CN105408367B - Actinic-radiation curable composition, active energy ray-curable printer's ink and printed article using it - Google Patents

Abstract

Provide active energy ray-curable compositions that exhibit high curability when used in printing inks and have excellent emulsification and offset printing suitability, and active energy ray-curable compositions that have excellent curability, emulsification, and offset printing suitability Sexual printing ink and its printed matter. Specifically, the active energy ray-curable composition contains a polymerizable unsaturated group-containing resin (A) and a polymerization initiator (B) as essential components, and the polymerizable unsaturated group-containing resin (A) is A polymerizable unsaturated group-containing resin obtained by reacting an epoxy resin with a monocarboxylic acid having a polymerizable unsaturated group, and relative to the total number of terminal structural sites originating from or derived from glycidyl ether oxy groups, α- The ratio of the glycol group was 5 mol % or less in the measurement result of ¹³ C-NMR.

Description

Active energy ray-curable composition, and active energy ray-curable composition using the same Printing Inks and Printed Materials

technical field

It relates to an active energy ray curable composition useful as a raw material for active energy ray curable ink and the like. Furthermore, it is related with the active energy ray curable printing ink and printed matter using this composition.

Background technique

The active energy ray-curable composition is used for protection of various plastic substrates such as home appliances, mobile phones, etc., as hard coating agents and paper due to the advantages of less heat history on the coating substrate, coating film hardness, and excellent scratch resistance. It is used in various fields such as adhesives for printing inks and solder resists. Among them, epoxy acrylate resins obtained by adding acrylic acid or methacrylic acid to epoxy resins are widely used in various fields as materials with excellent adhesion and adhesiveness to substrates (for example, refer to Patent Document 1.).

However, when the above-mentioned epoxy acrylates are used as binders for printing inks, especially when used as offset printing inks, there is a disadvantage that the required emulsification suitability is poor. That is, in offset printing, in which ink and water are simultaneously and continuously supplied to the plate surface, and image formation is performed by utilizing the repelling action of ink and water, high emulsification adaptability is required for the ink, and as a result, the aforementioned epoxy acrylate has strong hydrophilicity and appropriately releases Since the property of emulsified water is poor, the ink is excessively emulsified during printing, and printing failures such as decreased printing density often occur. On the other hand, as an active energy ray-curable UV ink excellent in emulsification properties, a technique using a combination of a rosin-modified phenolic resin as a varnish and an active energy ray-curable monomer is known (for example, refer to Patent Document 2). However, the aforementioned rosin-modified phenolic resin does not have polymerizability to active energy rays, and therefore, there is a problem that curability of the ink itself is lowered.

Thus, as an active energy ray-curable printing ink, it is currently impossible to obtain a printing ink that exhibits high curability and high emulsification suitability.

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 61-218620

Patent Document 2: Japanese Patent No. 4734490

Contents of the invention

The problem to be solved by the invention

Therefore, the problem to be solved by the present invention is to provide an active energy ray-curable composition that exhibits high curability when used in printing ink, and has excellent emulsification suitability and offset printing suitability, and has both excellent curability and emulsification properties. , Active energy ray-curable printing ink suitable for offset printing and its printed matter.

solutions to problems

In order to solve the above-mentioned problems, the inventors of the present invention have repeatedly studied intensively, and as a result, found that the polymerizable unsaturated group-containing resin obtained by modifying an epoxy resin with a monocarboxylic acid (B) having a polymerizable unsaturated group , and the ratio of α-glycol groups to the total number of terminal structural parts of the resin is adjusted to a ratio of 5 mol% or less in the ¹³ C-NMR measurement results, so that excellent curability can be reflected, and the emulsifying properties of the printing ink itself The present invention has been completed by achieving dramatic improvement and obtaining good printing characteristics.

That is, the present invention provides an active energy ray-curable composition characterized by comprising a polymerizable unsaturated group-containing resin (A) and a polymerization initiator (B) as essential components, and the polymerizable unsaturated group-containing The group resin (A) is obtained by reacting an epoxy resin with a monocarboxylic acid having a polymerizable unsaturated group, and is derived from or derived from the glycidyl ether oxygen group in the aforementioned epoxy resin. The ratio of the total number of α-glycol groups was 5 mol% or less in the measurement results of ¹³ C-NMR.

The present invention further provides an active energy ray-curable printing ink characterized by comprising the aforementioned active energy ray-curable composition.

The present invention further provides a printed matter obtained by printing using the aforementioned active energy ray-curable printing ink.

The effect of the invention

According to the present invention, it is possible to provide an active energy ray-curable composition that exhibits high curability when used in printing ink and has excellent emulsification suitability and offset printing suitability, and has excellent curability, emulsification properties, and offset printing suitability. The active energy ray curable printing ink and its printed matter.

Description of drawings

Fig. 1 is a cross-sectional view of a Ducted tester (manufactured by Riken Kawamura) used in an emulsification suitability evaluation test.

detailed description

The active energy ray-curable composition of the present invention is characterized in that the polymerizable unsaturated group-containing resin obtained by reacting an epoxy resin with a monocarboxylic acid having a polymerizable unsaturated group has The abundance ratio of the α-glycol structural site is 5 mol% or less.

Here, in the polymerizable unsaturated group-containing resin, the terminal structural site originating from or derived from the glycidyl ether oxygen group in the epoxy resin refers to the epoxy group in the raw epoxy resin and the polymerizable unsaturated group. Various terminal structural parts generated by the reaction of monocarboxylic acids of saturated groups, or unreacted epoxy groups that remain as they are, are specifically various terminals represented by the following structural formulas (i) to (vi). structure,

(In the structural formulas (i) to (iv), R ¹ and R ² are hydrogen atoms or methyl groups.).

In the present invention, among the total number of terminal structures that can be measured by ¹³ C-NMR, the content of the α-glycol structural site represented by the above-mentioned structural formula (v) is adjusted to a ratio of 5 mol% or less, and the content is used. The printing ink of the polymerizable unsaturated group resin has good curability and exhibits excellent emulsification properties. When the said content rate is 3 mol% or less, when using as printing ink and performing offset printing, it is especially preferable at the point which becomes especially excellent in printing characteristics.

It should be noted that in the present invention, it is not necessary to contain all of the above-mentioned various terminal structures (the foregoing structural formulas (i) to (vi)), and the total number of terminal structures selected from them is used as a basis for the above-mentioned α-glycol structure. The content rate should just be 5 mol% or less.

Here, the abundance ratio of the aforementioned structural formulas (i) to (vi) can be measured by ¹³ C-NMR as described above, specifically, it can be derived from the area ratio of each peak of carbon atoms indicated by * below. In addition, when each peak overlaps with another carbon atom in another structure, the ratio can be calculated|required by dividing by the area part based on this other carbon atom.

(In structural formulas (i) to (iv), R ¹ and R ² are hydrogen atoms or methyl groups.)

Here, the measuring method of ¹³ C-NMR is performed under the following conditions.

[Device type] "JNM-ECA500" manufactured by JEOL Ltd.

[measurement conditions]

Sample concentration: 30% (w/v)

Determination solvent: DMSO-d6

Cumulative times: 4000 times

In the present invention, the ratio of the terminal structural sites of the aforementioned structural formulas (i) to (vi) may be 5 mol% or less of the α-glycol structural site represented by the structural formula (v) as described above, and is particularly preferably 3 Mole % or less, for other terminal structural sites, for example, the α-addition structural site shown in structural formula (i) is more than 70 mol%, more specifically, the α-addition structural site shown in structural formula (i) is 70 moles % or more, and the sum of the α-addition structural site represented by the structural formula (i) and the β-addition structural site represented by the structural formula (ii) is a ratio of 84% or more, from the viewpoint of curability and emulsification Departure is preferred. In addition, when the αβ addition structure site represented by the above-mentioned structural formula (iii) is 5 mol% or less, it is preferable from the viewpoint of emulsifying properties, and in the above-mentioned α-addition structure, further Michael addition of a compound having a polymerizable unsaturated group It is preferable from the viewpoint of good curability that the ratio of the Michael addition structure obtained from the monocarboxylic acid, that is, the structural site represented by the aforementioned structural formula (iv) is 8 mol % or less. In addition, the epoxy group represented by the above-mentioned structural formula (vi) is an epoxy group that remains unreacted, and its abundance ratio is preferably 2 mol % or less, particularly 1 mol % or less.

Next, the above-mentioned epoxy resin is preferably a compound having two or more epoxy groups in one molecule, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol S type epoxy resin, etc. Oxygen resin, bisphenol AD epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, hydrogenated bisphenol S epoxy resin, hydrogenated bisphenol AD epoxy resin, tetrabromobis Bisphenol type epoxy resin such as phenol A type epoxy resin; o-cresol novolak type epoxy resin; phenol novolak type epoxy resin, naphthol novolak type epoxy resin, bisphenol A novolak type epoxy resin , Brominated phenol novolac epoxy resin, alkylphenol novolac epoxy resin, bisphenol S novolac epoxy resin, methoxyl-containing novolak epoxy resin, brominated phenol novolak epoxy resin Novolak-type epoxy resins such as resins; and phenol aralkyl-type epoxy resins (epoxides commonly known as ZYLOCK resin), diglycidyl ether of resorcinol, diglycidyl ether of hydroquinone, phthalate Diglycidyl ether of phenol, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin and other bifunctional epoxy resins; triglycidyl isocyanurate, triphenylmethane type epoxy resin, Tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl modified novolak type epoxy resin (polyphenol obtained by connecting phenol nucleus with double methylene group) Resin epoxy), methoxy phenol-containing aralkyl resin, etc. In addition, the said epoxy resin may be used individually, and may mix 2 or more types.

Among them, bisphenol-type epoxy resins and novolac-type epoxy resins are preferable from the viewpoint of printability, and are bisphenol-type epoxy resins having an epoxy equivalent in the range of 170 to 500 g/eq, especially bisphenol A In the case of an epoxy resin, it is particularly preferable because it has excellent emulsification properties and excellent printability when used as a printing ink.

On the other hand, the monocarboxylic acid having a polymerizable unsaturated group that reacts with the above-mentioned epoxy resin includes, for example, acrylic acid, methacrylic acid, and crotonic acid. In particular, acrylic acid, methacrylic acid, and crotonic acid are preferable from the viewpoint of printability. Methacrylic acid, especially acrylic acid is preferred.

The polymerizable unsaturated group-containing resin (A) used in the present invention can be produced by reacting an epoxy resin with the aforementioned monocarboxylic acid having a polymerizable unsaturated group as described above. When the reaction is carried out in the presence of a basic catalyst, it is preferable from the viewpoint that the amount of α-glycol can be easily reduced to 5 mol % or less.

The aforementioned nitrogen atom-containing basic catalyst used here is a basic compound having a nitrogen atom. As this nitrogen atom-containing basic catalyst, for example, primary amines such as n-butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, benzylamine, diethylamine, dipropylamine, Straight-chain secondary amines such as diisopropylamine and dibutylamine, cyclic secondary amines such as aziridine, azetidine, pyrrolidine, piperidine, azepane, and Azocane, and these alkyl-substituted Secondary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, quinine Aliphatic tertiary amines such as cyclic and 3-quinoniol, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as isoquinoline, pyridine, collidine, β-picoline, etc., imidazole, purine , triazole, guanidine and other secondary amidines, pyrimidine, triazine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0 ]Non-atom-containing basic catalysts such as tertiary amidines such as non-5-ene (DBN). These nitrogen atom-containing basic catalysts may be used alone or in combination of two or more.

Among these nitrogen-atom-containing basic catalysts, triethylamine or tetramethylammonium chloride is preferable because it is easy to reduce the amount of α-glycol in the polymerizable unsaturated group-containing resin to 5% or less.

Here, when the amount of the aforementioned nitrogen-atom-containing basic catalyst is in the range of 0.01 to 0.6 parts by mass, particularly 0.03 to 0.5 parts by mass, especially 0.05 to 0.3 parts by mass, relative to 100 parts by mass of the total mass of the raw material components, It is preferable from the viewpoint of reducing the amount of α-glycol in the produced polymerizable unsaturated group-containing resin and improving emulsification properties.

In addition, for the method of producing the above-mentioned polymerizable unsaturated group-containing resin (A), the following method is preferable from the point of view of easily reducing the amount of α-glycol in the polymerizable unsaturated group-containing resin to 5% or less, The method is to make epoxy resin and monocarboxylic acid with polymerizable unsaturated group in the presence of nitrogen-containing basic catalyst, with epoxy group and carboxyl group being 0.9/1.0～1.0/0.9 (molar ratio) range, and relative to 100 parts by mass of the total weight of the raw material components, use a nitrogen atom-containing basic catalyst at a ratio of 0.01 to 0.6 parts by mass, preferably 0.03 to 0.5 parts by mass, especially 0.05 to 0.3 parts by mass, and use a reaction temperature of 80 to 125 The range of °C, preferably the range of 90 to 110 °C, is reacted until the epoxy equivalent becomes 8000 g/eq or more or the acid value becomes 2.0 or less.

Furthermore, the reaction of the epoxy resin and the monocarboxylic acid having a polymerizable unsaturated group can also be carried out in a reaction solvent using a radically polymerizable monomer that does not contain a site that reacts with a carboxyl group and an epoxy group as a reaction solvent. .

Examples of radically polymerizable monomers that do not contain a site that reacts with a carboxyl group or an epoxy group include N-vinylpyrrolidone, acryloylmorpholine, and dicyclopentadienyl (meth)acrylate. , Dicyclopentenyloxyethyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Phenoxyethyl (meth)acrylate, (Meth) ) butoxyethyl acrylate, isobornyl (meth)acrylate, mono(meth)acrylate of bisphenol F, mono(meth)acrylate of alkylene oxide added bisphenol F, etc. ) acrylates; ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate ester, dimethyloltricyclodecane diacrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate ) acrylate, alkylene oxide addition 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Di(meth)acrylate, di(meth)acrylate of neopentyl glycol hydroxytert-valerate, di(meth)acrylate of bisphenol A, di(meth)acrylate of bisphenol F, Di(meth)acrylate of alkylene oxide added bisphenol A, di(meth)acrylate of alkylene oxide added bisphenol F and other di(meth)acrylates; trimethylolpropane tri(meth)acrylate base) acrylate, alkylene oxide addition trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate and other tri(meth)acrylates; dipentaerythritol hexaacrylate, etc.

The thus obtained polymerizable unsaturated group-containing resin (A) preferably has an epoxy equivalent of 8000 g/eq or more or an acid value of 2.0 or less as described above. In addition, when the solution viscosity of the polymerizable unsaturated group-containing resin (A) is in the range of 0.5 to 30 Pa·s in an 80% by mass solution of non-volatile components when dissolved in butyl acetate, it is easy to adjust the viscosity from the time of forming the printing ink. Viscosity is preferable because it is excellent in flying ink resistance and roll transfer properties when forming printing ink, and it is particularly preferable because these effects become prominent when it is in the range of 1.0 to 10.0 Pa·s.

Next, examples of the polymerization initiator (B) used in the present invention include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of intramolecular cleavage photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzil dimethyl ketal , 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) Ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl -propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1 -Acetophenone compounds such as ketones; 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzyl) Acyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) and other oxime compounds, 3,6-bis(2-methyl-2-morpholinopropyl)-9-butane Carbazole compounds such as carbazole, benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoin compounds;

2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl)- 1-(4-morpholinylphenyl)butan-1-one, 2-methyl-2-morpholinyl((4-methylthio)phenyl)propan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)-butanone and other aminoalkyl phenyl ketones; bis(2,4,6-trimethylbenzoyl)-phenyl oxide Phosphine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Acyl phosphine oxide compounds; benzil, methyl benzoylformate, etc.

On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate-4-phenylbenzophenone, 4,4'-dichlorodiphenyl Methanone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylylated benzophenone, 3,3',4,4'-tetra(tert-butyl Carbonyl peroxide) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone and other benzophenone compounds; 2-isopropylthioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and other thioxanthone compounds; 4,4'-bisdimethylaminobenzophenone, 4,4 Aminobenzophenone compounds such as '-bisdiethylaminobenzophenone; and 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone Wait. These photopolymerization initiators may be used alone or in combination of two or more. Among these, aminoalkyl phenyl ketone compounds are particularly preferred from the viewpoint of excellent curability. In addition, when using a UV-LED light source that generates ultraviolet light in the range of 350 to 420 nm in emission peak wavelength as the active energy ray source, a combination of It is particularly preferable to use an aminoalkylphenone-based compound, an acylphosphine oxide-based compound, and an aminobenzophenone-based compound from the viewpoint of excellent curability.

The usage-amount of these polymerization initiators (B) is preferably the range of 1-20 mass parts as the total usage-amount with respect to 100 mass parts of nonvolatile components in the active energy ray-curable composition of this invention. That is, when the total amount of the polymerization initiator (B) is 1 mass part or more, good curability can be obtained, and when it is 20 mass parts or less, it is possible to avoid unreacted polymerization initiator (B) remaining in the cured product. Migration, solvent resistance, weather resistance and other physical properties are reduced. From the standpoint that the balance of these properties becomes better, it is more preferable that the total amount used is in the range of 3 to 15 parts by mass relative to 100 parts by mass of the non-volatile components in the active energy ray-curable composition of the present invention. .

Moreover, when forming a cured coating film by irradiating ultraviolet rays which are active energy rays, curability can be further improved by using a photosensitizer in addition to the said polymerization initiator (B). Examples of the photosensitizer include: amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate, homobenzylisothiouronium-p-toluenesulfonate, etc. Wait. The amount of these photosensitizers used is preferably 1 to 20 parts by mass relative to 100 parts by mass of non-volatile components in the active energy ray-curable composition of the present invention, from the viewpoint that the curability improvement effect becomes good. range of parts by mass.

The active energy ray-curable composition of the present invention contains the above-mentioned polymerizable unsaturated group-containing resin (A) and polymerization initiator (B) as essential components. Body (C). Examples of the above-mentioned radically polymerizable monomer (C) include: N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, N,N-dimethyl(meth)propylene Amide, acrylamide, acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth)acrylate, isobutoxymethyl(meth)acrylamide, t-octyl(meth)acrylamide Amide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl di Ethylene glycol (meth)acrylate, lauryl (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentadiene (meth)acrylate Cyclopentenyl ester, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromobenzene (meth)acrylate Oxyethyl ester, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, (meth)acrylate ) bornyl acrylate, methyl triethylene glycol (meth)acrylate, isobornyl (meth)acrylate, mono(meth)acrylate of bisphenol F, mono(meth)acrylate of alkylene oxide added bisphenol F Meth) acrylate; mono{2-(meth)acryloyloxyethyl} acid phosphate and other phosphate-containing vinyl monomers; vinyl sulfonic acid, allyl sulfonic acid, 2- Methallylsulfonic acid, 4-vinylbenzenesulfonic acid, 2-(meth)acryloyloxyethanesulfonic acid, 3-(meth)acryloyloxypropanesulfonic acid, 2-acrylamide-2 -Methylpropanesulfonic acid and other vinyl monomers containing sulfonic acid groups; CH ₂ =CHCOO(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O] _n Si(CH ₃ ) ₃ , CH ₂ =C( CH ₃ )COOC ₆ H ₄ [Si(CH ₃ ) ₂ O) _n Si(CH ₃ ) ₃ 、CH ₂ ＝C(CH ₃ )COO(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O] _n Si( CH ₃ ) ₃ , CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ [Si(CH ₃ )(C ₆ H ₅ )O] _n Si(CH ₃ ) ₃ , or CH ₂ =C(CH ₃ ) COO(CH ₂ ) ₃ [Si(C ₆ H ₅ ) ₂ O] _n Si(CH ₃ ) ₃ (where n in each formula is 0 or an integer of 1 to 130.) etc. represented by the general formula , various polysiloxane-containing monomers; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-( Meth)acrylic Acyloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropyltriisopropenyloxy Silane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyl(tri-beta-methoxyethoxy)silane, Vinyltriacetoxysilane, Vinyltrichlorosilane or N-beta -(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane and its hydrochloride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyl (meth)acrylates such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, and ε-caprolactone adducts of these monomers; 2-dimethyl Aminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, 4-diethylaminobutyl vinyl ether, 6-dimethylamino Various vinyl ethers with tertiary amines such as hexyl vinyl ether; various vinyl ethers with hydroxyl groups such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, etc.; or 2-hydroxyethoxyallyl ether, 4-hydroxybutoxyallyl ether, monoallyl ether of trimethylolpropane, or diallyl ether of trimethylolpropane, of pentaerythritol Allyl ethers with hydroxyl groups such as monoallyl ether or diallyl ether of pentaerythritol, and ε-caprolactone adducts of these monomers; methyl vinyl ether, ethyl vinyl ether, n- Propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether and other vinyl ethers; ethylene glycol di (meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tricyclodecane di( Meth)acrylate, Dimethyloltricyclodecane Diacrylate, Tripropylene Glycol Di(meth)acrylate, 1,4-Butanediol Di(meth)acrylate, 1,6-Hexanediol Di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol tertiary valerate Di(meth)acrylates of esters, di(meth)acrylates of bisphenol A or F, di(meth)acrylates of alkylene oxide-added bisphenol A or F; maleic acid, fumaric acid , itaconic acid, citraconic acid and other unsaturated dibasic acids such as divinyl esters of various dibasic carboxylic acids and other bifunctional monomers: trimethylolpropane tri(meth)acrylate, cyclo Alkane oxide addition trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, alkylene oxide addition pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, cyclo Tri(meth)acrylates such as pentaerythritol tetra(meth)acrylate added to oxane; penta(meth)acrylate of dipentaerythritol, penta(meth)acrylate added to dipentaerythritol by alkylene oxide, dipentaerythritol Hexa(meth)acrylate of alkylene oxide, hexa(meth)acrylate of dipentaerythritol added to alkylene oxide, etc., and ε-caprolactone adducts of these monomers.

Among these, penta(meth)acrylate of dipentaerythritol, penta(meth)acrylate of alkylene oxide added dipentaerythritol, and hexa(meth)acrylate of dipentaerythritol are particularly preferable from the viewpoint of excellent curability as printing ink. base) acrylate or hexa(meth)acrylate with addition of alkylene oxide to dipentaerythritol.

The active energy ray-curable composition of the present invention is particularly useful as an active energy ray-curable printing ink. In the above case, as other compounds of the above-mentioned components, pigments, dyes, extender pigments, organic or inorganic fillers, Organic solvents, antistatic agents, defoamers, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, ultraviolet absorbers, antioxidants, leveling agents, pigment dispersants, waxes and other additives.

The active energy ray-curable composition and further the active energy ray-curable printing ink of the present invention can form a cured coating film by irradiating an active energy ray after printing on a substrate. Examples of the active energy rays include ionizing radiation rays such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, ultraviolet rays are particularly preferable from the viewpoint of curability.

As the active energy rays for curing the active energy ray-curable composition of the present invention, as described above, they are ionizing radiation rays such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. As a specific energy source or curing device , For example, germicidal lamps, fluorescent lamps for ultraviolet rays, UV-LEDs, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, and Ultraviolet light as a light source such as natural light, or electron beams using scanning type or curtain type electron beam accelerators, etc.

In addition, as the pigment used in the active energy ray-curable printing ink of the present invention, known and public organic pigments for coloring can be mentioned, for example, "Organic Pigment Handbook" (Author: Hashimoto, publishing house: Kara Orfis, 2006 The organic pigments for printing inks described in "First Edition)" can be used: soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, pyrene Pigments, perionone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolo Pyrrole pigments, carbon black pigments, and polycyclic pigments, etc.

Moreover, the inorganic fine particle which is an extender pigment can be used for the active energy ray curable printing ink of this invention. Examples of inorganic particles include: inorganic coloring pigments such as titanium oxide, graphite, and zinc; lime carbonate powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, and alum. Inorganic extender pigments such as earth white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, whetstone; and other inorganic pigments, silicon, glass beads, etc. When these inorganic fine particles are used in the range of 0.1 to 20 parts by mass in the ink, the effects of adjusting the fluidity of the ink, preventing ink flying, and preventing penetration into printing substrates such as paper can be obtained.

Moreover, it is suitable as a printing base material of the active energy ray curable printing ink of this invention. Examples include: catalogs, posters, leaflets, CD cases, mail advertisements, brochures, cosmetics, beverages, pharmaceuticals, toys, equipment, etc.; Films used in various food packaging materials such as polyethylene glycol ester (PET) films, aluminum foil, synthetic paper, and various substrates conventionally used as printing substrates.

Moreover, examples of the printing method of the active energy ray-curable printing ink of the present invention include lithographic offset printing, letterpress printing, gravure printing, gravure offset printing, flexographic printing, and screen printing.

The present invention can be used preferably in lithographic offset printing in which water is continuously supplied to the plate surface in order to improve the emulsification properties of the ink. Offset printing machines that continuously supply water are manufactured and sold by a large number of printing machine manufacturers. Examples include: Heidelberg Co., Ltd., KOMORI Corporation, Mitsubishi Heavy Industries Printing Paper Machinery Co., Ltd., Manroland AG, RYOBI Co., Ltd., KBA Corporation, etc. , In addition, the present invention can be preferably utilized in any paper supply method, such as a sheet offset printing machine using printing paper in the form of a sheet, an offset rotary printing machine using printing paper in the form of a roll, or any paper supply method. More specifically, offset printing machines such as Speedmaster systems manufactured by Heidelberg Corporation, Lithrone series manufactured by KOMORI Corporation, and DIAMOND series manufactured by Mitsubishi Heavy Industries Printing & Paper Machinery Co., Ltd. may be mentioned.

Example

Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited to these Examples.

[Analysis Method of Glycol Terminal Group Amount of Epoxy Acrylate]

The amounts of glycol terminal groups of the polymerizable unsaturated group-containing resins (1) to (4) and (R1) to (R3) produced in Examples 1 to 4 and Comparative Examples 1 to 3 were analyzed by ¹³ C-NMR.

Specifically, the terminal structure of each polymerizable unsaturated group-containing resin, that is, the α-addition structure, β-addition structure, αβ-addition structure, αglycol, and the aforementioned α-addition structure represented by the following structural formulas are further The molar ratio of each functional group was calculated from the peak area ratio of the ¹³ C-NMR chart of the Michael addition structure formed by Michael addition of acrylic acid, and the carbon atoms represented by the remaining epoxy groups with * marks, and their ratios Percentages are evaluated.

Here, the chemical shifts of the carbon atoms represented by A to G in the following structural formulas (1) to (7) are as follows when the peak of DMSO-d6 as the measurement solvent is set at 39.5 ppm shown.

The chemical shift of the carbon atom shown in A: 71.1ppm

Chemical shift of carbon atom shown in B: 65.6ppm

The chemical shift of the carbon atom indicated by C: 63.0ppm

Chemical shift of carbon atom shown in D: 62.5ppm

Chemical shift of carbon atom indicated by E: 59.7ppm

Chemical shift of carbon atom indicated by F: 60.0ppm

Chemical shift of carbon atom indicated by G: 43.9ppm

In addition, the peak of the carbon atom (carbon atom represented by B) marked with * in the α-addition structure of the following structural formula (1) is different from the structural site present in the resin structure represented by the following structural formula (6). *The marked carbon atom (carbon atom represented by B) overlaps, therefore, the abundance ratio of the α-addition structure is obtained by subtracting the peak area of the carbon atom represented by A in the following structural formula (6) from the peak area of B. get the value.

(measurement conditions of ¹³ C-NMR)

[Device type] "JNM-ECA500" manufactured by JEOL Ltd.

[measurement conditions]

Sample concentration: 30% (w/v)

Determination solvent: DMSO-d6

Cumulative times: 4000 times

Example 1

Drop into liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent 188g/eq. manufactured by DIC Co., Ltd.; hereinafter, abbreviated as " liquid BPA type epoxy Resin") 435.1 parts by mass, 163.6 parts by mass of acrylic acid and 0.1 parts by mass of methoxyphenol (inhibitor; hereinafter, abbreviated as "MQ"), warming up to 100°C, and then adding triethylamine (catalyst; hereinafter, Abbreviated as "TEA") 1.2 parts by mass. Reaction was carried out for 15 hours at 100° C. to obtain an epoxy equivalent of 18000 g/eq., an acid value of 0.4 mgKOH/g, and a solution viscosity (80 mass solution of butyl acetate non-volatile components) ) of polymerizable unsaturated group-containing resin (1) at 1.8 Pa·s. Table 1 shows the abundance ratio of each terminal structural site based on ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (1) .

Example 2

Drop into liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent 188g/eq. manufactured by DIC Co., Ltd.; hereinafter, abbreviated as " liquid BPA type epoxy Resin") 435.1 parts by mass, 163.6 parts by mass of acrylic acid and 0.1 parts by mass of methoxyphenol (inhibitor; hereinafter, abbreviated as "MQ"), warming up to 100°C, and then adding tetramethylammonium chloride (catalyst; Hereinafter, abbreviated as "TMAC") 1.2 parts by mass. Reaction was carried out for 15 hours at 100° C. to obtain an epoxy equivalent of 14000 g/eq., an acid value of 0.8 mgKOH/g, a solution viscosity (butyl acetate non-volatile component 80 mass solution) of polymerizable unsaturated group-containing resin (2) at 1.3 Pa·s. The abundance ratio of each terminal structural site based on the ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (2) is shown in Table 1.

Example 3

Drop into liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent 188g/eq. manufactured by DIC Co., Ltd.; hereinafter, abbreviated as " liquid BPA type epoxy Resin") 435.1 parts by mass, 163.6 parts by mass of acrylic acid and 0.1 parts by mass of methoxyphenol (polymerization inhibitor; hereinafter, abbreviated as "MQ"), heated to 100°C, and then added 2-ethyl-4-methyl Imidazole (catalyst; hereinafter, abbreviated as "2E4MZ") 1.2 parts by mass. Reaction was carried out for 15 hours at 100° C. to obtain an epoxy equivalent of 24000 g/eq., an acid value of 0.3 mgKOH/g, and a solution viscosity (butyl acetate non-volatile component (80 mass solution) of polymerizable unsaturated group-containing resin (3) of 1.4 Pa·s. Based on the measurement of the obtained polymerizable unsaturated group-containing resin (3) ¹³ C-NMR of each terminal structure The abundance ratio is shown in Table 1.

Example 4

Phenol novolak type epoxy resin ("EPICLON N-660 manufactured by DIC Co., Ltd., epoxy equivalent 210g/eq.; hereinafter, abbreviated as "PN-type ring Oxygen resin") 448.4 parts by mass, 150.9 parts by mass of acrylic acid and 0.1 part by mass of methoxyphenol (inhibitor; hereinafter, abbreviated as "MQ"), warming up to 100°C, and then adding triethylamine (catalyst; below , abbreviated as "TEA".) 0.6 parts by mass. Reaction was carried out at 100°C for 15 hours to obtain an epoxy equivalent of 18000g/eq., an acid value of 0.4mgKOH/g, a solution viscosity (butyl acetate non-volatile component 80 mass solution) of polymerizable unsaturated group-containing resin (4) at 14.5 Pa·s. The abundance ratio of each terminal structural site based on the measured ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (4) is shown in Table 1.

Comparative example 1

In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, drop into a liquid bisphenol A type epoxy resin ("EPICLON 850 manufactured by DIC Corporation, epoxy equivalent 188g/eq.; hereinafter, abbreviated as "liquid BPA type ring Oxygen resin") 435.1 parts by mass, 163.6 parts by mass of acrylic acid and methoxyphenol (inhibitor; hereinafter, abbreviated as "MQ".) 0.1 parts by mass, heated to 100 ° C, then added triphenylphosphine (catalyst; Hereinafter, abbreviated as "TPP") 1.2 parts by mass. Reaction was carried out for 15 hours at 100° C. to obtain an epoxy equivalent of 20000 g/eq., an acid value of 0.5 mgKOH/g, a solution viscosity (butyl acetate non-volatile component 80 mass solution) of polymerizable unsaturated group-containing resin (R1) at 1.8 Pa·s. The abundance ratio of each terminal structural site based on the measured ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (R1) is shown in Table 2.

Comparative example 2

In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, drop into a liquid bisphenol A type epoxy resin ("EPICLON 850 manufactured by DIC Corporation, epoxy equivalent 188g/eq.; hereinafter, abbreviated as "liquid BPA type ring Oxygen resin") 435.1 parts by mass, 163.6 parts by mass of acrylic acid and methoxyphenol (inhibitor; hereinafter, abbreviated as "MQ".) 0.1 parts by mass, heated to 130 ° C, then added triethylamine (catalyst; Hereinafter, abbreviated as "TEA") 1.2 parts by mass. Reaction was carried out for 15 hours at 130° C. to obtain an epoxy equivalent of 25000 g/eq., an acid value of 0.2 mgKOH/g, a solution viscosity (butyl acetate non-volatile component 80 mass solution) of polymerizable unsaturated group-containing resin (R2) at 2.0 Pa·s. The abundance ratio of each terminal structural site based on the measured ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (R2) is shown in Table 2.

Comparative example 3

Drop into liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent 188g/eq. manufactured by DIC Co., Ltd.; hereinafter, abbreviated as " liquid BPA type epoxy Resin ") 435.1 mass parts, acrylic acid 163.6 mass parts and methoxyphenol (inhibitor; hereinafter, abbreviated as "MQ ".) 0.1 mass parts, be warming up to 100 ℃, then add triethylamine (catalyst; hereinafter , abbreviated as "TEA") 6.0 parts by mass. Reaction was carried out for 15 hours at 100°C to obtain an epoxy equivalent of 20000g/eq., an acid value of 0.2mgKOH/g, a solution viscosity (butyl acetate non-volatile component 80 mass solution) 1.2 Pa·s polymerizable unsaturated group-containing resin (R3). The abundance ratio of each terminal structural site based on the measured ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (R3) is shown in the table 2.

[Preparation of active energy ray-curable binder for evaluation of emulsification suitability]

In order to more clearly show the effect of improving the emulsification adaptability in the present invention, by adding 83 parts by mass of each of the above-mentioned polymerizable unsaturated group-containing resins (1) to (4) and (R1) to (R3) as active 17 parts by mass of ethylene oxide-modified pentaerythritol tetraacrylate ("SR494" manufactured by Sartomer Co. Ltd., manufactured by Sartomer Co. Ltd.) was mixed as an energy ray-polymerizable acrylate monomer to obtain an active energy ray-curable product for emulsification suitability evaluation. Sexual binders (T1)~(T4) and (TR1)~(TR3).

[Evaluation method of emulsification of active energy ray-curable adhesive]

Emulsification suitability evaluation of the prepared active energy ray-curable adhesives (T1)-(T4) and (TR1)-(TR3) was implemented using the Ducted tester (made by Riken Kawamura).

A cross-sectional view of the Ducted testing machine is shown in FIG. 1 . The outer cylinder 3 is a cylindrical metal hollowed out and has a bottom surface, and has a structure in which the evaluation adhesive 7 can be injected into the inside. After dropping into the binding agent 7 (5 grams), the cylindrical rod-shaped metal, that is, the inner cylinder 2, as shown in Figure 1, is inserted until approaching the bottom surface of the outer cylinder 3 at a distance of 1 millimeter. Thereafter, the inner cylinder was rotated clockwise at 2000 rpm, the outer cylinder was also rotated clockwise at 60 rpm, and the speed difference was set to apply shear to the adhesive 7 and stir. After stirring, after 3 minutes, distilled water was dripped directly above the binder 7 at a speed of 0.5 (g/min) while continuing to stir, so that the binder 7 and the dripped distilled water were immediately stirred and mixed (emulsified) ). The dropwise addition of distilled water was continued for 10 minutes, and ended when the total amount of added distilled water reached 5 g.

The Ducted testing machine has a structure in which the outer cylinder 3 is rotated by the drive motor 5 for the outer cylinder, and the inner cylinder 2 is rotated by the drive motor 1 for the inner cylinder, and is equipped with a constant temperature water tank 4 in which the temperature of the adhesive 7 inside the outer cylinder 3 is constant, and tap water The temperature of 6 is usually kept at 30°C.

After the stirring and mixing of binder 7 (5 grams) and distilled water (5 grams), weigh the weight (grams) of the remaining distilled water (the remaining water that does not enter the binder) inside the inner cylinder 2 . Thus, the total weight Y of the distilled water entering in the binder 7 is shown in the following formula,

Y (grams) = put all the distilled water (5 grams) - the weight of the remaining distilled water

The emulsification rate Z of binder 7 is shown in the formula,

Z(%)=Y÷(binder 7 (5 grams)+Y)×100.

(Here, for example, 5 grams of distilled water dropped into all enters in the binder, and when remaining distilled water is 0 grams, calculate as Y=5 (gram), Z=50 (%).)

The lower the value of the binder emulsification rate Z (%), the better the property of properly excluding emulsified water, the better the offset printing suitability of the ink described below, and the less likely to occur over-emulsification or the concentration caused by over-emulsification Reduce other printing failures. The emulsification suitability was evaluated according to the following criteria.

3: The emulsification rate Z (%) is less than 25%, and the emulsification suitability is good.

2: The emulsification ratio Z (%) is 25% or more to less than 35%, and the emulsification suitability is moderate.

1: The emulsification rate Z (%) is 35% or more, and the emulsification suitability is poor.

[Preparation of Active Energy Ray Curable Printing Ink]

Using a mixer (uniaxial dissolver), 34.5 parts by mass of the polymerizable unsaturated group-containing resin (1) obtained in the above-mentioned Example 1, blue pigment ("HELIOGEN BLUE D7079" manufactured by BASF Corporation, Pigment Blue 15:3) 19 parts by mass, dipentaerythritol hexaacrylate as an active energy ray-curable acrylate monomer ("DPHA" manufactured by Sartomer Co. Ltd.) 10 parts by mass, and 21.95 parts by mass of bis(trimethylol)propane tetraacrylate ("SR355NS" manufactured by Sartomer Co. Ltd.), and trimethylolpropane triacrylate ("MIRAMER" manufactured by MIWON Co., Ltd. M-300") 5 parts by mass, 2 parts by mass of an extender ("イフィラー#5000PJ" hydrous magnesium silicate manufactured by Matsumura Sangyo Co., Ltd.) and basic magnesium carbonate ("Carbonated Carbonate" manufactured by Naikai Salt Industries Co., Ltd. Magnesium TT") 0.5 parts by mass, as a wax ("S-381-N1" polyolefin wax manufactured by Shamrock Inc.) 1 part by mass, as a photopolymerization initiator ("Irgacure907" manufactured by BASF Corporation) Base-1-[4-(methylthio)phenyl]-2-morpholino-1-acetone) 3.5 parts by mass, as a photoinitiator ("EAB-SS" manufactured by Daido Kasei Kogyo Co., Ltd. 4, 2.5 parts by mass of 4'-bis(diethylamino)benzophenone), 0.05 parts by mass of ("Q1301" N-nitrosophenylhydroxylamine aluminum manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor After stirring, kneading was performed using a three-roll mill to obtain an active energy ray-curable ink (I1).

Hereinafter, the other polymerizable unsaturated group-containing resins (2) to (4) and (R1) to (R3) are similarly manufactured using the same parts by mass of the above-mentioned raw materials to obtain active energy ray-cured resins. Sexual ink (I2) ~ (I4) and (IR1) ~ (IR3).

[Manufacturing method of color vehicle for evaluation of curability and solvent resistance]

The active energy ray curable inks (I1) to (I4) and (IR1) to (IR4) thus obtained were uniformly spread on On the rubber roller and metal roller of the RI tester, on the surface of coated paper ("OK topcoat plus 57.5kg, ^A -SIZE" manufactured by Oji Paper Co., Ltd.), the blue concentration of 1.6 (within The SpectroEye densitometer manufactured by X-Rite Co., Ltd. was used for measurement) and the color development was carried out by uniform coating to prepare a color development object. It should be noted that the RI tester refers to a testing machine for developing ink on paper and film, and can adjust the ink transfer amount and printing pressure.

[Curing method using UV light source]

Ultraviolet (UV) radiation is applied to the vehicle after ink application to cure the ink coating. Using a water-cooled metal halide lamp (power 100W/cm1 lamp) and a UV irradiation device equipped with a belt conveyor (manufactured by EYE GRAPHICS CO., LTD., with a cold mirror), place the developed object on the conveyor belt, It was passed directly under the lamp (irradiation distance 11 cm) under the predetermined conditions shown below. The ultraviolet irradiation amount under each condition was measured using the ultraviolet cumulative light amount system (Ushio Ltd., UNIMETER UIT-150-A/light receiver UVD-C365).

[Evaluation method of active energy ray curable ink: curability]

Regarding curability, the presence or absence of scratches on the surface of the developed object was confirmed by the paw scratch method immediately after irradiation. While changing the conveyor speed (m/min) of the above-mentioned UV irradiation device, ultraviolet rays are irradiated to the developed material, and the fastest conveyor speed (m/min) that does not scratch even after curing with claws is recorded. . Therefore, the larger the numerical value of the conveyor belt speed, the better the curability of the ink.

[Evaluation method of active energy ray curable ink: solvent resistance]

For solvent resistance, the presence or absence of scratches on the surface of the printed matter was checked by a solvent rubbing method immediately after irradiation. The ink was cured by irradiating the developed object with ultraviolet light at a conveyor speed of 50 (m/min) of the aforementioned UV irradiation device. After curing, the state change after rubbing the surface of the cured coating film with the ink for evaluation was repeated 30 times by visual observation with a cotton swab containing ethanol, and the solvent resistance was evaluated according to the following criteria.

3: no change

2: Friction marks remain

1: The ink-cured coating film disappears, and the substrate (paper) can be confirmed

[Offset printing method of active energy ray curable ink]

The offset printing suitability was evaluated about the manufactured active energy ray curable ink (I1)-(I4) and (IR1)-(IR3). As the ultraviolet irradiation device, an offset printing machine (Roland R700 printing machine, 40-inch width machine) manufactured by Manroland AG equipped with a water-cooled metal halide lamp manufactured by EYE GRAPHICS CO., LTD. (power 160W/cm, using 3 lamps) was used ), offset printing is implemented at a printing speed of 9,000 sheets per hour. As printing paper, OKtopcoat plus (57.5 kg, A-SIZE) manufactured by Oji Paper Co., Ltd. was used. As the dampening solution supplied to the plate surface, an aqueous solution obtained by mixing 98 parts by mass of tap water and 2 parts by mass of an etching solution (FST-700, manufactured by DIC Corporation) was used.

[Evaluation method of active energy ray curable ink: printability]

As an evaluation method for the printing suitability of offset printing ink, at first, the water supply dial of the printing machine is set to 40 (standard water volume), and the concentration of the printed matter is changed to a standard process blue concentration of 1.6 (SpectroEye concentration manufactured by X-Rite Co., Ltd. Operate the ink supply key in such a way as to measure with the meter), and fix the ink supply key when the concentration is stable.

Afterwards, under the condition that the ink supply key is kept fixed, the water supply dial is changed from 40 to 55, 300 sheets are printed under the condition of increasing the water supply amount, and the blue density of the printed matter after 300 sheets is measured. In the state where the water supply amount is increased, the lower the concentration of the printed matter is, the better the emulsification suitability is, and it can be evaluated as an ink having excellent printing suitability. The printability of the active energy ray curable ink was evaluated according to the following criteria.

3: The blue density of the printed matter is 1.5 or more

2: The blue density of the printed matter is 1.4 or more to less than 1.5

1: The blue density of the printed matter is less than 1.4

[Table 1]

Table 1

[Table 2]

Table 2

Explanation of reference signs

1: Drive motor for inner cylinder

2: Inner cylinder

3: Outer cylinder

4: constant temperature water tank

5: Drive motor for outer cylinder

6: Tap water

7: Evaluate the binder

Claims (4)

1. a kind of Actinic-radiation curable composition is in the ink of the lithographic offset printing of water is continuously fed to the space of a whole page Purposes, it is characterised in that the Actinic-radiation curable composition is with the resin of unsaturated group containing polymerism (A) and poly- Initiator (B) is closed as essential component,

The resin of unsaturated group containing polymerism (A) is to make epoxy resin and monocarboxylic acid with polymerism unsaturated group anti- Should obtained from, and relative to resulting from or come from the end structure portion of the glycidol ether epoxide in the epoxy resin The sum of position, the ratio of α-glycol base exists¹³Turn into 5 moles of below % ratio in C-NMR measurement results.

2. purposes according to claim 1, wherein, result from or come from the glycidyl ether oxygen in the epoxy resin The end structure position of base be selected from the group being made up of following structural formula (i)~(vi),

In structural formula (i)~(iv), R¹And R²For hydrogen atom or methyl.

3. purposes according to claim 1, wherein, epoxy resin is bisphenol-type epoxy resin.

4. purposes according to claim 1, wherein, the monocarboxylic acid with polymerism unsaturated group is (methyl) third Olefin(e) acid.