogen bonding. When the cohesive strength of the ink is increased, the ink resilience with respect to the non-image area is improved, and as a result, the soil resistance is improved.
- the ink contained in the lithographic printing ink set of the present invention contains a resin having a hydrophilic group
- the ink becomes soluble in an aqueous cleaning liquid containing water as a main component, and a non-petroleum cleaning agent can be applied.
- the surface tension of the lithographic printing ink is increased / decreased by adjusting the type and / or content of the resin having a hydrophilic group, and the difference in the surface tension of the lithographic printing ink applied on the substrate is 3.5 mN / It contributes to adjustment within m.
- hydrophilic group of the resin having a hydrophilic group examples include a hydroxyl group, an amino group, a mercapto 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 30 mgKOH / g or more because good solubility of the resin in an aqueous cleaning solution, pigment dispersibility, and soil resistance can be obtained. More preferably, it is 60 mgKOH / g or more, More preferably, it is 75 mgKOH / g or more.
- the acid value is 200 mgKOH / g or less, interaction such as hydrogen bonding can be suppressed, so that the fluidity of the lithographic printing ink of the present invention can be maintained and tack (adhesiveness) can be reduced. preferable.
- the acid value is within the above range, the pigment dispersibility, stain resistance, and fluidity of the ink can be kept good.
- the solubility of the resin having a hydrophilic group in water is preferably 0.1 g / (100 g-H 2 O) or more. When the solubility is within the above range, cleaning with an aqueous cleaning solution is facilitated.
- the solubility of the resin having a hydrophilic group in water is more preferably 0.3 g / (100 g-H 2 O) or more, and further preferably 0.5 g / (100 g-H 2 O) or more. .
- so the solubility of the resin having a hydrophilic group in water is 100 g / (100 g-H 2 O) or less is preferable, 50 g / (100 g-H 2 O) or less is more preferable, and 10 g / (100 g-H 2 O) or less is more preferable.
- the solubility is the mass (g) of resin dissolved in 100 g of water at 25 ° C.
- the resin having a hydrophilic group has a weight average molecular weight of 5,000 or more because the soil resistance of the lithographic printing ink is improved. More preferably, it is 15,000 or more, More preferably, it is 20,000 or more.
- the weight average molecular weight is preferably 100,000 or less because the fluidity of the lithographic printing ink is maintained and tack (adhesiveness) can be reduced. More preferably, it is 75,000 or less, More preferably, it is 50,000 or less.
- the weight average molecular weight of the resin can be obtained by measuring in terms of polystyrene using gel permeation chromatography (GPC).
- the resin having a hydrophilic group examples include an acrylic resin, a styrene acrylic resin, a styrene maleic acid resin, a rosin modified maleic resin, a rosin modified acrylic resin, an epoxy resin, a polyester resin, a polyurethane resin, and a phenol resin. It is not particularly limited. Among the resins listed above, acrylic resins, styrene acrylic resins, styrene malees are available from the viewpoints of availability of monomers, low cost, ease of synthesis, compatibility with other components in the ink, and dispersibility of pigments. An acid resin is preferably used as the resin having the hydrophilic group.
- acrylic resin, styrene acrylic 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 Such as amino group-containing monomers such as 2- (mercaptoacetoxy) ethyl acrylate, mercapto group-containing monomers such as acrylamide t-butylsulfonic acid, phosphoric acid such as 2-methacryloxyethyl acid phosphate, etc.
- carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate or their acid anhydrides
- 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 because it is easily cured by active energy rays.
- the iodine value of the ethylenically unsaturated group in the resin having a hydrophilic group and an ethylenically unsaturated group is preferably 0.5 mol / kg or more and 3.0 mol / kg or less. When the iodine value is within the above range, the ink is easily cured by active energy rays, and the acid value of the resin having the hydrophilic group and the ethylenically unsaturated group is easily adjusted to a suitable range.
- the iodine value of the ethylenically unsaturated group is preferably 1.0 mol / kg or more, and more preferably 1.5 mol / kg or more in order to promote the curing of the ink.
- the acid value of the resin having a hydrophilic group and an ethylenically unsaturated group is preferably 2.7 mol / kg or less, more preferably 2.4 mol / kg or less, which facilitates adjustment of the acid value to a more suitable range.
- the resin having the hydrophilic group and the ethylenically unsaturated group can be prepared by the following method. That is, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, an acrylic acid chloride, or a methacrylic acid chloride with respect to a mercapto group, amino group, hydroxyl group or carboxyl group which is an active hydrogen-containing group in a resin having a hydrophilic group Alternatively, a resin having a hydrophilic group and an ethylenically unsaturated group can be obtained by addition reaction of 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 ink contained in the lithographic printing ink set of the present invention is preferably such that the content of the resin having a hydrophilic group is 5% by mass or more because the pigment dispersibility and the stain resistance of the ink are improved. . More preferably, it is 8 mass% or more, More preferably, it is 11.5 mass% or more. Moreover, since content of the resin which has the said hydrophilic group is 30 mass% or less, since the fluidity
- the ink contained in the lithographic printing ink set of the present invention may contain a polyfunctional (meth) acrylate. Since the polyfunctional (meth) acrylate has a double bond group, the ink is easily cured by active energy rays. Also, the surface tension of the lithographic printing ink is increased or decreased by adjusting the type and / or content of the polyfunctional (meth) acrylate, and the difference in the surface tension of the lithographic printing ink applied on the substrate is 3.5 mN / It contributes to adjustment within m.
- the polyfunctional (meth) acrylate is not particularly limited as long as it is a compound having two or more (meth) acrylate groups.
- the number of (meth) acrylate groups (hereinafter sometimes referred to as “functional group number”) is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
- the number of functional groups of the polyfunctional (meth) acrylate is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
- the polyfunctional (meth) acrylate preferably has a polar group.
- the polar group include a hydroxy group and a carboxy group, among which a hydroxyl group is preferable.
- the polar group such as the hydroxyl group is considered to improve the fluidity of the ink in order to stabilize the dispersion of the pigment. By improving the fluidity of the ink, the ink transferred to the substrate tends to be smooth, and the gloss of the printed matter is improved.
- the polar group such as the hydroxyl group enhances the cohesive strength of the ink under high shear during printing due to interaction such as hydrogen bonding. When the cohesive strength of the ink is increased, the ink resilience with respect to the non-image area is improved, and as a result, the soil resistance is improved.
- the hydroxyl value of the polyfunctional (meth) acrylate is preferably 50 mgKOH / g or more because the pigment dispersibility of the ink and the stain resistance are improved. More preferably, it is 75 mgKOH / g or more, More preferably, it is 100 mgKOH / g or more. Moreover, since the hydroxyl value is 200 mgKOH / g or less, interaction such as hydrogen bonding can be suppressed, and the fluidity of the ink can be kept good, so that the tack (adhesiveness) can be reduced. . More preferably, it is 180 mgKOH / g or less, More preferably, it is 160 mgKOH / g or less.
- the molecular weight of the polyfunctional (meth) acrylate is 100 or more because the soil stain resistance of the ink is improved. More preferably, it is 200 or more, More preferably, it is 250 or more.
- the molecular weight is preferably 1,000 or less because the fluidity of the ink can be kept good and tack (adhesiveness) can be reduced. More preferably, it is 700 or less, More preferably, it is 500 or less.
- polyfunctional (meth) acrylate examples include bifunctional ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, 1,3 butylene glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc.
- sid adduct examples include tetraerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, diglycerin tetra (meth) acrylate, and ethylene oxide adducts and propylene oxide adducts.
- dipentaerythritol hexa (meth) acrylate these ethylene oxide adducts, and propylene oxide adducts can be mentioned.
- Preferred specific examples of the polyfunctional (meth) acrylate having a hydroxyl group include poly (meta) of polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, diglycerin, ditrimethylolpropane, isocyanuric acid, and dipentaerythritol. ) Acrylates, and their alkylene oxide adducts.
- trimethylolpropane di (meth) acrylate trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di or tri (meth) acrylate, diglycerin di or tri (meth) acrylate, ditrimethylolpropane
- di- or tri (meth) acrylate dipentaerythritol di-, tri-, tetra- or penta (meth) acrylate, and ethylene oxide adducts, propylene oxide adducts, tetraethylene oxide adducts, and the like.
- the lithographic printing ink of the present invention has excellent fluidity and pigment dispersibility, and has improved soil stain resistance, so pentaerythritol tri (meth) acrylate, diglycerin tri (meth) acrylate, and ditrimethylol.
- pentaerythritol tri (meth) acrylate diglycerin tri (meth) acrylate, and ditrimethylol.
- Propane tri (meth) acrylate is particularly preferred.
- the pigment dispersibility and the stain resistance of the ink are preferably improved. More preferably, it is 30 mass% or more, More preferably, it is 40 mass% or more. Moreover, since the fluidity
- the surface tension of the ink basically, the surface tension increases as the amount of polar groups in the ink increases, and the surface tension decreases as the amount of polar groups in the ink decreases.
- the content of the resin having the hydrophilic group and the polyfunctional (meth) acrylate having a hydroxyl group By adjusting the content of the resin having the hydrophilic group and the polyfunctional (meth) acrylate having a hydroxyl group, the amount of the polar group in the ink is changed, and the surface tension of the ink contained in the lithographic printing ink set It becomes easy to adjust the difference of 3.5 mN / m or less.
- the difference in the surface tension of the ink applied on the substrate may be adjusted depending on the type and / or content of the resin having a hydrophilic group and the polyfunctional (meth) acrylate, and in addition to these, or independently.
- the difference in the surface tension of the ink applied on the substrate may be adjusted according to the type and / or content of the surfactant
- the acid value of the resin having a hydrophilic group is preferably 60 mgKOH / g to 200 mgKOH / g
- the content of the resin having a hydrophilic group is 11.5% to 14% by mass
- the hydroxyl value of the polyfunctional (meth) acrylate having a hydroxyl group is 50 mgKOH / g to 200 mgKOH / g.
- the content of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 20% by mass or more and 30% by mass or less.
- the acid value of the resin having a hydrophilic group is preferably 60 mgKOH / g in order to easily adjust the tack value to 5.0 or more and 8.0 or less while ensuring the soil resistance.
- 200 mgKOH / g or less the weight average molecular weight of the resin having a hydrophilic group is 15,000 or more and 50,000 or less, the content of the resin having a hydrophilic group is 11.5% by mass or more and 14% by mass or less, a hydroxyl group
- the polyfunctional (meth) acrylate having a hydroxyl value of 50 mgKOH / g to 200 mgKOH / g and the content of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 20% by mass to 30% by mass.
- the ink contained in the lithographic printing ink set of the present invention may contain a surfactant.
- the content of the surfactant adjusts the difference between the surface tension of the lithographic printing ink and the surface tension of the ink contained in the lithographic printing ink set, in addition to improving the fluidity of the lithographic printing ink. Therefore, the content is preferably 5% by mass or more and 50% by mass or less with respect to the pigment.
- surfactant examples include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)”, “Disperbyk-101” manufactured by BYK Chemie.
- the ink included in the lithographic printing ink set of the present invention may contain a pigment.
- a pigment one or more selected from inorganic pigments and organic pigments generally used in lithographic printing ink compositions can be used.
- inorganic pigments 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 and the like. It is done.
- 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.
- the pigment concentration 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 ink contained in the lithographic ink set of the present invention may contain one or more components selected from silicone liquid, alkyl (meth) acrylate, hydrocarbon solvent, vegetable oil, fatty acid ester derived from vegetable oil, and fluorocarbon. preferable.
- the component has the effect of reducing the 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 contained in the ink diffuses out of the ink by contact with the silicone rubber surface and covers the silicone rubber surface in a thin film. 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 (meth) acrylate is preferable because it cures when irradiated with active energy rays, and thus improves the physical properties of the cured film of the ink and at the same time the sensitivity to the active energy rays.
- Specific compounds of the above components are as follows.
- 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 (meth) acrylate nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate
- Examples include hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and isooctadecyl (meth) acrylate.
- hydrocarbon solvent examples include polyolefin oil, naphthene oil, paraffin oil 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.
- 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.
- the ink contained in the lithographic printing ink set of the present invention is resistant to one or more components selected from the silicone liquid, alkyl (meth) acrylates, hydrocarbon solvents, vegetable oils, vegetable oil-derived fatty acid esters, and fluorocarbons.
- the content is preferably 0.5% by mass or more. More preferably, it is 1 mass% or more, More preferably, it is 2 mass% or more.
- the ink contained in the lithographic printing ink set of the present invention preferably contains an oil-soluble surfactant (emulsifier).
- emulsifier here refers to a surfactant that dissolves in oil (an organic compound insoluble in water) and takes in water to form a W / O emulsion.
- an appropriate amount generally said to be 10 to 20% by mass of the total amount of ink
- dampening water is taken in and emulsified, so that the non-image area can be repelled with dampening water.
- the ink stain resistance is improved.
- the ratio between the hydrophilic group and the hydrophobic group of the emulsifier is represented by the HLB value.
- the HLB value mentioned here is a value representing the degree of affinity of the surfactant with water and oil.
- the HLB value takes a value from 0 to 20, and the closer to 0, the higher the lipophilicity and the closer to 20, Means high hydrophilicity.
- the HLB value of the emulsifier is preferably 10 or more because it dissolves water well. More preferably, it is 11 or more. Further, it is preferably 18 or less because it dissolves well in the lithographic printing ink. More preferably, it is 17 or less.
- the emulsifier 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, polyoxy Alkylene stearyl ether, polyoxyalkylene cetyl ether Polyoxyalkylene palmitic ether, sorbitan acid mono, di, trialkyl ether, sorbitan acid mono, di, trilauryl ether, sorbitan acid mono, di, trioleyl ether, sorbitan acid mono, di, di
- the ink contained in the lithographic printing ink set of the present invention preferably contains 0.01% by mass or more of an emulsifier because 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 0.10 mass% or more. Further, since the lithographic printing ink does not take in dampening water excessively during printing and is incompatible with dampening water, the emulsifier is preferably 5.00% by mass or less. More preferably, it is 3.00 mass% or less, More preferably, it is 1.00 mass% or less.
- the ink contained in the lithographic printing ink set of the present invention preferably contains a photopolymerization initiator and has ultraviolet curing properties.
- the lithographic printing ink preferably contains a sensitizer in addition to the photopolymerization initiator.
- the photopolymerization initiator preferably generates active radical species.
- active radical species include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone (also known as Michler's ketone), 4, 4-bis (diethylamino) benzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, 1-hydroxycyclohexyl-phenyl ketone, 4-phenylbenzophenone, hydroxybenzophenone, dibenzyl ketone, fluorenone, 2, 2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy)- Phenyl] -2-hydr Roxy-2-methyl-1-propan-1-one, pt-butyldichloroacetophenone,
- the sensitizer examples include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,3-bis (4-diethylaminobenzal) Cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, 4,4-bis (dimethylamino) -benzophenone ( Alias: Michler's ketone), 4,4-bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethyl Aminobenzyliden
- the ink contained in the lithographic printing ink set of the present invention can use one or more of these photopolymerization initiators and sensitizers.
- the ink contained in the lithographic printing ink set preferably contains 0.1% by mass or more of the photopolymerization initiator because good sensitivity can be obtained. More preferably, it is contained in an amount of 1.0% by mass or more, and more preferably 3.0% by mass or more. Further, it is preferable that the photopolymerization initiator is contained in an amount of 20.0% by mass or less because the storage stability of the ink is improved. 15.0 mass% or less is more preferable, and 10.0 mass% or less is further more preferable.
- the content thereof is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, based on the fact that the ink can obtain good sensitivity. More preferably, the content is 0.0% by mass or more. From the viewpoint of improving the storage stability of the ink, the content is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and still more preferably 10.0% by mass or less based on the ink.
- a polymerization inhibitor is preferably added in order to improve stability during storage.
- the polymerization inhibitor include hydroquinone, monoetherified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, and pyrogallol.
- the addition amount of the polymerization inhibitor is preferably 0.01% by mass or more and 5.00% by mass or less based on the ink because good storage stability can be obtained.
- the ink contained in the lithographic printing ink set of the present invention can use additives such as waxes, antifoaming agents, and transferability improvers as necessary.
- 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 0.7 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer consisting of 30% by mass of methyl methacrylate, 25% by mass of styrene, and 45% 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 27,000, an acid value of 70 mgKOH / g, and an iodine value of 2.3 mol / kg.
- Resin 3 A resin 3 having a hydrophilic group composed of 42% by mass of methyl methacrylate, 25% by mass of styrene, and 33% by mass of methacrylic acid was obtained.
- the obtained resin 3 had a weight average molecular weight of 13,000 and an acid value of 183 mgKOH / g.
- Resin 4 Resin 4 having a hydrophilic group composed of 45% by mass of methyl methacrylate, 20% by mass of styrene, and 35% by mass of methacrylic acid was obtained.
- the obtained resin 4 had a weight average molecular weight of 25,000 and an acid value of 232 mgKOH / g.
- Resin 5 Isopap (Daiso Chemicals, diallyl phthalate resin, no hydrophilic group, weight average molecular weight 30,000, acid value 0 mgKOH / g)
- 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
- Multifunctional (meth) acrylate 2 A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate “Aronix” (registered trademark) M-306 (manufactured by Toagosei Co., Ltd.) with hydroxyl group, hydroxyl value of 171 mg KOH / g Multifunctional (meth) acrylate 3: Glycerin dimethacrylate “NK ester” (registered trademark) 701 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Hydroxyl group, hydroxyl value 240 mgKOH / g Polyfunctional
- Pigment 1 Carbon black MA8 (Mitsubishi Chemical Corporation)
- Pigment 2 Seikacyanin Blue 4920 (manufactured by Dainichi Seika Co., Ltd.)
- Pigment 3 Carmine 6B 1483LT (manufactured by Dainichi Seika Co., Ltd.)
- Pigment 4 Fast Yellow 2300 (manufactured by Dainichi Seika Co., Ltd.)
- Surfactant 1 “Disperbyk” (registered trademark) 111 (manufactured by ALTANA) Acid value 129 mg KOH / g
- Surfactant 2 “Disperbyk” (registered trademark) 2152 (manufactured by ALTANA Corporation) Acid value 0 mg KOH / g
- Surfactant 3 “Plisurf” (registered trademark) A208F (Daiichi Kogyo Seiyaku Co., Ltd.) Acid value 180 mgKOH / g
- Surfactant 4 “Disparon” (registered trademark) DA-325 (manufactured by Enomoto Kasei Co., Ltd.) Acid value 14 mg KOH / g
- the weight average molecular weight of the resin is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase.
- GPC gel permeation chromatography
- column is TSKgel SuperHM-H (manufactured by Tosoh Corp.), TSKgel SuperHM-H (manufactured by Tosoh Corp.), TSKgel SuperH2000 (manufactured by Tosoh Corp.)
- the RI detection was performed using an RI detector built in the GPC. A calibration curve was prepared using a polystyrene standard substance, and the weight average molecular weight of the sample was calculated.
- a method for preparing a measurement sample will be described.
- the sample was diluted with tetrahydrofuran so that the concentration became 0.25% by mass, and the diluted solution was stirred and dissolved at 100 rpm for 5 minutes with a mix rotor (MIX-ROTAR VMR-5, manufactured by ASONE Co., Ltd.).
- the solution was filtered through a 2 ⁇ m filter (Z227536-100EA, manufactured by SIGMA), and the filtrate was used as a measurement sample.
- the measurement conditions will be described.
- the amount of implantation was 10 ⁇ L, the analysis time was 30 minutes, the flow rate was 0.4 mL / min, and the column temperature was 40 degrees.
- 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 the inks of Examples 1 to 8 and Comparative Examples 1 to 9 are used. Used, printed on 5000 sheets of coated paper (OK Top Coat, Oji Paper), UV irradiation device (120 W / cm, 1 ultra high pressure meta-hara lamp) manufactured by USHIO Co., Ltd., and belt conveyor speed of 80 m / min. UV was irradiated to cure the ink, and a printed matter was obtained.
- Ink is black ink (hereinafter sometimes referred to as “black”), cyan ink (hereinafter sometimes referred to as “indigo”), magenta ink (hereinafter sometimes referred to as “red”), A printed matter was obtained by transferring in the order of yellow ink (hereinafter sometimes referred to as “yellow”).
- a lithographic printing plate with water (XP-F, manufactured by Fuji Film Co., Ltd.) is attached to an offset printing machine (Oliver 266EPZ, manufactured by Sakurai Graphic System), and an etchant (SOLAIA-505, manufactured by T & K TOKA) in dampening water. ) was printed on 5000 sheets of coated paper (OK Top Coat, Oji Paper Co., Ltd.) using each of the inks of Example 9 and Comparative Examples 10 and 11, using USHIO Co., Ltd.
- ultraviolet irradiation device 120 W / cm, one ultra-high pressure meta-hara lamp
- ultraviolet rays were irradiated at a belt conveyor speed of 80 m / min, and the ink was cured to obtain a printed matter.
- the printed matter was obtained by transferring ink in the order of black, indigo, red, and yellow.
- 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 (Murakami Color Research Laboratory Co., Ltd.). If the gloss value is 25 or less, the gloss value is poor. If the gloss value is more than 25 and less than 30, the gloss value can be used. If the gloss value is 30 or more, it is good. If the gloss value is 35 or more, it is very good.
- Tack value 1.31 ml of ink weighed with an ink pipette was measured at an rpm of 400 rpm and 38 ° C. using an incometer (Tester Sangyo Co., Ltd., INKO-GRAPH TYPE V). The measured value 1 minute after the start of measurement is taken as the tack value in the present invention.
- Examples 1 to 3 and Comparative Examples 1 and 2 In the composition shown in Table 1, a resin, polyfunctional (meth) acrylate, pigment, surfactant, additive, photopolymerization initiator, polymerization inhibitor, and wax are weighed, and a three-roll mill “EXAKT” (registered trademark) Using M-80S (manufactured by EXAKT), black ink, cyan ink, magenta ink, and yellow ink were obtained by passing the roller gap 1 5 times at a speed of 500 rpm.
- EXAKT registered trademark
- the obtained lithographic printing ink was subjected to surface tension measurement, viscosity measurement, tack measurement, waterless printing test and evaluation as described above, and surface tension, viscosity, stain resistance, glossiness and tack value were evaluated. did.
- the results are shown in Table 1.
- Comparative Examples 1 and 2 since the maximum value of the difference in the surface tension of the ink is larger than 3.5 mN / m, the gloss value of the four-color overlapping portion is lower than those in Examples 1 to 3.
- the maximum value of the difference in the surface tension of the ink is higher in Comparative Example 2 than in Comparative Example 1, and the gloss value of the four-color overlapping portion is lower in Comparative Example 2 than in Comparative Example 1.
- the surface tension of the ink does not satisfy 45 mN / m or more and 60 mN / m or less except for a part, and the gloss of the single color part is lower than that of Examples 1 to 3.
- Comparative Example 1 has a higher viscosity (A) than Examples 1 to 3 and Comparative Example 2, the gloss of the monochromatic part is lower than that of Examples 1 to 3 and Comparative Example 2.
- Comparative Example 2 has a lower viscosity (B) and (C) than Examples 1 to 3 and Comparative Example 1, and a viscosity ratio (C) / (B) compared to Examples 1 to 3 and Comparative Example 1. Since it is low, the soil resistance is poor compared to Examples 1 to 3 and Comparative Example 1.
- Examples 1 and 4 and Comparative Examples 3 and 4 A black ink, a cyan ink, a magenta ink, and a yellow ink were obtained in the same manner as in Example 1 except that the composition shown in Table 2 was used.
- the obtained lithographic printing ink was subjected to surface tension measurement, viscosity measurement, tack measurement, waterless printing test and evaluation as described above, and surface tension, viscosity, stain resistance, glossiness and tack value were evaluated. did. The results are shown in Table 2.
- Example 1 and 4 since the difference in the surface tension of the ink is within 3.5 mN / m and the tack value of the black ink is 8.0 or less, the gloss of the four-color overlapping portion is good.
- the difference in the surface tension of the ink is smaller in Example 1 than in Example 4, and the gloss value of the four-color overlapping portion is higher in Example 1 than in Example 4.
- the surface tensions of the inks of Examples 1 and 4 are 45 mN / m or more and 60 mN / m or less and the viscosity (A) is 200 Pa ⁇ s or less, the gloss of the monochromatic part is good.
- the viscosities (B) and (C) are 5 Pa ⁇ s or more and the viscosity ratio (C) / (B) is 0.75 or more and 1.00 or less, the soil resistance is good.
- Comparative Examples 3 and 4 since the difference in the surface tension of the ink is larger than 3.5 mN / m, the gloss value of the four-color overlapping portion is lower than those in Examples 1 and 4.
- the maximum value of the difference in the surface tension of the ink is higher in Comparative Example 4 than in Comparative Example 3, and the gloss value of the four-color overlapping portion is lower in Comparative Example 4 than in Comparative Example 3.
- the surface tension of the ink does not satisfy 45 mN / m or more and 60 mN / m or less except for a part, and the gloss of the single color part is lower than that of Examples 1 and 4.
- Comparative Example 3 has a higher viscosity (A) than Examples 1 and 4 and Comparative Example 4, the gloss of the monochromatic portion is lower than that of Examples 1 and 4 and Comparative Example 4.
- Comparative Example 4 has a lower viscosity (B) and (C) than Examples 1, 4 and Comparative Example 3, and a viscosity ratio (C) / (B) as compared with Examples 1, 4 and Comparative Example 3. Since it is low, the soil resistance is poor as compared with Examples 1 and 4 and Comparative Example 3.
- Examples 1, 5, 6 and Comparative Examples 5 to 7 A black ink, a cyan ink, a magenta ink, and a yellow ink were obtained in the same manner as in Example 1 except that the composition shown in Table 3 was used.
- the obtained lithographic printing ink was subjected to surface tension measurement, viscosity measurement, tack measurement, waterless printing test and evaluation as described above, and surface tension, viscosity, stain resistance, glossiness and tack value were evaluated. did. The results are shown in Table 3.
- Example 1 has an ink surface tension of 45 mN / m or more and 60 mN / m or less, and Examples 5 and 6 do not satisfy the ink surface tension of 45 mN / m or more and 60 mN / m or less. Compared with Examples 5 and 6, the gloss of the monochromatic part is better.
- the viscosities (B) and (C) are 5 Pa ⁇ s or more and the viscosity ratio (C) / (B) is 0.75 or more and 1.00 or less. Good properties.
- Comparative Examples 5 to 7 since the difference in the surface tension of the ink is larger than 3.5 mN / m, the gloss value of the four-color overlapping portion is lower than those in Examples 1, 5, and 6. In Comparative Examples 5 to 7, since the viscosity (A) is 200 Pa ⁇ s or less, the gloss of the single color portion is good. However, Comparative Example 5 has an ink surface tension of 45 mN / m or more and 60 mN / m or less, but Comparative Examples 6 and 7 do not satisfy the ink surface tension of 45 mN / m or more and 60 mN / m or less. 6 and 7 have lower gloss values in the single color part than in Comparative Example 5. In Comparative Examples 5 to 7, the viscosities (B) and (C) are 5 Pa ⁇ s or more and the viscosity ratio (C) / (B) is 0.75 or more and 1.00 or less. It is good.
- Examples 1, 7, and 8 and Comparative Examples 1, 8, and 9 A black ink, a cyan ink, a magenta ink, and a yellow ink were obtained in the same manner as in Example 1 except that the composition shown in Table 4 was used.
- the obtained lithographic printing ink was subjected to surface tension measurement, viscosity measurement, tack measurement, waterless printing test and evaluation as described above, and surface tension, viscosity, stain resistance, glossiness and tack value were evaluated. did. The results are shown in Table 4.
- Example 7 For Examples 1, 7 and 8, the difference in the surface tension of the ink in each example is within 3.5 mN / m, so the gloss of the four-color overlapping portion is good.
- the surface tension of the ink is 45 mN / m or more and 60 mN / m or less and the viscosity (A) is 200 Pa ⁇ s or less, the gloss of the monochromatic part is good.
- Example 7 since the tack value of black ink is lower than that in Example 1, the gloss value of the black single color part and the four-color overlapping part is high, but the black ink has less stain resistance in comparison with Example 1. .
- Example 8 since the tack value of black ink is higher than that in Example 1, the gloss value of the black single color portion and the four-color overlapping portion is low, but the black ink has higher stain resistance than that in Example 1. .
- Comparative Examples 1, 8, and 9 the difference in the surface tension of the ink is larger than 3.5 mN / m, and thus the gloss of the four-color overlapping portion is poor.
- the ink surface tension does not satisfy 45 mN / m or more and 60 mN / m or less except for a part, and the viscosity (A) does not satisfy 200 Pa ⁇ s or less except for a part.
- the gloss value of the single color portion is lower than those of Examples 1, 7, and 8.
- Comparative Examples 8 and 9 have a lower black ink tack value than Comparative Example 1, the gloss values of the black single-color portion and the four-color overlapping portion are higher, but the black ink stain resistance is higher than that of Comparative Example 1. Is low.
- Example 9 and Comparative Examples 10 and 11 A black ink, a cyan ink, a magenta ink, and a yellow ink were obtained in the same manner as in Example 1 except that the composition shown in Table 5 was used.
- the obtained lithographic printing ink is subjected to surface tension measurement, viscosity measurement, tack measurement, printing test with water and its evaluation as described above, and surface tension, viscosity, stain resistance, glossiness and tack value are evaluated. did. The results are shown in Table 5.
- Example 9 since the difference in the surface tension of the ink is within 3.5 mN / m, the gloss of the four-color overlapping portion is good. In Comparative Examples 10 and 11, since the difference in the surface tension of the ink is greater than 3.5 mN / m, the gloss of the four-color overlapping portion is poor. About Example 9 and Comparative Examples 10 and 11, since the surface tension of the ink is 45 mN / m or more and 60 mN / m or less and the viscosity (A) is 200 Pa ⁇ s or less, the gloss of the single color part is good.
- Example 9 an emulsifier having an HLB value of 8.0 is contained, and the ink cannot be taken in a dampening water during printing to obtain a stable emulsified state. Therefore, an appropriate concentration is required unless the ink supply amount is increased. Cannot be obtained, and as a result, the soil resistance is poor.
- Example 9 and Comparative Example 10 since the emulsifier having an HLB value of 12.1 is contained and the ink can take in dampening water during printing and take a stable emulsified state, the ink supply amount is not increased. Therefore, a printed matter having an appropriate concentration can be obtained, and as a result, the soil resistance is good.
Abstract
Description
一般的に、印刷物の色合いは、ブラックインキ、シアンインキ、マゼンタインキ、及びイエローインキを用いて表現される。本発明の印刷物の製造方法は、少なくとも平版印刷用ブラックインキ、平版印刷用シアンインキ、平版印刷用マゼンタインキ、及び平版印刷用イエローインキを、基材上に塗布する工程を含むことを特徴とする。
酸価は、JIS K 0070:1992の試験方法第3.1項の中和滴定法に準拠して求めることができる。
エチレン性不飽和基のヨウ素価はJIS K 0070:1992の試験方法第6.0項に記載の方法により求めることができる。
多官能(メタ)アクリレートの水酸基価は、JIS K 0070:1992の試験方法第7.1項に記載の方法により求めることができる。
前記成分の具体的な化合物は次のとおりである。
本発明の平版印刷用インキセットは、少なくともブラックインキ、シアンインキ、マゼンタインキ、及びイエローインキを含む平版印刷用インキセットであって、前記平版印刷用インキセットに含まれるインキの表面張力の差が3.5mN/m以内であることを特徴とする。これは平版印刷用インキセットを構成するブラックインキ、シアンインキ、マゼンタインキ、及びイエローインキのそれぞれの表面張力について、最大の表面張力と最小の表面張力の差が3.5mN/m以下であることを意味する。前記表面張力の差が3.5mN/m以内であることによって、多色が重なり合う印刷部にて下層インキに対する上層インキの濡れ性が良くなり、上層インキが平滑になりやすく、印刷物の光沢が向上する。インキの表面張力の差は、より好ましくは3.0mN/m以内であり、さらに好ましくは2.5mN/m以内である。各インキの表面張力は、各インキに組成する樹脂、多官能(メタ)アクリレート、 界面活性剤から選ばれる少なくとも1つの種類および/または含有量により調節することができる。したがって、インキの表面張力の差は、各インキを組成する樹脂、多官能(メタ)アクリレートおよび/または界面活性剤の種類を変更したり、これらの含有量を増減することにより調節することができる。
前記成分の具体的な化合物は次のとおりである。
樹脂1:25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0.55当量のグリシジルメタクリレートを付加反応させて、エチレン性不飽和基と親水性基を有する樹脂1を得た。得られた樹脂1は重量平均分子量34,000、酸価105mgKOH/g、ヨウ素価2.0mol/kgであった。
樹脂2:30質量%のメタクリル酸メチル、25質量%のスチレン、45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0.7当量のグリシジルメタクリレートを付加反応させて、エチレン性不飽和基と親水性基を有する樹脂2を得た。得られた樹脂2は重量平均分子量27,000、酸価70mgKOH/g、ヨウ素価2.3mol/kgであった。
樹脂3:42質量%のメタクリル酸メチル、25質量%のスチレン、33質量%のメタクリル酸からなる親水性基を有する樹脂3を得た。得られた樹脂3は重量平均分子量13,000、酸価183mgKOH/gであった。
樹脂4:45質量%のメタクリル酸メチル、20質量%のスチレン、35質量%のメタクリル酸からなる親水性基を有する樹脂4を得た。得られた樹脂4は重量平均分子量25,000、酸価232mgKOH/gであった。
樹脂5:イソダップ(ダイソー化学社製、ジアリルフタレート樹脂、親水性基なし、重量平均分子量30,000、酸価0mgKOH/g)
多官能(メタ)アクリレート2: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“アロニックス”(登録商標)M-306(東亜合成社製)ヒドロキシル基あり、水酸基価171mgKOH/g
多官能(メタ)アクリレート3: グリセリンジメタクリレート“NKエステル”(登録商標)701(新中村化学社製)ヒドロキシル基あり、水酸基価240mgKOH/g
多官能(メタ)アクリレート4:ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物“アロニックス”(登録商標)M-402(東亜合成社製)ヒドロキシル基あり、水酸基価28mgKOH/g
多官能(メタ)アクリレート5:ペンタエリスリトールテトラアクリレートエチレンオキシド付加物“Miramer”(登録商標)M4004(MIWON社製)ヒドロキシル基なし
顔料2:セイカシアニンブルー4920(大日精化(株)製)
顔料3:カーミン6B 1483LT(大日精化(株)製)
顔料4:ファストイエロー2300(大日精化(株)製)
界面活性剤2:“Disperbyk”(登録商標)2152(ALTANA(株)社製)酸価0mgKOH/g
界面活性剤3:“プライサーフ”(登録商標)A208F(第一工業製薬(株)製)酸価180mgKOH/g
界面活性剤4:“ディスパロン”(登録商標)DA-325(楠本化成(株)製)酸価14mgKOH/g
光重合開始剤:“イルガキュア”(登録商標)907(BASF社製)
重合禁止剤:p-メトキシフェノール(和光純薬工業(株)製)
ワックス:ポリテトラフルオロエチレンの微粉末“KTL-4N”(登録商標)((株)喜多村製)
乳化剤1:ポリオキシエチレンラウリルエーテル“エマルゲン”(登録商標)108(花王(株)社)HLB値12.1
乳化剤2:ポリオキシエチレンラウリルエーテル“EMALEX”(登録商標)505H(花王(株)製)HLB値8.0
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。GPCはHLC-8220(東ソー(株)製)、カラムはTSKgel SuperHM-H(東ソー(株)製)、TSKgel SuperHM-H(東ソー(株)製)、TSKgel SuperH2000(東ソー(株)製)の順で連結したものを用い、RI検出は前記GPCに内蔵されたRI検出器を用い測定した。検量線はポリスチレン標準物質を用いて作成し、試料の重量平均分子量を計算した。測定試料の作成方法を説明する。濃度が0.25質量%となるように試料をテトラヒドロフランで希釈し、希釈溶液をミックスローター(MIX-ROTAR VMR-5、アズワン(株)社製)にて5分間100rpmで攪拌し溶解させ、0.2μmフィルター(Z227536-100EA、SIGMA社製)でろ過して、ろ液を測定試料とした。測定条件を説明する。打ち込み量は10μL、分析時間は30分、流量は0.4mL/min、カラム温度は40度として、測定した。
水なし平版印刷版(TAN-E、東レ(株)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1~9の各インキを用いて、コート紙(OKトップコート、王子製紙製)5000枚に印刷、USHIO(株)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。インキをブラックインキ(以下、「墨」と記すことがある。)、シアンインキ(以下、「藍」と記すことがある。)、マゼンタインキ(以下、「紅」と記すことがある。)、イエローインキ(以下、「黄」と記すことがある。)の順で転写することで印刷物を得た。
水あり平版印刷版(XP-F、富士フィルム(株)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9、および比較例10、11の各インキを用いて、コート紙(OKトップコート、王子製紙製)5000枚に印刷、USHIO(株)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。インキを墨、藍、紅、黄の順で転写することで印刷物を得た。
(1)表面張力
ガラス基材(5cmガラス板(厚さ1mmT×縦50mm×横50mm)、(株)石田理化社製)の表面を洗浄し不純物を除去する処理を行った後、ガラス基材上に塗布したインキについて、自動接触角計(Drop Master DM-501,協和界面科学(株)社製)を用いて液滴法にて接触角を測定し、インキの表面張力を算出した。詳細については前述参照。
レオメーター(MCR301、アントン・パール(Anton Paar)社製)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のインキについて、25℃での、0.5rpm、20rpm、50rpmにおける各粘度を測定し、粘度(A)、粘度(B)、粘度(C)とした。また粘度比(C)/(B)を求めた。
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(Gretag Macbeth社製、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、反射濃度が0.10を超え0.15以下であると耐地汚れ性がやや良好であり、反射濃度が0.10以下であると耐地汚れ性が良好であり、反射濃度が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製)を用いて測定角度60度で光沢値を測定した。光沢値は25以下では不良であり、光沢値は25を超え30未満であれば使用可能であり、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。
インキピペットで秤量した1.31mlのインキを、インコメーター(テスター産業(株)社製、INKO-GRAPH TYPE V)を用いて、回転数400rpm、38℃において測定した。測定開始1分後の測定値を、本発明におけるタック値とする。
表1に示す組成で、樹脂、多官能(メタ)アクリレート、顔料、界面活性剤、添加剤、光重合開始剤、重合禁止剤、およびワックスを秤量し、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5回500rpmの速度で通すことでブラックインキ、シアンインキ、マゼンタインキ、およびイエローインキを得た。得られた平版印刷用インキについて、上記の通り表面張力測定、粘度測定、タック測定、水なし印刷試験およびその評価を実施し、表面張力、粘度、耐地汚れ性、光沢性およびタック値を評価した。結果を表1に示す。
表2の組成とする以外は実施例1と同様の操作を行い、ブラックインキ、シアンインキ、マゼンタインキ、およびイエローインキを得た。得られた平版印刷用インキについて、上記の通り表面張力測定、粘度測定、タック測定、水なし印刷試験およびその評価を実施し、表面張力、粘度、耐地汚れ性、光沢性およびタック値を評価した。結果を表2に示す。
表3の組成とする以外は実施例1と同様の操作を行い、ブラックインキ、シアンインキ、マゼンタインキ、およびイエローインキを得た。得られた平版印刷用インキについて、上記の通り表面張力測定、粘度測定、タック測定、水なし印刷試験およびその評価を実施し、表面張力、粘度、耐地汚れ性、光沢性およびタック値を評価した。結果を表3に示す。
表4の組成とする以外は実施例1と同様の操作を行い、ブラックインキ、シアンインキ、マゼンタインキ、およびイエローインキを得た。得られた平版印刷用インキについて、上記の通り表面張力測定、粘度測定、タック測定、水なし印刷試験およびその評価を実施し、表面張力、粘度、耐地汚れ性、光沢性およびタック値を評価した。結果を表4に示す。
表5の組成とする以外は実施例1と同様の操作を行い、ブラックインキ、シアンインキ、マゼンタインキ、およびイエローインキを得た。得られた平版印刷用インキについて、上記の通り表面張力測定、粘度測定、タック測定、水あり印刷試験およびその評価を実施し、表面張力、粘度、耐地汚れ性、光沢性およびタック値を評価した。結果を表5に示す。
Claims (23)
- 少なくとも平版印刷用ブラックインキ、平版印刷用シアンインキ、平版印刷用マゼンタインキ、及び平版印刷用イエローインキを、基材上に塗布する工程を含み、前記基材上に塗布するインキの表面張力の差が3.5mN/m以内である、印刷物の製造方法。
- 前記基材上に塗布するインキの表面張力が45mN/m以上60mN/m以下である、請求項1に記載の印刷物の製造方法。
- 前記平版印刷用ブラックインキ、平版印刷用シアンインキ、平版印刷用マゼンタインキ、平版印刷用イエローインキの順で基材上に塗布され、かつ、前記平版印刷用ブラックインキの、38℃、インコメーターで計測した400rpmでのタック値(1分値)が5.0以上8.0以下である、請求項1または2に記載の印刷物の製造方法。
- 活性エネルギー線を照射して硬化する工程を含む、請求項1~3のいずれかに記載の印刷物の製造方法。
- 前記基材上に塗布するインキの、25℃、コーンプレート型回転粘度計で測定した回転数0.5rpmにおける粘度(A)、回転数20rpmにおける粘度(B)、および回転数50rpmにおける粘度(C)が、いずれも5Pa・s以上200Pa・s以下であり、かつ粘度比(C)/(B)が0.75以上1.00以下である、請求項1~4のいずれかに記載の印刷物の製造方法。
- 前記基材上に塗布するインキが、親水性基を有する樹脂、多官能(メタ)アクリレート、顔料、および界面活性剤を含む、請求項1~5のいずれかに記載の印刷物の製造方法。
- 前記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、ヒドロキシル基のいずれかである、請求項6に記載の印刷物の製造方法。
- 前記親水性基を有する樹脂の酸価が、30mgKOH/g以上200mgKOH/g以下である、請求項6または7に記載の印刷物の製造方法。
- 前記多官能(メタ)アクリレートがヒドロキシル基を有する、請求項6~8のいずれかに記載の印刷物の製造方法。
- 前記多官能(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6~9のいずれかに記載の印刷物の製造方法。
- 前記基材上に塗布するインキが、HLB値10以上18以下の乳化剤を含む、請求項1~10のいずれかに記載の印刷物の製造方法。
- 基材としてグロス系塗工紙を用いる、請求項1~11のいずれかに記載の印刷物の製造方法。
- 少なくともブラックインキ、シアンインキ、マゼンタインキ、及びイエローインキを含む平版印刷用インキセットであって、前記平版印刷用インキセットに含まれるインキの表面張力の差が3.5mN/m以内である、平版印刷用インキセット。
- 前記平版印刷用インキセットに含まれるインキの表面張力が45mN/m以上60mN/m以下である、請求項13に記載の平版印刷用インキセット。
- 前記平版印刷用インキセットに含まれるブラックインキの、38℃、インコメーターで計測した400rpmでのタック値(1分値)が5.0以上8.0以下である、請求項13または14に記載の平版印刷用インキセット。
- 前記平版印刷用インキセットに含まれるインキの、25℃、コーンプレート型回転粘度計で測定した回転数0.5rpmにおける粘度(A)、回転数20rpmにおける粘度(B)、および回転数50rpmにおける粘度(C)が、いずれも5Pa・s以上200Pa・s以下であり、かつ粘度比(C)/(B)が0.75以上1.00以下である、請求項13~15のいずれかに記載の平版印刷用インキセット。
- 前記平版印刷用インキセットに含まれるインキが、親水性基を有する樹脂、多官能(メタ)アクリレート、顔料、光重合開始剤、および界面活性剤を含む、請求項13~16のいずれかに記載の平版印刷用インキセット。
- 前記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、ヒドロキシル基のいずれかである、請求項17に記載の平版印刷用インキセット。
- 前記親水性基を有する樹脂の酸価が、30mgKOH/g以上200mgKOH/g以下である、請求項17または18に記載の平版印刷用インキセット。
- 前記多官能(メタ)アクリレートがヒドロキシル基を有する、請求項17~19のいずれかに記載の平版印刷用インキセット。
- 前記多官能(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17~20のいずれかに記載の平版印刷用インキセット。
- 前記平版印刷用インキセットに含まれるインキが、HLB値10以上18以下の乳化剤を含む、請求項13~21のいずれかに記載の平版印刷用インキセット。
- 請求項13~22のいずれかに記載の平版印刷用インキセットを用いて印刷された印刷物。
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KR1020197001900A KR102196647B1 (ko) | 2016-09-30 | 2017-09-25 | 평판인쇄용 잉크를 사용한 인쇄물의 제조 방법, 및 평판인쇄용 잉크 셋트 |
CN201780058923.4A CN109789715B (zh) | 2016-09-30 | 2017-09-25 | 使用平版印刷用墨水的印刷物的制造方法和平版印刷用墨水套件 |
JP2017551352A JP6915546B2 (ja) | 2016-09-30 | 2017-09-25 | 平版印刷用インキを用いた印刷物の製造方法、および平版印刷用インキセット |
US16/332,551 US11434384B2 (en) | 2016-09-30 | 2017-09-25 | Method for manufacturing printed material using lithographic printing ink, and lithographic printing ink set |
ES17856059T ES2924139T3 (es) | 2016-09-30 | 2017-09-25 | Procedimiento para fabricar material impreso utilizando tinta de impresión litográfica y conjunto de tintas de impresión litográfica |
EP17856059.5A EP3521047B1 (en) | 2016-09-30 | 2017-09-25 | Method for manufacturing printed matter using planographic printing ink, and planographic printing ink set |
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JP2016-193541 | 2016-09-30 | ||
JP2016193541 | 2016-09-30 |
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PCT/JP2017/034564 WO2018062108A1 (ja) | 2016-09-30 | 2017-09-25 | 平版印刷用インキを用いた印刷物の製造方法、および平版印刷用インキセット |
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US (1) | US11434384B2 (ja) |
EP (1) | EP3521047B1 (ja) |
JP (1) | JP6915546B2 (ja) |
KR (1) | KR102196647B1 (ja) |
CN (1) | CN109789715B (ja) |
ES (1) | ES2924139T3 (ja) |
TW (1) | TW201821553A (ja) |
WO (1) | WO2018062108A1 (ja) |
Cited By (2)
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EP3381988A4 (en) * | 2015-11-25 | 2019-06-26 | Toray Industries, Inc. | LITHOGRAPHIC INK |
WO2022163623A1 (ja) * | 2021-01-29 | 2022-08-04 | 東レ株式会社 | 活性エネルギー線硬化型平版印刷用インキセット、印刷物の製造方法および活性エネルギー線硬化型平版印刷用インキ |
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- 2017-09-25 US US16/332,551 patent/US11434384B2/en active Active
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- 2017-09-28 TW TW106133291A patent/TW201821553A/zh unknown
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EP3521047A4 (en) | 2020-06-03 |
EP3521047A1 (en) | 2019-08-07 |
CN109789715B (zh) | 2021-10-08 |
ES2924139T3 (es) | 2022-10-04 |
KR20190058449A (ko) | 2019-05-29 |
JP6915546B2 (ja) | 2021-08-04 |
JPWO2018062108A1 (ja) | 2019-07-11 |
US20210284852A1 (en) | 2021-09-16 |
KR102196647B1 (ko) | 2020-12-30 |
US11434384B2 (en) | 2022-09-06 |
TW201821553A (zh) | 2018-06-16 |
CN109789715A (zh) | 2019-05-21 |
EP3521047B1 (en) | 2022-07-27 |
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