WO2023281971A1 - Composition de résine durcissable par rayonnement d'énergie active, dispersion de pigment durcissable par rayonnement d'énergie active, composition d'encre pour encre offset, et composition d'encre pour encre flexographique - Google Patents

Composition de résine durcissable par rayonnement d'énergie active, dispersion de pigment durcissable par rayonnement d'énergie active, composition d'encre pour encre offset, et composition d'encre pour encre flexographique Download PDF

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Publication number
WO2023281971A1
WO2023281971A1 PCT/JP2022/023195 JP2022023195W WO2023281971A1 WO 2023281971 A1 WO2023281971 A1 WO 2023281971A1 JP 2022023195 W JP2022023195 W JP 2022023195W WO 2023281971 A1 WO2023281971 A1 WO 2023281971A1
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Prior art keywords
active energy
energy ray
resin
meth
curable
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PCT/JP2022/023195
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English (en)
Japanese (ja)
Inventor
達也 塩澤
和哉 岡本
良寿 福地
隼也 末永
Original Assignee
東洋インキＳｃホールディングス株式会社
東洋インキ株式会社
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Priority claimed from JP2021111773A external-priority patent/JP2022094287A/ja
Priority claimed from JP2021198619A external-priority patent/JP2023084439A/ja
Application filed by 東洋インキＳｃホールディングス株式会社, 東洋インキ株式会社 filed Critical 東洋インキＳｃホールディングス株式会社
Publication of WO2023281971A1 publication Critical patent/WO2023281971A1/fr

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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
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • 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
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints

Definitions

  • One embodiment of the present invention provides an active energy ray-curable resin composition, an active energy ray-curable pigment dispersion, and an ink composition for offset ink, which are excellent in curability and can be widely used as various paints including printing inks. and an ink composition for flexo ink.
  • the active energy ray-curable ink contains an unsaturated compound having active energy ray-curable properties such as a (meth)acrylic ester compound as a constituent component, and instantly cures when irradiated with an active energy ray, and the unsaturated compound Forms a tough film by three-dimensional cross-linking. Because it cures instantly, post-processing can be performed immediately after printing, so active energy ray curing is used in package printing for packaging and form printing in the commercial field, which require a strong film to improve productivity and protect designs.
  • a neutral ink is preferably used.
  • Unsaturated compounds used in active energy ray-curable inks include (meth)acrylic ester compounds obtained by the reaction of polyols and (meth)acrylic acid, or polyesters obtained by the reaction of polyester polyols and (meth)acrylic acid. Oligomers such as (meth)acrylates and urethane (meth)acrylates obtained by reaction of polyisocyanate and hydroxy (meth)acrylate can be mentioned.
  • Patent Documents 1 to 3 disclose resins obtained by introducing (meth)acrylic groups into polyester polyols via isocyanate compounds. However, in these documents, the introduction amount of (meth)acrylic groups is small.
  • Patent Document 1 no alcohol having a valence of 3 or higher is used in the synthesis of the polyester polyol.
  • the ratio (OH/COOH) of OH contained in the alcohol used and COOH contained in the monobasic acid and polybasic acid is less than 1.10.
  • Patent Document 3 does not mention that the ratio of trihydric or higher alcohol to the total amount of alcohol used is 13.0 mol % or more.
  • the hydroxyl value of the resulting polyester resin is low, and the amount of (meth)acrylic groups introduced into the resin through the hydroxyl groups is limited, making it impossible to improve curability. Therefore, a compound having a large number of hydroxyl groups, specifically a polyester having a high hydroxyl value, is desired for introducing a large number of (meth)acrylic groups for improving curability.
  • active energy ray-curing ink has poorer fluidity than oil-based ink, so there is a problem that the ink is not scraped off from the ink fountain by the roller during printing (ink fountain escape), and the dot gain of printed matter is reduced. There is a problem that the print reproducibility is lowered due to the low density.
  • active energy ray-curable inks use pigments as colorants, and it is necessary to uniformly and finely disperse the pigments in order to obtain beautiful prints.
  • Dispersants such as surfactants, non-reactive polymeric pigment dispersants, and pigment derivatives are conventionally added to disperse pigments.
  • polymer dispersants are known to be excellent in dispersion stability because they adsorb to the surface of pigments and prevent pigment aggregation due to steric hindrance.
  • Patent Document 4 a proposal has been made to achieve both pigment dispersibility and curability when irradiated with active energy rays by using a polymer pigment dispersion having an ethylenically unsaturated bond in order to increase curability
  • a monomer mixture containing acrylic monomers having hydroxyl groups is copolymerized, and the hydroxyl groups of the obtained copolymer are reacted with acryloyloxyisocyanate to prepare a polymeric dispersant with pendant acrylic groups.
  • acrylic copolymers must be synthesized in a solution from the viewpoint of heat generation, and the subsequent modification and pigment dispersion are also carried out in a solution.
  • Some active energy ray-curable inks and paints are supplied as solvent systems, but offset inks, flexographic inks, inkjets, etc. are non-solvent-based, making it difficult to use active energy ray-curable polymer dispersants. is.
  • the use of organic solvents has recently been restricted due to environmental concerns, and it has become generally difficult to use materials that are supplied as solutions.
  • An embodiment of the present invention stably synthesizes a polyester with a high hydroxyl value in order to eliminate the ink fountain trouble during printing, improve the dot gain of the printed matter, and improve the curability.
  • an active energy ray-curable resin composition having a very large number of (meth)acrylic groups and having extremely high curability is provided.
  • An object of the present invention is to provide an active energy ray-curable resin composition which is friendly to the environment by reducing photoinitiator or irradiation energy.
  • an active energy ray-curable compound having an ethylenically unsaturated bond which can be synthesized without using a solvent and has a high affinity for pigments, was synthesized, and the compound was used as a dispersant to form an active energy ray-curable compound.
  • An object of the present invention is to prepare a pigment dispersion and to provide highly curable inks, paints, etc. using this dispersion.
  • the present inventors reacted a polyester resin containing many hydroxyl groups, an isocyanate compound, and a hydroxyl group-containing (meth)acrylic compound under appropriate conditions to achieve active energy ray-curable It was found that a resin containing many (meth)acrylic groups can be obtained, and an active energy ray-curable resin composition containing the resin can provide an ink or the like with excellent curability, leading to the present embodiment. rice field.
  • polyester was selected as a compound that can be synthesized without using a solvent and has a high affinity for pigments, and an active energy ray-curable compound with an ethylenically unsaturated bond with polyester as the main skeleton is used as a dispersant for pigments.
  • the present inventors have found that the ink and paint can be cured with less energy than usual because the pigment dispersion has active energy ray curability. In addition, if it is solvent-free, it does not require heat energy for drying, and can be cured with less energy than before when curing with active energy rays. The form has been completed.
  • One aspect of the present embodiment is a first resin (A) obtained by reacting a hydroxyl-containing polyester resin (a1), an isocyanate compound (a2), and a hydroxyl-containing (meth)acrylic compound (a3);
  • the hydroxyl-containing polyester resin (a1) is a resin obtained by reacting under conditions in which the amount of trihydric or higher alcohol with respect to the entire polyhydric alcohol is 13 mol% or more. It relates to an active energy ray-curable resin composition.
  • Another aspect of the present embodiment relates to the active energy ray-curable resin composition, wherein the hydroxyl group-containing polyester resin (a1) has a weight average molecular weight of 2,500,000 to 100,000.
  • Another aspect of the present embodiment relates to the active energy ray-curable resin composition, wherein the trihydric or higher alcohol contains glycerin.
  • the first resin (A) is a compound containing a (meth)acrylic group and a secondary amino group in the first resin (A) that undergoes a Michael addition reaction.
  • the present invention relates to the active energy ray-curable resin composition containing a resin having a tertiary amine structure obtained by
  • Another aspect of the present embodiment relates to an ink composition for offset ink containing the active energy ray-curable resin composition.
  • Another aspect of the present embodiment relates to an ink composition for flexographic ink containing the active energy ray-curable resin composition.
  • Another aspect of the present embodiment relates to the ink composition for flexo ink, wherein the hydroxyl group-containing polyester resin (a1) has a weight average molecular weight of 250 to 3,000.
  • Another aspect of the present embodiment is a first resin (A) obtained by reacting a hydroxyl group-containing polyester resin (a1), an isocyanate compound (a2), and a hydroxyl group-containing (meth)acrylic compound (a3), And an active energy ray-curable pigment dispersion containing a pigment (C), wherein the hydroxyl group-containing polyester resin (a1) is a polyhydric alcohol containing a trihydric or higher alcohol and a polybasic acid, OH / COOH It is a resin obtained by reacting under conditions where the molar ratio is 1.10 or more, the hydroxyl value of the hydroxyl group-containing polyester resin (a1) is 50 mgKOH/g or more, and the weight average molecular weight of the hydroxyl group-containing polyester resin (a1) is , 250 to 3000, it relates to an active energy ray-curable pigment dispersion.
  • the first resin (A) is a compound containing a (meth)acrylic group and a secondary amino group in the first resin (A) that undergoes a Michael addition reaction.
  • the active energy ray-curable pigment dispersion containing a resin having a tertiary amine structure obtained by
  • the active energy ray-curable resin composition of the present embodiment can be used in a wide range of applications as inks, coating agents, etc. with excellent curability, and is extremely useful industrially.
  • the active energy ray-curable pigment dispersion of the present embodiment can be used for a wide range of applications such as active energy ray-curable offset or flexographic inks, coating agents, etc., which have excellent curability, and is extremely useful industrially. be.
  • the activation energy in this embodiment means the energy required to excite the starting material of the curing reaction from the ground state to the transition state, and the activation energy ray in this embodiment means ultraviolet rays or electron beams.
  • (Meth)acryl in this specification means "acryl or methacryl”.
  • the active energy ray-curable resin composition contains a resin (A) and a polyfunctional (meth)acrylic compound (B).
  • the resin (A) is obtained by reacting a hydroxyl group-containing polyester resin (a1), an isocyanate compound (a2), and a hydroxyl group-containing (meth)acrylic compound (a3).
  • the reactions with the hydroxyl group-containing polyester resin (a1), the isocyanate compound (a2), and the hydroxyl group-containing (meth)acrylic compound (a3) may be carried out simultaneously, and the isocyanate compound (a2) and the hydroxyl group-containing (meth)acrylic compound ( After reacting a3) in advance, the hydroxyl group-containing polyester resin (a1) may be reacted.
  • the molar ratio of the total hydroxyl groups of the hydroxyl-containing polyester resin (a1) and the hydroxyl-containing (meth)acrylic compound (a3) to the isocyanate groups of the isocyanate compound (a2) is preferably 1 or less in terms of NCO/OH.
  • a catalyst can also be used.
  • Usable catalysts include, for example, tertiary amine-based catalysts such as triethylamine and dimethylaniline, and metal-based catalysts such as tin and zinc.
  • the reaction can be carried out in a solvent, but the reaction can also be carried out in a polyfunctional (meth)acrylic compound (B) described later, and the resin (A) is dissolved in the polyfunctional (meth)acrylic compound. It is preferable because the step of removing the solvent and the step of removing the solvent can be omitted.
  • the resin (A) has two or more functional groups having an ethylenically unsaturated bond, and is a condensation reaction of a dicarboxylic acid and/or an anhydride of a dicarboxylic acid as a polybasic acid and a polyhydric alcohol as a hydroxyl group-containing compound.
  • the hydroxyl group-containing polyester resin (a1) is a compound obtained by reacting a polyhydric alcohol containing a trihydric or higher alcohol with a polybasic acid in an OH/COOH molar ratio of 1.10 or more.
  • a polyhydric alcohol containing a trihydric or higher alcohol as the hydroxyl group-containing compound, the hydroxyl group-containing polyester resin (a1) can have a hydroxyl group, so that it is easy to introduce an ethylenically unsaturated double bond in the next step. Become.
  • OH is the number of moles of hydroxyl groups in the polyhydric alcohol
  • COOH is the number of moles of carboxyl groups that can theoretically react with the alcohol.
  • the COOH is 2 mol.
  • a trihydric or higher alcohol and reacting a polyhydric alcohol with a polybasic acid in an OH/COOH molar ratio of 1.10 or more, introducing many hydroxyl group terminals into the hydroxyl group-containing polyester resin (a1). It becomes possible to introduce a large number of active energy ray-curable acrylic groups by the reaction with the isocyanate compound (a2) and the hydroxyl group-containing (meth)acrylic compound (a3) in the next step.
  • the hydroxyl group-containing polyester resin (a1) can be easily obtained by subjecting the above polyhydric alcohol and polybasic acid to a conventional heating and dehydration condensation reaction.
  • the condensation reaction proceeds without a catalyst, but catalysts such as sulfuric acid, paratoluenesulfonic acid, and methanesulfonic acid may be used.
  • a suitable solvent such as xylene can also be used if desired.
  • the weight average molecular weight of the hydroxyl group-containing polyester resin (a1) is 2,500 to 100,000. If the weight-average molecular weight is less than 250, polyester cannot be obtained.
  • the weight average molecular weight can be measured, for example, by gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation.
  • a calibration curve can be generated with standard polystyrene samples.
  • the measurement can be performed, for example, using tetrahydrofuran as an eluent, three columns of TSKgel Super HM-M (manufactured by Tosoh Corporation), a flow rate of 0.6 ml/min, an injection volume of 10 ⁇ l, and a column temperature of 40°C.
  • the hydroxyl value of the hydroxyl-containing polyester resin (a1) is preferably 50 mgKOH/g or more, and if it is less than 50 mgKOH/g, the reaction of the hydroxyl-containing (meth)acrylic compound (a3) via the isocyanate compound (a2) is insufficient. The effect of improving the curability becomes small, which is not preferable.
  • the hydroxyl value of the hydroxyl-containing polyester resin (a1) is preferably 100 mgKOH/g or more, more preferably 150 mgKOH/g or more, and even more preferably 200 mgKOH/g or more.
  • the hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of the target resin sample is acetylated. can ask.
  • the target resin is dissolved in a solvent in which diethyl ether and ethanol are mixed at a weight ratio of 1:1, and then a 0.1 mol/L potassium hydroxide-ethanol solution is added. Titration is performed by potentiometric titration. Then, the hydroxyl value can be calculated using the titration amount read from the obtained titration curve.
  • the trihydric or higher polyhydric alcohol is not particularly limited, and examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, sorbitan, sorbitol, dipentaerythritol, inositol, and tripentaerythritol.
  • glycerin and diglycerin which have two primary hydroxyl groups and other hydroxyl groups of which are secondary or higher, are particularly desirable.
  • a dihydric alcohol can also be used as the polyhydric alcohol.
  • the dihydric alcohol is not particularly limited, and examples thereof include linear alkylene dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, ,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2 -dodecanedio
  • the polybasic acid is not particularly limited, and examples thereof include aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecenylsuccinic acid, penta Alkenyl succinic acids such as decenyl succinic acid, offsoftaric acid, isophthalic acid, terephthalic acid, hymic acid, 3-methylhimic acid, 4-methylhimic acid, trimellitic acid, and pyromellitic acid as aromatic polybasic acids , 1,8-naphthalic acid and their anhydrides, 1,2,3,6-tetrahydrophthalic acid as alicyclic polybasic acids, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4- methyl-1,2,3,6-tetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid,
  • a monohydric alcohol and a monobasic acid can also be used in combination during the reaction between the polyfunctional alcohol and the polybasic acid.
  • Examples of monohydric alcohols include n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, isopentyl alcohol, amyl alcohol and tert-pentyl alcohol. , cyclohexyl alcohol, benzyl alcohol, ⁇ -phenylethyl alcohol and the like.
  • monobasic acids examples include benzoic acid, methylbenzoic acid, t-butylbenzoic acid, naphthoic acid, orthobenzoylbenzoic acid, propionic acid, butyric acid, ⁇ -methylbutyric acid, valeric acid, and cyclohexanecarboxylic acid.
  • lactic acid oxyacids such as 12-hydroxystearic acid
  • cyclic esters such as caprolacurone
  • the isocyanate compound (a2) is not particularly limited. 4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1 , 3-bis(is
  • the hydroxyl group-containing (meth)acrylic compound (a3) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylates, glycerin (meth) acrylate, glycerin di ( meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)
  • (Secondary amine) A secondary amine is used to introduce a tertiary amine into the resin (A) by undergoing a Michael addition reaction with the (meth)acrylic group of the resin (A) in the active energy ray-curable resin composition.
  • This tertiary amine has the effect of promoting the radical cross-linking reaction of the surface, which is the interface with the air, by suppressing the cross-linking inhibition caused by oxygen during the radical cross-linking reaction of the (meth)acrylic group during the active energy ray curing process. be.
  • secondary amines examples include dipropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, butylmethylamine, methylhexylamine, di-N-octylamine, di(2-ethylhexyl)amine, and ethylisoamylamine.
  • methylethylamine methylisopropylamine, butylethylamine, 2-(hydroxymethylamino)ethanol, diethanolamine, 4-methylaminobutanol, dibenzylamine, methylbenzylamine, piperidine, 2-pipecoline, 3-pipe Choline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, N-methyl-3-piperidinemethanol, 4-piperidinemethanol, 2-piperidineethanol , 4-piperidine ethanol, methyl isonicopetate, ethyl isonipecotate, 4-piperidinol, N-methyl-4-piperidinol, N-benzyl-4-piperidinol, N,N-dimethyl-4-piperidinamine, 2, 2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, pyrrolidine, 3-pyrrolidinol, 1-acetylpiperazine, 1-cyclopentylpiperazine, 1-
  • Michael addition of a secondary amine to an acrylic group is performed by adding a secondary amine to the synthesized active energy ray-curable resin composition.
  • a secondary amine is added dropwise to the active energy ray-curable resin composition charged in a flask while stirring, and after the dropwise addition is completed, the mixture is gradually heated and held at around 80°C (for example, 80 to 100°C) for several hours.
  • the Michael addition reaction is completed.
  • the content of the polyfunctional (meth)acrylic compound (B) is 10 to 90% by weight, preferably 40 to 80% by weight, based on the total composition.
  • the content of the radical polymerization inhibitor is 0.01 to 5% by weight, preferably 0.1 to 1% by weight.
  • the resin (A) in the active energy ray-curable resin composition of the first configuration comprises a hydroxyl group-containing polyester resin (a1) obtained by condensation reaction of a polybasic acid and a polyhydric alcohol, an isocyanate compound (a2), and a hydroxyl group-containing (meth)acrylic compound (a3) obtained by addition reaction,
  • the hydroxyl group-containing polyester resin (a1) is a polyhydric alcohol containing a trihydric or higher alcohol and a polybasic acid
  • the OH / COOH molar ratio is a compound reacted in the range of 1.50 or more.
  • a trihydric or higher alcohol and reacting a polyhydric alcohol with a polybasic acid in the range of an OH/COOH molar ratio of 1.50 or more to introduce a large number of hydroxyl group terminals into the hydroxyl group-containing polyester resin (a1). It becomes possible to do so, and many active energy ray-curable (meth)acrylic groups can be introduced by the reaction with the isocyanate compound (a2) and the hydroxyl group-containing (meth)acrylic compound (a3) in the next step.
  • Polyhydric alcohol and polybasic acid are reacted at an OH/COOH molar ratio of 1.50 or more, preferably 1.50 to 4.0, more preferably 1.50 to 3.0. , 1.60 to 3.0 is more preferable, and may be 1.50 to 2.25, 1.50 to 2.0, or 1.60 to 2.0. If it is less than 1.50, the number of terminal hydroxyl groups will decrease, which is not preferable.
  • hydroxyl groups In order to introduce sufficient hydroxyl groups, it is preferable to contain 50 mol% or more of trihydric or higher alcohol, more preferably 60 mol% to 100 mol%, based on the total polyhydric alcohol. If it is less than 50 mol %, the amount of introduced hydroxyl groups is small, and as a result, the density of (meth)acrylic groups in the hydroxyl group-containing polyester resin becomes low, so that curability cannot be improved.
  • the weight average molecular weight of the hydroxyl group-containing polyester resin (a1) in the first configuration is 250-3000, preferably 250-2000, and may be 280-3000 or 400-2000. If the weight average molecular weight is less than 250, it does not become a polyester, and when it is made into a highly curable active energy ray-curable resin composition exceeding 3000, the viscosity is too high, and the amount that can be added as an ink composition for flexographic ink and a coating agent is small. , and the effect of high curability is reduced, which is not preferable.
  • the hydroxyl value of the hydroxyl-containing polyester resin (a1) is preferably 200 mgKOH/g or more, more preferably 290 mgKOH/g or more. The reaction of the meth)acrylic compound (a3) is not sufficiently carried out, and the effect of improving the curability becomes small, which is not preferable.
  • the resin (A) in the active energy ray-curable resin composition of the second configuration comprises a hydroxyl group-containing polyester resin (a1) obtained by condensation reaction of a polybasic acid and a polyhydric alcohol, an isocyanate compound (a2), and a hydroxyl group-containing (meth)acrylic compound (a3) obtained by addition reaction,
  • the hydroxyl group-containing polyester resin (a1) is a polyhydric alcohol containing a trihydric or higher alcohol and a polybasic acid
  • the OH / COOH molar ratio is a compound reacted in the range of 1.10 to 2.20.
  • a hydroxyl group terminal is formed in the hydroxyl group-containing polyester resin (a1).
  • a large number of active energy ray-curable acrylic groups can be introduced in the reaction with the isocyanate compound (a2) and the hydroxyl group-containing (meth)acrylic compound (a3) in the next step.
  • Polyhydric alcohol and polybasic acid are reacted at an OH/COOH molar ratio of 1.10 to 2.20, preferably 1.10 to 2.02, more preferably 1.10 to 1.94.
  • the range of 1.10 to 1.50 is more preferable, and the range of 1.14 to 1.41 is particularly preferable. If it is less than 1.10, the number of terminal hydroxyl groups will decrease, and if it exceeds 2.20, it will be difficult to increase the molecular weight, which is not preferable.
  • trihydric or higher alcohol In order to introduce sufficient hydroxyl groups, it is preferable to contain 13 mol% or more of trihydric or higher alcohol, more preferably 20 mol% or more and 50 mol% or less, based on the total polyhydric alcohol. If it exceeds 50 mol %, gelation tends to occur during the synthesis of the hydroxyl group-containing polyester resin (a1). However, if a monobasic acid such as benzoic acid is used in combination, 50 mol % or more of trihydric or higher alcohol can be used with respect to the total polyhydric alcohol.
  • the weight average molecular weight of the hydroxyl group-containing polyester resin (a1) in the second configuration is 2,500 to 100,000, preferably 3,000 to 100,000, more preferably 5,000 to 20,000. When the weight average molecular weight is 3000 or more, the effect of improving the curability is sufficiently exhibited, which is more preferable. A weight-average molecular weight of 100,000 or less is preferable because a viscosity suitable for the finally obtained active energy ray-curable resin composition (ink composition for offset ink) can be secured.
  • the hydroxyl value of the hydroxyl-containing polyester resin (a1) is preferably 50 mgKOH/g or more, more preferably 79 mgKOH/g or more, and still more preferably 96 mgKOH/g or more. The reaction of the hydroxyl group-containing (meth)acrylic compound (a3) through the isocyanate compound (a2) is not sufficiently carried out, and the effect of improving the curability becomes small, which is not preferable.
  • additives such as radical polymerization inhibitors can be appropriately added to the active energy ray-curable resin composition depending on the required physical properties of the cured film.
  • additives such as radical polymerization inhibitors can be appropriately added to the active energy ray-curable resin composition depending on the required physical properties of the cured film.
  • monofunctional (meth)acrylic compounds, vinyl compounds, or active energy ray-curable oligomers can be used.
  • Examples of monofunctional (meth)acrylic compounds include 2-ethylhexyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-vinyloxy ethoxy)ethyl (meth)acrylate, acryloylmorpholine and the like.
  • Examples of vinyl compounds include N-vinylpyrrolidone and divinylbenzene.
  • Examples of active energy ray-curable oligomers include polyester acrylate, polyurethane (meth)acrylate, and epoxy (meth)acrylate.
  • radical polymerization inhibitors examples include (alkyl)phenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p- Benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cupferron, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino -1,3-dimethylbutylidene)aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methylethylketoxime, cyclohexan
  • the ink composition is also referred to as active energy ray-curable ink or active energy ray-curable ink.
  • the active energy ray-curable ink contains 0 to 30% by weight of pigment, 5 to 40% by weight of binder resin, 30 to 95% by weight of monomer, and 30 to 95% by weight of radical polymerization inhibitor.
  • the composition is adjusted to 0.01 to 1% by weight, 0 to 20% by weight of a photopolymerization initiator and/or sensitizer, and 0 to 10% by weight of other additives.
  • the resin (A) in the active energy ray-curable resin composition disclosed in this embodiment corresponds to a binder resin.
  • the content of the resin (A) in the active energy ray-curable resin composition is preferably 5-40% by weight, more preferably 10-30% by weight, relative to the total ink. If it is 5% by weight or more, the effect of the present embodiment can be sufficiently exhibited, and if it is 40% by weight or less, the viscosity of the ink will be in a range suitable for printing, which is preferable.
  • a binder resin other than the resin (A) can be used for the active energy ray-curable ink, if necessary.
  • binder resins other than resin (A) include diallyl orthophthalate resin, diallyl isophthalate resin, diallyl terephthalate resin, polyester resin, polyvinyl chloride, poly(meth)(meth)acrylate, epoxy resin, and polyurethane resin. , petroleum (based) resins, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, polyamide resins, polyvinyl acetal resins, butadiene-(meth)acrylonitrile Synthetic rubbers such as copolymers can be used. One or more of these resins can be used.
  • the active energy ray-curable ink does not contain a pigment as a coloring agent and has a transparent structure, it becomes an OP varnish, and if it contains the pigments shown below, it becomes a color printing ink.
  • Pigments (C) include inorganic pigments and organic pigments.
  • inorganic pigments include yellow lead, zinc yellow, Prussian blue, barium sulfate, cadmium red, titanium oxide, zinc oxide, red iron oxide, alumina white, calcium carbonate, ultramarine blue, carbon black, graphite, aluminum powder, and red iron oxide.
  • organic pigments include soluble azo pigments such as ⁇ -naphthol, ⁇ -oxynaphthoic acid, ⁇ -oxynaphthoic anilide, acetoacetic anilide, pyrazolone, ⁇ -naphthol, Insoluble azo pigments such as ⁇ -oxynaphthoic anilides, acetoacetate anilide monoazo, acetoacetate anilide disazo, pyrazolone, copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue , phthalocyanine pigments such as metal-free phthalocyanines, quinacridones, dioxazines, threnes (pyranthrone, anthanthrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo, anthraquinone, per
  • An active energy ray-curable resin composition for example, is cured by light, which is an active energy ray.
  • the photo-curing method generally uses a light source that emits ultraviolet rays, such as a metal halide lamp, a high-pressure mercury lamp, or an LED. Also, an electron beam can be used as a light source, and in that case curing is generally possible without using a photopolymerization initiator.
  • a photoradical polymerization initiator When using ultraviolet rays as active energy rays, a photoradical polymerization initiator is blended into the photocurable composition as a photopolymerization initiator.
  • a photopolymerization initiator As the radical photopolymerization initiator, a molecular cleavage type or a hydrogen abstraction type is suitable.
  • benzoin isobutyl ether 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butan-1-one, bis(2,4,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 1,2-octanedione, 1-(4-( Phenylthio)-2,2-(O-benzoyloxime)), oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone, and the like are preferably used.
  • Examples of molecularly cleaved types include 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)- 2-Hydroxy-2-methylpropan-1-one and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one may be used in combination, and hydrogen abstraction type photopolymerization Benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenylsulfide, etc., which are initiators, can also be used in combination.
  • photocleavable initiators include, for example, ⁇ -(dimethyl)aminoalkylphenone compounds and ⁇ -morpholinoalkylphenone compounds.
  • ⁇ -(dimethyl)aminoalkylphenone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 or 2-dimethylamino-2-( 4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one and the like
  • ⁇ -morpholinoalkylphenone compounds include 2-methyl-1-[4- (methylthio)phenyl]-2-morpholinopropan-1-one and the like. These may be used alone or in combination of two or more.
  • examples of hydrogen abstraction type initiators include dialkylbenzophenone compounds and thioxanthone compounds.
  • dialkylaminobenzophenone compounds such as 4,4'-dialkylaminobenzophenones such as 4,4'-bis-(dimethylamino)benzophenone and 4,4'-bis-(diethylamino)benzophenone
  • Dialkylaminobenzophenone compounds such as 4-benzoyl-4'-methyldiphenyl sulfide may be used alone or in combination of two or more.
  • Thioxanthone compounds include, for example, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N,N,N-trimethyl -1-propanamine hydrochloride, etc. These may be used alone or in combination of two or more.
  • sensitizers for the above photopolymerization initiators include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3 ,3′-dimethyl-4-methoxybenzophenone, 4-(1,3-acryloyl-1,4,7,10,13-pentoxotridecyl)benzophenone, methyl-o-benzoylbenzoate, [4-(methylphenyl Thio)phenyl]phenylmethanone, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-2-methyl -1-phenylpropan-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone,
  • the photopolymerization initiator it is particularly preferable to use, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
  • the radical photopolymerization initiator and the sensitizer are preferably used in an amount of 1 to 15% by weight based on the total solid content of the photopolymerizable composition.
  • the above radical polymerization inhibitor can be exemplified as an additive that imparts storage stability to the ink.
  • Additives that impart abrasion resistance, antiblocking properties, smoothness, and scratch resistance include, for example, natural waxes such as carnauba wax, Japan wax, lanolin, montan wax, paraffin wax, microcrystalline wax, fishart Rops wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and synthetic waxes such as silicone compounds can be exemplified.
  • additives such as ultraviolet absorbers, infrared absorbers, and antibacterial agents can be added according to the required performance.
  • the method for producing the active energy ray-curable ink may be performed by a method similar to that for conventional active energy ray-curable inks. Kneading, mixing and adjusting machines such as kneaders, triple rolls, attritors, sand mills, gate mixers, etc. Manufactured using
  • Examples of the printing method include lithographic printing (ordinary lithographic printing using dampening water and waterless lithographic printing not using dampening water), letterpress printing, intaglio printing, stencil printing, flexographic printing, etc., preferably flexographic printing. Print.
  • the base material of the printed material is not particularly limited, and includes printing on all materials such as paper, plastic, stickers, labels, and metals, preferably printing on paper.
  • the active energy ray-curable pigment dispersion contains the resin (A) and the pigment (C).
  • the active energy ray-curable pigment dispersion is obtained by treating the resin (A) and the pigment (C) with a disperser.
  • the mixing ratio of the resin (A) and the pigment (C), which are active energy ray-curable pigment dispersants in the active energy ray-curable pigment dispersion is preferably 5 to 100% by weight of the resin (A) with respect to the pigment (C). is 10 to 50% by weight.
  • the resin (A) and the pigment (C), optionally a diluent monomer or other resin, etc. are added, and depending on the equipment, an appropriate amount of dispersing media is added, followed by a kneader, three rolls, a ball mill, a sand mill, or a scandex.
  • An active energy ray-curable pigment dispersion is prepared using a dispersing device such as When the pigment dispersion is prepared, a suitable amount of the above-mentioned radical polymerization inhibitor may be added since radicals may be generated due to heat or the like during dispersion and gelation may occur. In addition, when the pigment dispersibility is insufficient only with the resin as the active energy ray-curable pigment dispersant, a commercially available pigment dispersant or the like may be used together.
  • pigment dispersants examples include DISPERBYK-194N, DISPERBYK-2008, DISPERBYK-2013, DISPERBYK-2014, DISPERBYK-2158, SOLSPERS32000, SOLSPERS75000, SOLSPERS88000, SOLSPERS39000, and SOLSPERS36000.
  • the resin (A) in the active energy ray-curable pigment dispersion is a reaction product having a polyester structure obtained by the condensation reaction of a dicarboxylic acid and/or an anhydride of a dicarboxylic acid as a polybasic acid and a hydroxyl group-containing compound. Obtained by subjecting a hydroxyl group-containing polyester resin (a1) to an addition reaction with an isocyanate compound (a2) and a hydroxyl group-containing (meth)acrylic compound (a3), and the hydroxyl group-containing polyester resin (a1) is a trihydric or higher alcohol. It is a compound obtained by reacting a contained polyhydric alcohol and a polybasic acid in an OH/COOH molar ratio of 1.10 or more.
  • the OH/COOH molar ratio is 1.10 or more, preferably 1.50 or more by reacting a polyhydric alcohol with a polybasic acid to obtain a hydroxyl group-containing polyester resin (a1) It is possible to introduce a large number of hydroxyl group terminals inside, and in the reaction with the isocyanate compound (a2) and the hydroxyl group-containing (meth)acrylic compound (a3) in the next step, many active energy ray-curable (meth)acrylic groups are generated. can be introduced.
  • the polyhydric alcohol and the polybasic acid are reacted at an OH/COOH molar ratio of 1.50 or more, preferably from 1.60 to 2.0. If it is less than 1.50, the number of terminal hydroxyl groups will decrease, which is not preferable.
  • hydroxyl groups In order to introduce sufficient hydroxyl groups, it is preferable to contain 50 mol% or more of trihydric or higher alcohol, more preferably 60 mol% to 100 mol%, based on the total polyhydric alcohol. If it is less than 50 mol %, the amount of hydroxyl groups introduced is small, and as a result, the density of (meth)acrylic groups in the hydroxyl group-containing polyester resin becomes low, so that the curability of the pigment dispersion cannot be improved.
  • the weight average molecular weight of the hydroxyl group-containing polyester resin (a1) in the active energy ray-curable pigment dispersion is preferably 200-3000, more preferably 220-2000. If the weight average molecular weight is less than 200, a polyester polyol having two or more hydroxyl groups cannot be synthesized, resulting in a decrease in the curability of the pigment dispersion. When used as the viscosity is too high, the wettability with the pigment is poor, making it difficult to prepare a dispersion, which is not preferable.
  • Resin (A), which is an active energy ray-curable dispersant preferably has a tertiary amino group or a quaternary ammonium salt.
  • a tertiary amino group or a quaternary ammonium salt By having a tertiary amino group or a quaternary ammonium salt, the surface of the pigment is usually acidic, so the amino group interacts with the acidic site, resulting in a resin that is an active energy ray-curable pigment dispersant.
  • (A) is expected to adsorb to the pigment to form a stable pigment dispersion.
  • a tertiary amino group can be obtained by Michael addition of a compound having a secondary amino group (secondary amine) to a (meth)acrylic group in the resin (A), which is an active energy ray-curable dispersant. .
  • the tertiary amino group may be neutralized with an acid and used as a quaternary ammonium salt.
  • Active energy ray-curable ink which is an ink composition, comprises 20 to 80% by weight of active energy ray-curable pigment dispersion, 30 to 70% by weight of active energy ray-curable monomer, and 0 of the above radical polymerization inhibitor, based on the total ink. 01 to 1% by weight, 0 to 20% by weight of a photopolymerization initiator and/or sensitizer, and 0 to 10% by weight of other additives.
  • the content of the active energy ray-curable pigment dispersion is preferably 20 to 60% by weight, more preferably 25 to 50% by weight, based on the total ink composition. If the amount is less than 20% by weight, the ink may not be sufficiently colored and hardened, and the hiding effect may not be exhibited sufficiently.
  • the active energy ray-curable monomers used in the ink composition are active energy ray-curable and generally include polyfunctional (meth)acrylic compounds, monofunctional (meth)acrylic compounds, vinyl compounds, allyl compounds, active energy Line-curable oligomers may be mentioned.
  • the content of the polyfunctional (meth)acrylic compound is 30 to 70% by weight, preferably 40 to 60% by weight, based on the total composition.
  • Examples of the polyfunctional (meth)acrylic compound include the polyfunctional (meth)acrylic compound (B).
  • Examples of monofunctional (meth)acrylic compounds include 2-ethylhexyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-vinyloxy ethoxy)ethyl (meth)acrylate, acryloylmorpholine and the like.
  • Examples of vinyl compounds include N-vinylpyrrolidone and divinylbenzene.
  • Examples of active energy ray-curable oligomers include polyester acrylate, polyurethane (meth)acrylate, and epoxy (meth)acrylate.
  • Examples of allyl compounds include pentaerythritol tetraallyl ether, trimethylolpropane triallyl ether, sorbitol triallyl ether, isosorbide diallyl ether, glycerin diallyl ether, bisphenol A diallyl ether, hydrogenated bisphenol A diallyl ether, and diallyl maleate.
  • diallyl fumarate diallyl succinate
  • diallyl itaconate diallyl malate
  • diallyl adipate diallyl dodecanedioate
  • diallyl citrate triallyl trimellitate
  • diallyl cyclohexenedicarboxylate diallyl fumarate, diallyl succinate, diallyl itaconate, diallyl malate, diallyl adipate, diallyl dodecanedioate, diallyl citrate, triallyl trimellitate, and diallyl cyclohexenedicarboxylate.
  • Acid esters As other additives, various resins may be added depending on the required physical properties. Acid esters, epoxy resins, polyurethane resins, petroleum (based) resins, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, polyamide resins, polyvinyl acetal resins , synthetic rubbers such as butadiene-(meth)acrylonitrile copolymers, and the like. One or more of these resins can be used.
  • cellulose derivatives e.g., ethyl cellulose, cellulose acetate, nitrocellulose
  • vinyl chloride vinyl acetate copolymers e.g., polyamide resins, polyvinyl acetal resins, polyamide resins, polyvinyl acetal resins , synthetic rubbers such as butadiene-(meth)acrylonitrile copolymers,
  • An active energy ray-curable ink composition (active energy ray-curable ink) is, for example, cured by light, which is an active energy ray.
  • the photo-curing method generally uses a light source that emits ultraviolet rays, such as a metal halide lamp, a high-pressure mercury lamp, or an LED. Also, an electron beam can be used as a light source, and in that case curing is generally possible without using a photopolymerization initiator.
  • photopolymerization initiator examples include the photocleavage initiator and the hydrogen abstraction polymerization initiator.
  • the sensitizer includes the sensitizers described above.
  • the above radical polymerization inhibitor can be exemplified as an additive that imparts storage stability to the ink.
  • Additives that impart abrasion resistance, anti-blocking properties, slip properties, and anti-scratch properties include the above-mentioned additives.
  • additives such as ultraviolet absorbers, infrared absorbers, and antibacterial agents can be added according to the required performance.
  • the method for producing the active energy ray-curable ink may be performed by a method similar to that for conventional active energy ray-curable inks. Kneading, mixing, and adjusting machines such as kneaders, triple rolls, attritors, sand mills, gate mixers, etc. Manufactured using
  • Examples of the printing method include offset printing (ordinary lithographic printing using dampening water and waterless lithographic printing not using dampening water), letterpress printing, intaglio printing, stencil printing, flexographic printing, etc., preferably flexographic printing. Print.
  • the base material of the printed material is not particularly limited, and includes printing on all materials such as paper, plastic, stickers, labels, and metals, preferably printing on paper.
  • this embodiment includes various embodiments not described here.
  • This embodiment includes the following configurations.
  • One aspect of the present embodiment is a resin (A) obtained by reacting a hydroxyl group-containing polyester resin (a1), an isocyanate compound (a2), and a hydroxyl group-containing (meth)acrylic compound (a3), and a polyfunctional (meth) )
  • Another aspect of the present embodiment is the active energy ray-curable resin composition, wherein the isocyanate compound (a2) contains a diisocyanate compound.
  • Another aspect of the present embodiment is the active energy ray-curable resin composition, wherein the trihydric or higher alcohol contains glycerin.
  • the resin (A) is a tertiary amine obtained by Michael addition reaction between a (meth)acrylic group in the resin (A) and a secondary amine compound.
  • the active energy ray-curable resin composition includes a resin having a structure.
  • Another aspect of the present embodiment is the active energy ray-curable resin composition, which is an ink composition.
  • Another aspect of the present embodiment is a printed material obtained by printing the active energy ray-curable resin composition on a substrate.
  • another aspect of the present embodiment is a resin (A) obtained by reacting a hydroxyl group-containing polyester resin (a1), an isocyanate compound (a2), and a hydroxyl group-containing (meth)acrylic compound (a3), and a polyfunctional An active energy ray-curable resin composition containing a (meth)acrylic compound (B), wherein the hydroxyl group-containing polyester resin (a1) comprises a polyhydric alcohol containing a trihydric or higher alcohol and a polybasic acid, OH /COOH molar ratio is in the range of 1.10 to 2.20, and a hydroxyl group-containing polyester resin is a resin obtained by reacting a trihydric or higher alcohol at a rate of 13 mol% or more with respect to the entire polyhydric alcohol.
  • the hydroxyl value of (a1) is 50 mgKOH/g or more, and the weight average molecular weight of the hydroxyl group-containing polyester resin (a1) is 3000 or more.
  • Another aspect of the present embodiment is the active energy ray-curable resin composition, wherein the isocyanate compound (a2) is a diisocyanate compound having two isocyanate groups.
  • Another aspect of the present embodiment is the active energy ray-curable resin composition, which is an ink composition.
  • the hydroxyl group-containing polyester resin (a1), the isocyanate compound (a2), and the hydroxyl group-containing (meth)acrylic compound (a3) are mixed in the polyfunctional (meth)acrylic compound (B).
  • Another aspect of the present embodiment is a printed material obtained by printing the active energy ray-curable resin composition on a substrate.
  • an active energy ray-curable pigment dispersion containing a pigment (C) and an active energy ray-curable dispersant, wherein the active energy ray-curable dispersant is
  • the pigment dispersion has two or more functional groups having ethylenically unsaturated bonds and has a polyester structure which is a reaction product of a dicarboxylic acid and/or an anhydride of a dicarboxylic acid and a hydroxyl group-containing compound.
  • the functional group having an ethylenically unsaturated bond includes at least one functional group selected from the group consisting of a vinyl group, an allyl group, and a (meth)acryloyl group. It is the active energy ray-curable pigment dispersion.
  • Another aspect of the present embodiment is the active energy ray-curable pigment dispersion, wherein the active energy ray-curable dispersant has a tertiary amino group or a quaternary ammonium salt.
  • the active energy ray-curable dispersant having a tertiary amino group comprises a functional group having an ethylenically unsaturated bond in the active energy ray-curable dispersant and a secondary
  • the active energy ray-curable pigment dispersion is a Michael addition reaction product with a compound containing an amino group.
  • another aspect of the present embodiment includes the active energy ray-curable pigment dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and contains substantially no solvent, an active energy It is a linear curable ink composition.
  • Another aspect of the present embodiment is the active energy ray-curable ink composition for flexographic ink or offset ink.
  • a numerical range indicated using "-" indicates a range that includes the numerical values before and after "-" as the minimum and maximum values, respectively.
  • the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step.
  • the present invention is the subject of Japanese Patent Application No. 2021-111773 filed on July 5, 2021, the subject of Japanese Patent Application No. 2021-148233 filed on September 13, 2021, and the Japanese patent filed on December 7, 2021 It relates to the subject matter of Application No. 2021-198619, the entire disclosure of which is incorporated herein by reference.
  • the weight average molecular weight was measured by gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation.
  • a calibration curve was prepared with standard polystyrene samples. Tetrahydrofuran was used as the eluent, and three columns of TSKgel Super HM-M (manufactured by Tosoh Corporation) were used as columns. The measurement was performed at a flow rate of 0.6 ml/min, an injection volume of 10 ⁇ l, and a column temperature of 40°C.
  • the term "molecular weight” indicates weight average molecular weight.
  • the hydroxyl value was obtained by a normal potassium hydroxide titration method, specifically, a method according to JIS K 0070.
  • Table 1 also shows the physical properties of the synthesized hydroxyl group-containing polyester compound.
  • trihydric or higher alcohol / total alcohol [mol%] in Table 1 is converted to the number of moles by dividing the weight part of each raw material by the respective molecular weight, and the number of moles of the trihydric or higher alcohol is the total alcohol is divided by the number of moles of
  • Example 1 Preparation of ink composition 1 (active energy ray-curable composition 1)
  • Examples 2-9, Comparative Examples 1-2 Preparation of Ink Compositions 2 to 9 and Comparative Ink Compositions 1 to 2
  • Ink compositions 2 to 9 and comparative ink compositions 1 to 2 were prepared in the same manner as the ink composition 1, except that the curable resin 1 was changed according to Table 3.
  • the obtained ink composition was evaluated by the following method. Table 3 shows the results.
  • viscosity The viscosity of the resulting ink composition was measured at 25° C. and 100 rpm using an E-type viscometer (TVE-25 viscometer, type E, manufactured by Toki Sangyo Co., Ltd.). A value of 2 or more is a level that poses no practical problem.
  • TI value The viscosity of the resulting ink composition was measured at 25° C. and 50 rpm and 100 rpm using an E-type viscometer (TVE-25 viscometer, type E, manufactured by Toki Sangyo Co., Ltd.). Then, the TI value was calculated by dividing the viscosity at 50 rpm by the viscosity at 100 rpm. A score of 3 or more is evaluated as a practically acceptable level. (Evaluation criteria) 5: 1.00 or more and less than 1.05 4: 1.05 or more and less than 1.10 3: 1.10 or more and less than 1.15 2: 1.15 or more and less than 1.20 1: 1.20 or more
  • the active energy ray-curable resin compositions presented in the examples exhibit excellent curability even when used alone or when incorporated into flexographic inks, while maintaining the same viscosity and TI value as compared to the comparative examples. I found out.
  • Table 4 shows the physical properties of the synthesized resin.
  • "trihydric or higher alcohol / total alcohol [mol%]" in Table 4 is obtained by dividing the weight part of each raw material by the respective molecular weight and converting the number of moles of the trihydric or higher alcohol to the total alcohol is divided by the number of moles of
  • Example 1A to 24A Samples of Examples 1A-24A and Comparative Examples 1A-8A were obtained by mixing resin compositions 1A-32A and an initiator according to the compositions in Table 6. A UV cured film of the obtained sample was prepared and evaluated by MEK (methyl ethyl ketone) rubbing test.
  • MEK methyl ethyl ketone
  • MEK rubbing is performed by applying a sample for MEK rubbing to a corona-treated PET substrate (A-PET sheet Novaclear A2012, thickness 0.25 mm manufactured by Mitsubishi Chemical Corporation) using an RI tester (simple color display machine), Curing was performed using a metal halide lamp (output: 96 W/cm, lamp distance: 10 cm, conveyor speed: 100 m/min, number of passages: 1 time).
  • a cotton swab impregnated with MEK was reciprocally rubbed against the UV cured film, and the number of reciprocations of the cotton swab when the UV cured film was damaged was judged. 3 or more is a practical level.
  • Examples 25A to 48A, Comparative Examples 11A to 18A According to the compositions in Table 7, active energy ray-curable inks of Examples 25A to 48A and Comparative Examples 11A to 18A were kneaded using a three-roll mill. The "viscosity” and “fluidity” of the obtained active energy ray-curable ink composition were measured, and the "dot gain" of the printed matter and the ink being scraped by the supply roller at the ink fountain during printing on the printing machine were measured. The phenomenon of "ink backing away” was investigated. The results are also shown in Table 7.
  • ⁇ Method for measuring viscosity> The viscosity was measured using a viscoelasticity measuring device (HAAKE RheoStress6000) manufactured by ThermoFisher Scientific Co., Ltd. under the conditions of a measurement temperature of 25° C. and a cone plate (diameter: 20 mm, inclination angle: 0.5°).
  • ⁇ Curability evaluation method> The curability was evaluated by spreading the ink on PE-coated paper using an RI tester (simple color development machine) at a coating amount of 1 g/m 2 , and testing it with a metal halide lamp (manufactured by Eye Graphics Co., Ltd., output: 96 W/cm, lamp Distance: 10 cm) and varying conveyor speeds (80, 100, 120 m/min) to cure and evaluate the surface condition of the ink coating by rubbing with a cotton cloth. 2 or more is a practical level. (Evaluation criteria) 4: No scratches at all 3: Slightly scratched 2: Scratched 1: No coating film
  • Examples 25A to 48A are superior to the inks of Comparative Examples 11A to 20A in curability and fluidity, and it was found that active energy ray-curable inks capable of solving problems during printing can be obtained.
  • Tolylene diisocyanate was added to 2330 parts of Aronix M400 (mixture of 55% DPHA (dipentaerythritol hexaacrylate) and 45% DPPA (dipentaerythritol pentaacrylate)) in a flask equipped with a separate stirrer, thermometer and gas inlet tube. 348 parts and 1.3 parts of methoquinone as a polymerization inhibitor were added, and the mixture was maintained at 110° C. for 2 hours under a stream of dry air to obtain a TDI-Aronix M400 reactant. 132 parts of the polyester compound synthesized above was added thereto, and the mixture was kept at 110° C. for 4 hours under a stream of dry air to obtain an active energy ray-curable dispersant 1B (dispersant 1B).
  • Aronix M400 mixture of 55% DPHA (dipentaerythritol hexaacrylate) and 45% DPPA (dipentaerythr
  • Dispersants 5B to 7B and Comparative Dispersant 1B were obtained according to the method described in Production Example 1B, except that the raw materials used and the blending amounts were changed according to Table 8.
  • "trihydric or higher alcohol / total alcohol [mol%]" in Table 8 is converted to the number of moles by dividing the weight part of each raw material by the respective molecular weight, and the number of moles of trihydric or higher alcohol is the total alcohol is divided by the number of moles of
  • Example 1B (Preparation of Pigment Dispersion and Preparation of Ink Composition Using the Pigment Dispersion) 68 parts of the active energy ray-curable dispersant 1B obtained in Production Example 1B, 100 parts of a yellow pigment "TCH-1407", and 232 parts of a UV monomer “Miramer M3130" are mixed, and a grind gauge is used on a 3-roll mill. It was dispersed until it became 5 ⁇ m or less to obtain an active energy ray-curable pigment dispersion 1B (pigment dispersion 1B).
  • Example 2B, 3B, 5B-7B Pigment Dispersions 2B, 3B, 5B and 2B were prepared in the same manner as in Example 1B, except that the dispersant, photopolymerization initiator, active energy ray-curable monomer type, and blending amount used were changed according to Table 9. 7B and ink compositions 2B, 3B, 5B-7B were made.
  • Example 4B 34 parts of the pigment dispersant 4B obtained in Production Example 4B, 100 parts of the yellow pigment "TCH-1407", and 266 parts of the UV monomer “Miramer M3130” were added and mixed, and the grind gauge was 5 ⁇ m with a 3-roll mill. Dispersed until the following was obtained to obtain Pigment Dispersion 4B. Further, to 72 parts of the resulting pigment dispersion 4B, 15 parts of Omnirad TPO as a photopolymerization initiator and 13 parts of "Miramer M3130" as an active energy ray-curable monomer are added, and the mixture is stirred well while being heated with a disper. Ink composition 4B was prepared by dissolving the agent.
  • Comparative pigment dispersions 1B to 3B and a comparative ink composition were prepared in the same manner as in Example 4B, except that the pigment dispersants, photopolymerization initiators, active energy ray-curable monomer types and blending amounts used were changed according to Table 9. 1B-3B were produced.
  • Dispersants used in Table 9 are described below.
  • ⁇ Shikou UV-1700B Mitsubishi Chemical Co., Ltd.
  • Isophorone diisocyanate (IPDI) and dipentaerythritol pentaacrylate (DPPA) are reacted to form a urethane acrylate that does not have a polyester skeleton
  • ⁇ SOLSPERS32000 Lubrizol Co., Ltd.
  • Polyethyleneimine is reacted with lactone dispersant
  • TI value The viscosity of the obtained pigment dispersion was measured at 25° C. and rotation speeds of 5 rpm and 20 rpm using an E-type viscometer (TVE-22 type viscometer manufactured by Toki Sangyo Co., Ltd.). Then, the TI value was calculated by dividing the viscosity at 5 rpm by the viscosity at 20 rpm. A level of 4 or more is evaluated as a practically acceptable level. (Evaluation criteria) 5: Less than 1.1 4: 1.1 or more and less than 1.2 3: 1.2 or more and less than 1.3 2: 1.3 or more and less than 1.4 1: 1.4 or more
  • Bar coater no. 2 was used to print on coated paper as a recording medium. After that, the conveyor speed is changed from 40 m/min to 160 m/min by 10 m/min increments, and the ink composition is cured with an LED lamp (“XP-9” manufactured by Air Motion System Co., Ltd., irradiation distance 10 mm, output 30%). rice field. After curing, the surface of the ink coating film was rubbed with a cotton swab, and the speed at which the ink did not rub off on the cotton swab was evaluated. It was judged according to the following criteria. A level of 4 or more is evaluated as a practically acceptable level.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne une composition de résine durcissable par rayonnement d'énergie active contenant : une première résine, qui est obtenue par réaction d'une résine de polyester contenant un groupe hydroxyle, d'un composé isocyanate et d'un composé (méth)acrylique contenant un groupe hydroxyle ; et un composé polyfonctionnel (méth)acrylique, la résine de polyester contenant un groupe hydroxyle étant obtenue par réaction d'un alcool polyhydrique comprenant un alcool trihydrique ou supérieur et un acide polybasique dans des conditions telles que le rapport molaire OH/COOH est de 1,10 ou plus, et la valeur hydroxyle de la résine de polyester contenant un groupe hydroxyle est de 50 mg KOH/g ou plus.
PCT/JP2022/023195 2021-07-05 2022-06-08 Composition de résine durcissable par rayonnement d'énergie active, dispersion de pigment durcissable par rayonnement d'énergie active, composition d'encre pour encre offset, et composition d'encre pour encre flexographique WO2023281971A1 (fr)

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JP2021-111773 2021-07-05
JP2021111773A JP2022094287A (ja) 2020-12-14 2021-07-05 活性エネルギー線硬化型樹脂組成物、その製造方法、および印刷物
JP2021-148233 2021-09-13
JP2021148233 2021-09-13
JP2021198619A JP2023084439A (ja) 2021-12-07 2021-12-07 顔料分散体、活性エネルギー線硬化型組成物
JP2021-198619 2021-12-07

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5493096A (en) * 1977-09-29 1979-07-23 Union Carbide Corp Polyurethane having radiationncurable acrylate group
JPS614719A (ja) * 1984-06-11 1986-01-10 ハイテク・ポリマーズ・インコーポレーテド 放射線硬化性アクリル化ポリウレタンオリゴマー組成物
JPH02202507A (ja) * 1989-01-31 1990-08-10 Dainippon Ink & Chem Inc 活性エネルギー線硬化樹脂組成物
JPH0431414A (ja) * 1990-05-28 1992-02-03 Dainippon Ink & Chem Inc 光学用活性エネルギー線硬化型樹脂組成物
JPH04311714A (ja) * 1991-04-09 1992-11-04 Nippon Paint Co Ltd 光硬化性樹脂組成物
JP2015038162A (ja) * 2010-04-20 2015-02-26 日本ビー・ケミカル株式会社 ポリエステル樹脂及びその用途
JP2020090603A (ja) * 2018-12-05 2020-06-11 Dic株式会社 活性エネルギー線硬化性樹脂組成物、印刷インキ及び印刷物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5493096A (en) * 1977-09-29 1979-07-23 Union Carbide Corp Polyurethane having radiationncurable acrylate group
JPS614719A (ja) * 1984-06-11 1986-01-10 ハイテク・ポリマーズ・インコーポレーテド 放射線硬化性アクリル化ポリウレタンオリゴマー組成物
JPH02202507A (ja) * 1989-01-31 1990-08-10 Dainippon Ink & Chem Inc 活性エネルギー線硬化樹脂組成物
JPH0431414A (ja) * 1990-05-28 1992-02-03 Dainippon Ink & Chem Inc 光学用活性エネルギー線硬化型樹脂組成物
JPH04311714A (ja) * 1991-04-09 1992-11-04 Nippon Paint Co Ltd 光硬化性樹脂組成物
JP2015038162A (ja) * 2010-04-20 2015-02-26 日本ビー・ケミカル株式会社 ポリエステル樹脂及びその用途
JP2020090603A (ja) * 2018-12-05 2020-06-11 Dic株式会社 活性エネルギー線硬化性樹脂組成物、印刷インキ及び印刷物

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