WO2015093394A1 - Composition d'encre offset durcissable par des rayons énergétiques actifs et article imprimé utilisant ladite composition - Google Patents

Composition d'encre offset durcissable par des rayons énergétiques actifs et article imprimé utilisant ladite composition Download PDF

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WO2015093394A1
WO2015093394A1 PCT/JP2014/082862 JP2014082862W WO2015093394A1 WO 2015093394 A1 WO2015093394 A1 WO 2015093394A1 JP 2014082862 W JP2014082862 W JP 2014082862W WO 2015093394 A1 WO2015093394 A1 WO 2015093394A1
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active energy
energy ray
acrylate
ink composition
range
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PCT/JP2014/082862
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English (en)
Japanese (ja)
Inventor
圭佑 若原
育男 松尾
智昭 南部
正和 吉澤
義信 出口
栄寿 一ノ瀬
山口　浩一
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Dic株式会社
Ｄｉｃグラフィックス株式会社
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Priority to JP2015553509A priority Critical patent/JPWO2015093394A1/ja
Publication of WO2015093394A1 publication Critical patent/WO2015093394A1/fr

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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
    • 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

Definitions

  • the present invention relates to an active energy ray-curable offset ink composition useful as a raw material for an active energy ray-curable offset ink. Furthermore, the present invention relates to a printed material using the composition.
  • the active energy ray-curable offset ink composition has been evaluated for its instantaneous curing characteristics and is widely used mainly for package printing of paper containers.
  • oligomers having a polymerizable group such as an acrylate group such as epoxy acrylate, urethane acrylate, and polyester acrylate are frequently used so as to have an instantaneous curing property (for example, patents). Reference 1).
  • the required emulsification ability was inferior. That is, in the offset printing in which the ink and water are continuously supplied to the printing plate at the same time and image formation is performed by utilizing the repulsive action of the ink and water, the ink is required to have high emulsification ability. Due to the strong hydrophilicity and inferior properties of properly releasing emulsified water, the ink is excessively emulsified during printing, and printing troubles such as a decrease in printing density often occur.
  • the problem to be solved by the present invention is to develop high energy curability when used in printing ink, as well as an active energy ray curable composition having excellent emulsification ability and offset printing ability, excellent curability,
  • An object of the present invention is to provide an active energy ray-curable printing ink having emulsifying properties and offset printing suitability, and a printed matter thereof.
  • an epoxy acrylate compound obtained by reacting a bisphenol A type epoxy resin and acrylic acid, and the glycidyloxy of the bisphenol A type epoxy resin.
  • the ratio of ⁇ -glycol groups to the total number of terminal structural sites attributable to or derived from groups is adjusted to a ratio of 5 mol% or less in 13C-NMR measurement results, and two or more acrylic groups per specific molecule.
  • the active energy ray-curable offset ink composition of the present invention is an epoxy acrylate compound obtained by reacting a bisphenol A type epoxy resin and acrylic acid, and is derived from the glycidyloxy group of the bisphenol A type epoxy resin.
  • the epoxy acrylate compound (A) in which the ratio of ⁇ -glycol group to the total number of derived terminal structural sites is 5 mol% or less in 13C-NMR measurement results is contained in the range of 10 to 60 mass% of the total amount.
  • a polymerizable acrylate monomer (B) having a viscosity at 25 ° C.
  • the present invention further relates to an active energy ray-curable offset ink comprising the active energy ray-curable offset ink composition.
  • the present invention further relates to a printed matter obtained by printing using the active energy ray-curable offset ink.
  • an active energy ray-curable offset ink that exhibits high curability when used in a printing ink composition and also has excellent curability, emulsification property, and offset printability, and a printed matter thereof are provided. it can.
  • the active energy ray-curable offset ink composition of the present invention is an epoxy acrylate compound obtained by reacting a bisphenol A type epoxy resin and acrylic acid, and is derived from or derived from the glycidyloxy group of the bisphenol A type epoxy resin.
  • the polymerizable acrylate monomer having a ratio of ⁇ -glycol group to the total number of terminal structure sites to be adjusted to a ratio of 5 mol% or less in 13C-NMR measurement results, and further having two or more acrylic groups per specific molecule
  • the effects of the present invention can be achieved by mixing a suitable amount of.
  • the terminal structure site derived from or derived from the glycidyloxy group is various terminal structure sites generated by the reaction of the epoxy group in the raw material epoxy resin and the carboxylic acid having a polymerizable unsaturated group. Or an epoxy group remaining unreacted, specifically, the following structural formulas (i) to (vi)
  • R 1 and R 2 are hydrogen atom or a methyl group.
  • the ⁇ glycol structure site which is an epoxy acrylate impurity, is particularly strong in new water and tends to reduce the emulsification suitability of the printing ink. Therefore, it is preferable to control the content of the ⁇ glycol structure site.
  • the proportion of the ⁇ glycol structure moiety represented by the structural formula (v) to 5 mol% or less of the total number of terminal structures measurable by 13 C-NMR.
  • the curability of the printing ink using the polymerizable unsaturated group-containing resin is good, and excellent emulsification characteristics are exhibited.
  • the content is 3 mol% or less as printing ink and when offset printing is performed, the printing characteristics are excellent.
  • the ⁇ glycol structural site is based on the total number of terminal structures selected from these. It is sufficient that the content of is 5 mol% or less.
  • the abundance ratio of the structural formulas (i) to (vi) can be measured by 13 C-NMR as described above. Specifically, each of the carbon atoms indicated by * below is indicated. It can be derived by the peak area ratio. When each peak overlaps with another carbon atom in another structure, the ratio may be obtained by excluding the area due to the other carbon atom.
  • R 1 and R 2 are hydrogen atom or a methyl group.
  • the proportion of each terminal structural site in the structural formulas (i) to (vi) is, as described above, if the ⁇ glycol structural site represented by the structural formula (v) is 5 mol% or less. In particular, it is preferably 3 mol% or less, but the other terminal structure site is, for example, that the ⁇ -addition structure site represented by the structural formula (i) is 70 mol% or more, more specifically, The ⁇ -addition structure moiety represented by the structural formula (i) is 70 mol% or more, and the ⁇ -addition structure moiety represented by the structural formula (i) is represented by the structural formula (ii).
  • the total amount with the ⁇ -addition structure site is 84% or more.
  • the ⁇ addition structure site represented by the structural formula (iii) is preferably 5 mol% or less from the viewpoint of emulsification, and the monocarboxylic acid further having a polymerizable unsaturated group in the ⁇ addition structure. It is preferable from the point that sclerosis
  • the epoxy group represented by the structural formula (vi) is an epoxy group remaining unreacted, and its abundance ratio is 2 mol% or less, particularly 1 mol% or less. Is preferred.
  • the epoxy resin is preferably a compound having two or more epoxy groups in one molecule, and bisphenol A type epoxy resin is an essential component, but one or more other epoxy resins are mixed.
  • the bisphenol-type epoxy resin and the novolac-type epoxy resin are preferable from the viewpoint of printability, and in particular, a bisphenol-type epoxy resin having an epoxy equivalent in the range of 170 to 500 g / eq, particularly a bisphenol A-type epoxy resin has excellent emulsification characteristics, This is preferable from the viewpoint of obtaining excellent printability when used as a printing ink.
  • examples of the monocarboxylic acid having a polymerizable unsaturated group to be reacted with the epoxy resin include acrylic acid, methacrylic acid, and crotonic acid.
  • Acrylic acid and methacrylic acid are particularly preferable from the viewpoint of printability. Since acrylic acid is preferable, in the present invention, an epoxy acrylate compound obtained by reacting a bisphenol A type epoxy resin and acrylic acid is used as an essential component.
  • the epoxy acrylate compound (A) used in the active energy ray-curable offset ink composition of the present invention can be produced by reacting a bisphenol A type epoxy resin with acrylic acid. Is preferably carried out in the presence of a nitrogen-containing basic catalyst from the viewpoint of easily reducing the amount of ⁇ glycol to 5 mol% or less.
  • the nitrogen-containing basic catalyst used here is a basic compound having a nitrogen atom.
  • the nitrogen-containing basic catalyst include primary amines such as n-butylamine, amylamine, hexylamine, cyclohexylamine, octylamine, and benzylamine, Linear secondary amines such as diethylamine, dipropylamine, diisopropylamine and dibutylamine, secondary secondary amines such as aziridine, azetidine, pyrrolidine, piperidine, azepane and azocan and their alkyl substituents Amines, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, 1,4-diazabicyclo [2.2.2] octane, quinuclidine, and aliphatic tertiary amines such as 3-quinuclidinol, dimethylaniline, etc.
  • Aromatic tertiary amines and heterocyclic tertiary amines such as isoquinoline, pyridine, collidine and betapicoline, secondary amidines such as imidazole, purine, triazole and guanidine, pyrimidines, triazines and 1,8-dia
  • Nitrogen atom-containing basic catalysts such as tertiary amidines such as bicyclo [5.4.0] undec-7-ene (DBU) and 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) Is mentioned. These nitrogen atom-containing basic catalysts may be used alone or in combination of two or more.
  • triethylamine or tetramethylammonium chloride is preferable because the amount of ⁇ -glycol in the polymerizable unsaturated group-containing resin can be easily reduced to 5% or less.
  • the amount of the nitrogen atom-containing basic catalyst used is 0.01 to 0.6% by mass, particularly 0.03 to 0.5% by mass, especially 0% to 100% by mass of the total weight of the epoxy acrylate compound.
  • a range of 0.05 to 0.3% by mass is preferable from the viewpoint that the amount of ⁇ -glycol in the produced polymerizable unsaturated group-containing resin is reduced and the emulsification characteristics are good.
  • the method for producing the epoxy acrylate compound (A) comprises an epoxy resin and acrylic acid in the presence of a nitrogen atom-containing basic catalyst such that the epoxy group and the carboxyl group are 0.9 / 1.0 to 1.
  • the ratio of 0 / 0.9 (molar ratio) and the nitrogen atom-containing basic catalyst is 0.01 to 0.6% by mass, preferably 0.03% with respect to 100% by mass of the total weight of the raw material components.
  • the method of making it react until an acid value becomes 2.0 or less is preferable from the point which is easy to reduce the alpha glycol amount in an epoxy acrylate compound (A) to 5% or less.
  • reaction between the bisphenol A type epoxy resin and acrylic acid can be carried out in a reaction solvent using a radical polymerizable monomer that does not contain a site that reacts with a carboxyl group and an epoxy group as a reaction solvent. .
  • the epoxy acrylate compound (A) thus obtained preferably has an epoxy equivalent of 8000 g / eq or more or an acid value of 2.0 or less.
  • the epoxy acrylate compound (A) can be used to adjust the viscosity when the printing ink has a solution viscosity of 0.5 to 30 Pa ⁇ s when dissolved in butyl acetate in a non-volatile content of 80% by mass.
  • the epoxy acrylate compound (A) is preferably contained in the range of 10 to 60% by mass of the total amount of the ink composition, and the viscosity at 25 ° C. is in the range of 40 to 200 millipascal seconds (mPa ⁇ s).
  • the polymerizable acrylate monomer (B) having two or more acrylic groups per molecule in a range of 250 to 550 is preferably contained in a range of 5 to 40% by mass of the total amount of the ink composition.
  • the polymerizable acrylate monomer (B) when a large amount of a monofunctional monomer having one acrylic group per molecule is used, it is difficult to obtain good curability, and when the molecular weight is less than 250, There is a possibility of causing expansion and deterioration of the rubber roller of the printing press. When the molecular weight exceeds 550, the monomer has a high viscosity. Therefore, the epoxy acrylate compound (A) in the ink composition is relatively used when used in a large amount. This is not preferable because it is difficult to obtain good curability and offset printing suitability.
  • the epoxy acrylate compound (A) is contained in a range of 33 to 60% by mass with respect to the total amount of the ink composition in view of a good balance between the curability and the offset printing suitability, and the polymerizable property.
  • the acrylate monomer (B) is contained in the range of 15.1 to 40% by mass of the total amount of the ink composition, and other components such as an initiator, a wax and a pigment may be contained in a proportion of 51.9% by mass or less. preferable.
  • the polymerizable acrylate monomer (B) is more preferably an active energy ray-curable monomer containing a bifunctional or trifunctional acrylic group, and the average number of moles of ethylene oxide added per mole of monomer molecules is 2 to 4.
  • Ethylene oxide modified trimethylolpropane triacrylate in the range is particularly preferred. Since ethylene oxide-modified trimethylolpropane triacrylate has a low viscosity, it can relatively contain more epoxy acrylate compound (A) in the printing ink composition, and also provides an extraordinar hydrophilic / hydrophobic balance. Thus, better offset printing suitability can be maintained.
  • examples of the photopolymerization initiator used when the active energy ray-curable offset ink composition of the present invention is an ultraviolet curable composition include an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator. It is done.
  • examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy.
  • examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, Hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; aminobenzophenone compounds such as 4,4′-bisdimethylaminobenzophenone and 4,4′-bisdiethylaminobenzophenone; Examples include butyl
  • photopolymerization initiators can be used alone or in combination of two or more.
  • aminoalkylphenone compounds are particularly preferred from the viewpoint of excellent curability, and particularly when a UV-LED light source that generates ultraviolet rays having an emission peak wavelength in the range of 350 to 420 nm is used as an active energy ray source.
  • the amount of these polymerization initiators used is preferably in the range of 1 to 20% by mass as the total amount used with respect to 100% by mass of the non-volatile components in the active energy ray-curable offset ink composition of the present invention. . That is, when the total amount of polymerization initiator used is 1% by mass or more, good curability can be obtained, and when it is 20% by mass or less, an unreacted polymerization initiator remains in the cured product. The problem of physical properties such as migration, solvent resistance, weather resistance and the like can be avoided. From the point that these performance balances become better, in particular, the range in which the total amount used is 3 to 15% by mass with respect to 100% by mass of the nonvolatile components in the active energy ray-curable ink composition of the present invention It is more preferable that
  • photosensitizers include, for example, amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. It is done.
  • the use amount of these photosensitizers is 1 as the total use amount with respect to 100% by mass of the non-volatile component in the active energy ray-curable ink composition of the present invention from the viewpoint that the effect of improving curability is good. It is preferably in the range of ⁇ 20% by mass, and in particular, the blending ratio of the epoxy acrylate compound (A) and the polymerizable acrylate monomer (B) can be increased to achieve a balance between curability and printability. Is preferably in the range of 1 to 10% by mass of the total amount of the ink composition.
  • the active energy ray-curable composition of the present invention contains the polymerizable acrylate monomer (B) in a range of 5 to 40% by mass, preferably in a range of 15 to 40% by mass, based on the total amount of the ink composition.
  • the polymerizable acrylate monomer (B) in a range of 5 to 40% by mass, preferably in a range of 15 to 40% by mass, based on the total amount of the ink composition.
  • other known and used monomer compounds having an ethylenic double bond may be used in combination.
  • a methacrylate monomer can be used in combination as appropriate, in the present invention, it is preferable to use an acrylate monomer having better curability.
  • a bifunctional or higher functional acrylate monomer which is more reactive than a monofunctional monomer, but depending on the application, adhesion to a printing substrate, flexibility of a cured coating film In order to obtain the necessary physical properties such as, it is possible to use a monofunctional acrylate monomer as appropriate.
  • Examples of the monofunctional acrylate monomer include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, tridecyl acrylate, hexadecyl acrylate, octadecyl acrylate, isoamyl acrylate, isodecyl acrylate, isostearyl acrylate, and cyclohexyl.
  • bifunctional or higher functional acrylate monomer examples include 1,4-butanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 2 -Methyl-1,8-octanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, tricyclodecane dimethanol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate Diacrylate of dihydric alcohol such as acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol A trivalent or more polyvalent polyacrylate such as acrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, trimethylolpropane triacrylate, penta
  • a wax can be added for the purpose of improving curability.
  • the wax include paraffin wax, carnauba wax, beeswax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, polytetrafluoroethylene wax, amide wax and the like, and C8-C18 grades such as coconut oil fatty acid and soybean oil fatty acid. The fatty acid etc. which are in the range can be mentioned.
  • melt-type wax has poor compatibility with the epoxy acrylate compound (A) used in the present invention, ink fluidity tends to decrease, but polyethylene wax and polyethylene oxide wax are representative.
  • a powder type or particle type polyolefin wax is preferred because it does not affect the compatibility and maintains good ink fluidity. More preferably, the polyolefin wax has a melting point in the range of 90 to 130 ° C. and an average particle diameter D50 in the range of 1 to 10 micrometers. When the average particle diameter D50 is less than 1 micrometer, it is difficult to improve the curability, and when it exceeds 10 micrometers, the ink transfer property on the printing press is remarkably deteriorated and the offset printability is impaired.
  • the total amount of wax used is preferably in the range of 0.1 to 5% by mass with respect to 100% by mass of the non-volatile component in the active energy ray-curable composition of the present invention.
  • pigments, dyes, extender pigments, organic or inorganic fillers, organic solvents, antistatic agents, antifoaming agents, viscosity adjustments as other blends of the above-described components Additives such as an agent, a light-resistant stabilizer, a weather-resistant stabilizer, a heat-resistant stabilizer, an ultraviolet absorber, an antioxidant, a leveling agent, and a pigment dispersant can be used.
  • the active energy ray-curable offset ink composition of the present invention can be formed into a cured coating film by irradiating active energy rays after printing on a substrate.
  • the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • ultraviolet rays are particularly preferable from the viewpoint of curability and convenience.
  • the active energy rays for curing the active energy ray-curable offset ink of the present invention are ionizing radiations such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • ionizing radiations such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • a curing device for example, germicidal lamp, ultraviolet fluorescent lamp, UV-LED (ultraviolet light emitting diode), carbon arc, xenon lamp, high pressure mercury lamp for copying, medium or high pressure mercury lamp, ultra high pressure mercury lamp, electrodeless lamp, Examples thereof include a metal halide lamp, ultraviolet rays using natural light as a light source, or an electron beam using a scanning type or curtain type electron beam accelerator.
  • Examples of the pigment used in the active energy ray-curable offset ink of the present invention include publicly known organic pigments for coloring.
  • Organic pigments for printing inks published in the first edition include soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinones Pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, other polycyclic pigments, and titanium oxide for white ink Can be mentioned.
  • the blending ratio of these pigments is, for example, preferably 40 to 70% by mass in the ink composition in the
  • inorganic fine particles may be used as extender pigments.
  • inorganic coloring pigments such as titanium oxide, kraftite, zinc white; lime carbonate powder, precipitated calcium carbonate, gypsum, clay (ChinaClay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, Examples thereof include inorganic extender pigments such as aluminum stearate, magnesium carbonate, barite powder, and abrasive powder, silicone, and glass beads.
  • These inorganic fine particles used as extender pigments can be used in the ink composition in the range of 0.1 to 20% by mass to adjust the fluidity of ink, prevent misting, and prevent penetration into printing substrates such as paper. An effect can be obtained.
  • the printing substrate suitable for the active energy ray-curable offset ink of the present invention includes a catalog, a poster, a flyer, a CD jacket, a direct mail, a brochure, a paper used for cosmetics, beverages, pharmaceuticals, toys, equipment packages, etc.
  • Base materials Films used for various food packaging materials such as polypropylene film and polyethylene terephthalate (PET) film, aluminum foil, synthetic paper, and other various base materials conventionally used as printing base materials.
  • the present invention can be suitably used particularly in lithographic offset printing in which water is continuously supplied to the plate surface in terms of improving the emulsification characteristics of the ink.
  • Offset printers that supply water continuously are manufactured and sold by a large number of printer manufacturers. Examples include Heidelberg, Komori Corporation, Mitsubishi Heavy Industries Printing Paper Machinery, Man Roland, Ryobi, and KBA.
  • the present invention can be suitably used in any sheet feeding system, such as a sheet-fed offset printing machine using a sheet form printing paper, an offset rotary printing machine using a reel form printing paper. More specifically, offset printing machines such as Heidelberg's Speedmaster series, Komori Corporation's Lithrone series, and Mitsubishi Heavy Industries Printing Paper Machine Co., Ltd.'s Diamond series can be mentioned.
  • the chemical shift of each carbon atom represented by A to G in the following structural formulas (1) to (7) is as follows when the peak of DMSO-d6 as the measurement solvent is 39.5 ppm: Become. Chemical shift of the carbon atom indicated by A: 71.1 ppm Chemical shift of the carbon atom indicated by B: 65.6 ppm Chemical shift of carbon atom indicated by C: 63.0 ppm Chemical shift of carbon atom indicated by D: 62.5 ppm Chemical shift of carbon atom represented by E: 59.7 ppm Chemical shift of carbon atom represented by F: 60.0 ppm Chemical shift of carbon atom indicated by G: 43.9 ppm
  • the peak of the carbon atom (shown by B) marked with * in the ⁇ addition structure of the following structural formula (1) is the * of the structural site present in the resin structure shown in the following structural formula (6). Since it overlaps with the carbon atom marked (marked with B), the existence ratio of the ⁇ -added structure is a value obtained by subtracting the peak area of the carbon
  • Synthesis example 2 In a four-necked flask equipped with a stirrer, a thermometer and a cooling pipe, a liquid bisphenol A type epoxy resin (“Epiclon 850, epoxy equivalent 188 g / eq. Manufactured by DIC Corporation; hereinafter abbreviated as“ liquid BPA type epoxy resin ”). 435.1 parts by mass, acrylic acid 163.6 parts by mass, and methoquinone (polymerization inhibitor; hereinafter abbreviated as “MQ”) 0.1 part by mass were charged and heated to 100 ° C. 1.2 parts by mass of triphenylphosphine (catalyst; hereinafter abbreviated as “TPP”) was added. By carrying out the reaction at 100 ° C.
  • MQ methoquinone
  • the tack value is a numerical value indicating the tackiness of the ink, that is, the larger the numerical value, the higher the tackiness and viscosity.
  • 1.31 ml of evaluation ink was placed on a rubber roll of an incometer (manufactured by Toyo Seiki Co., Ltd.), and the tack value at the time when the ink was rotated at 32 ° C. and 400 rpm for 1 minute was recorded.
  • indigo pigment Pigment Blue 15: 3, phthalocyanine blue
  • the active energy ray-curable ink composition thus obtained was used on a rubber roll and metal roll of the RI tester using a simple color developing machine (RI tester, manufactured by Toyoe Seiko Co., Ltd.) and using 0.10 ml of ink. Stretched uniformly over the surface of coated paper (“OK Top Coat Plus 57.5 kg, A size” manufactured by Oji Paper Co., Ltd.) over an area of 200 cm 2 with an indigo density of 1.6 (measured with a SpectroEye densitometer manufactured by X-Rite) The color was developed so that it could be applied uniformly, and a color-extracted product was produced.
  • the RI tester is a test machine that develops ink on paper or film, and can adjust the amount of ink transferred and the printing pressure.
  • UV ultraviolet rays
  • a UV irradiation device equipped with a water-cooled metal halide lamp (output: 100 W / cm1 light) and a belt conveyor (made by Eye Graphics Co., Ltd., with a cold mirror)
  • the color-exposed product is placed on the conveyor and directly under the lamp (irradiation distance: 11 cm) was passed through at a speed of 100 meters per minute to cure the ink film.
  • the amount of ultraviolet irradiation under each condition was measured using an ultraviolet integrating light meter (UNIMETER UIT-150-A / receiver UVD-C365 manufactured by USHIO INC.).
  • Offset printing method of active energy ray-curable ink composition With respect to the produced active energy ray-curable inks of Examples 1 and 2 and Comparative Examples 1 to 8, the offset printability was evaluated. 9000 sheets per hour using a Man Roland offset printing machine (Roland R700 printing machine, 40-inch wide machine) equipped with a water-cooled metal halide lamp (output: 160 W / cm, 3 lamps used) as an ultraviolet irradiation device. Offset printing was performed at a printing speed of. For the printing paper, OK Top Coat Plus (57.5 kg, A size) manufactured by Oji Paper Co., Ltd. was used. The fountain solution supplied to the printing plate was an aqueous solution in which 98% by mass of tap water and 2% by mass of an etchant (FST-700, manufactured by DIC) were mixed.
  • FST-700 etchant
  • the printability of the active energy ray-curable ink was evaluated according to the following criteria. 3: The indigo density of the printed material is 1.5 or more, and the offset printability is good 2: The indigo density of the printed material is 1.4 to 1.5 and the offset printability is moderate 1: The indigo density of the printed material is less than 1.4, and the offset printability is poor.
  • Miramar M3130 Ethylene oxide (average 3 mol) modified trimethylolpropane triacrylate (EO3-TMPTA), manufactured by MIWON, monomer viscosity at 25 ° C. 60 millipascal seconds, weight average molecular weight 428 Miramar M300: Trimethylolpropane triacrylate (TMPTA), manufactured by MIWON, monomer viscosity at 25 ° C. 100 millipascal seconds, weight average molecular weight 296 Miramar M410: ditrimethylolpropane tetraacrylate (DTMPTA), manufactured by MIWON, monomer viscosity at 25 ° C.
  • DTMPTA ditrimethylolpropane tetraacrylate
  • Miramar M600 Dipentaerythritol hexaacrylate (DPHA), manufactured by MIWON, monomer viscosity at 25 ° C., 5250 millipascal seconds, weight average molecular weight 578
  • Miramar M3160 ethylene oxide (average 6 mol) modified trimethylolpropane triacrylate (EO6-TMPTA), manufactured by MIWON, monomer viscosity at 25 ° C., 80 millipascal seconds, weight average molecular weight 560 PETA-K: Pentaerythritol tetraacrylate (PETA), manufactured by Daicel Ornex, monomer viscosity at 25 ° C., 800 millipascal seconds, weight average molecular weight 352 Miramer M240: ethylene oxide (average 4 mol) modified bisphenol A diacrylate (BisA-EO4-DA), manufactured by MIWON, monomer viscosity at 25 ° C.
  • BisA-EO4-DA modified bisphenol A
  • HELIOGEN BLUE D7079 Pigment Blue 15: 3 (phthalocyanine blue, indigo pigment), high filler manufactured by BASF # 5000PJ: talc (hydrous magnesium silicate), magnesium carbonate TT manufactured by Matsumura Sangyo Co., Ltd.
  • Irgacure 907 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one, EAB-SS manufactured by BASF: 4,4′-bis (diethylamino) benzophenone, Daido Kasei Kogyo Co., Ltd.
  • Q-1301 N-nitrosophenylhydroxylamine aluminum salt, manufactured by Wako Pure Chemical Industries

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne une composition d'encre d'imprimerie durcissable par des rayons énergétiques actifs qui présente une grande capacité de durcissement en plus d'une excellente capacité d'impression offset et d'une excellente capacité d'émulsification et un article imprimé associé. La composition d'encre offset durcissable par des rayons énergétiques actifs selon l'invention comprend: un composé époxy-acrylate (A) qui est obtenu par la réaction d'une résine époxy A bisphénol avec un acide acrylique, le rapport entre des groupes α-glycol et le nombre total de sites de structure terminale qui sont provoqués par ou qui prennent leur source dans les groupes glycidyloxy de la résine époxy A bisphénol étant inférieur ou égal à 5% (pourcentage molaire) selon les résultats d'une mesure 13C-NMR, et qui représente 10-60% en masse de la quantité totale de la composition; et un monomère d'acrylate polymérisable (B) qui présente une viscosité comprise dans la plage de 40-200 millipascals-seconde (mPa·s) à 25°C, qui présente un poids moléculaire de 250-500 par molécule, qui comprend deux ou plus de deux groupes acrylique et qui représente 5-40% en masse de la composition.
PCT/JP2014/082862 2013-12-19 2014-12-11 Composition d'encre offset durcissable par des rayons énergétiques actifs et article imprimé utilisant ladite composition WO2015093394A1 (fr)

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KR102636596B1 (ko) * 2019-01-31 2024-02-13 주식회사 엘지화학 항균성 고분자 코팅 조성물 및 항균성 고분자 필름

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JPH11152317A (ja) * 1997-11-19 1999-06-08 Mitsubishi Rayon Co Ltd プラスチックレンズ用組成物
JP2000302997A (ja) * 1999-04-19 2000-10-31 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化型組成物およびそれを用いた硬化皮膜の形成方法
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CN108774426B (zh) * 2018-07-06 2021-08-24 南雄市科鼎化工有限公司 一种高性能表面贴装油墨及其制备方法

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