CN105408367A - Active energy ray-curable composition, active energy ray-curable printing ink comprising same, and printed matter - Google Patents
Active energy ray-curable composition, active energy ray-curable printing ink comprising same, and printed matter Download PDFInfo
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- CN105408367A CN105408367A CN201480041088.XA CN201480041088A CN105408367A CN 105408367 A CN105408367 A CN 105408367A CN 201480041088 A CN201480041088 A CN 201480041088A CN 105408367 A CN105408367 A CN 105408367A
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- Prior art keywords
- methyl
- active energy
- energy ray
- epoxy resin
- acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
- C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
Abstract
Provided are: an active energy ray-curable composition which can exhibit high curability when used in a printing ink, and has excellent emulsion aptitude and offset printing aptitude; an active energy ray-curable printing ink which has all of excellent curability, emulsifying properties and offset printing aptitude; and a printed matter produced using the printing ink. Specifically, the active energy ray-curable composition contains, as essential components, (A) a resin containing a polymerizable unsaturated group and (B) a polymerization initiator, wherein the resin (A) is produced by reacting an epoxy resin with a monocarboxylic acid having a polymerizable unsaturated group, and wherein the ratio of the number of alpha-glycol groups relative to the total number of terminal structural moieties induced by or derived from a glycidyloxy group is 5 mol% or less as measured by 13C-NMR measurement.
Description
Technical field
Relate to as active energy ray-curable ink etc. raw material and useful Actinic-radiation curable composition.And then, relate to the active energy ray-curable printing ink and print that use said composition.
Background technology
Use in the various field such as protective material, printing ink binding agent, solder resist of the hard paint of various plastic basis materials, paper etc. of Actinic-radiation curable composition be in electrical article, mobile phone etc. due to the advantage of, hardness of film few to the thermal history of coated base, scratch resistance excellence.Wherein, to the acid of epoxy resin addition acrylic or methacrylic the Epocryl that obtain as the adaptation to base material, material excellent in adhesion and be widely used (such as reference patent documentation 1 in various field.)。
But, when using above-mentioned epoxy acrylate as printing ink binding agent, when particularly using as offset printing ink, the shortcoming of the emulsification bad adaptability needed for existence.Namely, continuously Mo Heshui is supplied to the space of a whole page simultaneously, utilize the repulsive interaction of ink and water and carry out in the offset printing of image formation, high emulsification adaptability is required to ink, the wetting ability of result aforementioned epoxy acrylate characteristic that is strong, that suitably release emulsification moisture is poor, therefore, ink excessively emulsification during printing, the situation producing the printing troubles such as printing concentration reduction is many.On the other hand, as the UV ink of the active energy ray curable of emulsification property excellence, there will be a known the technology (such as with reference to patent documentation 2) of rosin modified phenolic resin and the active energy ray curable monomer combinationally used as varnish.But aforementioned rosin modified phenolic resin does not have the polymerizability to active energy beam, therefore, the problem that the solidified nature that there is Miboin body reduces.
So, as the printing ink of active energy ray curable, cannot obtain the high solidified nature of embodiment and can obtain the adaptive printing ink of high emulsification is present situation.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 61-218620 publication
Patent documentation 2: Japanese Patent No. 4734490 publication
Summary of the invention
the problem that invention will solve
Therefore, the problem to be solved in the present invention is, embodies high solidified nature and have excellent emulsification adaptability and the adaptive Actinic-radiation curable composition of offset printing, the solidified nature of combined with superior, emulsifying property, the adaptive active energy ray-curable printing ink of offset printing and its print when being provided for printing ink.
for the scheme of dealing with problems
The present inventor etc. further investigate repeatedly in order to solve the problem, found that: by for by epoxy resin (A) with have polymerizability unsaturated group monocarboxylic acid (B) modification and obtain containing polymerizability unsaturated group resin, and the ratio of the sum at the end structure position of α-this resin of glycol fiduciary point exists
13in C-NMR measurement result, adjustment becomes the ratio of less than 5 % by mole, thus can embody excellent solidified nature, and the emulsification property of printing ink itself obtains tremendous improvement, can obtain good printing characteristic, thus complete the present invention.
Namely, the invention provides a kind of Actinic-radiation curable composition, it is characterized in that, using containing polymerizability unsaturated group resin (A) and polymerization starter (B) as essential component, describedly to obtain for making epoxy resin and there is the monocarboxylic acid reaction of polymerizability unsaturated group containing polymerizability unsaturated group resin (A), and relative to resulting from or coming from the sum at end structure position of the glycidyl ether oxygen base in aforementioned epoxy resins, the ratio of α-glycol base exists
13the ratio of less than 5 % by mole is become in C-NMR measurement result.
The present invention and then provide a kind of active energy ray-curable printing ink, is characterized in that, containing foregoing active energy ray-curable composition.
The present invention and then provide a kind of print, it uses foregoing active energy ray-curable printing ink to carry out printing and obtaining.
the effect of invention
According to the present invention, embody high solidified nature when can be provided for printing ink and there is excellent emulsification adaptability and the adaptive Actinic-radiation curable composition of offset printing, the solidified nature of combined with superior, emulsifying property, the adaptive active energy ray-curable printing ink of offset printing and its print.
Accompanying drawing explanation
Fig. 1 is the sectional view of the Ducted trier (Chuan Cun manages development and makes) used in the test of emulsification Adaptability Evaluation.
Embodiment
The feature of active energy ray-curable composition of the present invention is, for make epoxy resin and have polymerizability unsaturated group carboxylic acid reaction and obtain containing polymerizability unsaturated group resin, the ratio that exists of the α glycol structure position in its end structure position is less than 5 % by mole.
Herein, containing in polymerizability unsaturated group resin, the end structure position of the glycidyl ether oxygen base resulting from or come from epoxy resin refers to, the various end structure position that generates or unreacted by the epoxy group(ing) in raw material epoxy resin and the reaction of carboxylic acid with polymerizability unsaturated group and directly residual epoxy group(ing), specifically, for the various end structures shown in following structural formula (i) ~ (vi)
(in structural formula (i) ~ (iv), R
1and R
2for hydrogen atom or methyl.)。
In the present invention, can utilize
13in the sum of the end structure that C-NMR measures, by the adjustment of the containing ratio of the α shown in aforementioned structural formula (v)-glycol structure position being become the ratio of less than 5 % by mole, thus use this solidified nature containing the printing ink of polymerizability unsaturated group resin good, and embody excellent emulsification property.When aforementioned containing ratio is below 3 % by mole, when using as printing ink and carry out offset printing, become aspect excellent especially from printing characteristic, particularly preferably.
It should be noted that, in the present invention, without the need to whole containing above-mentioned various end structure (aforementioned structural formula (i) ~ (vi)), benchmark is add up to, as long as the containing ratio of aforementioned α-glycol structure position is less than 5 % by mole with the end structure selected from them.
Herein, there is ratio and can utilize as described above in aforementioned structural formula (i) ~ (vi)
13c-NMR measures, and specifically, can be derived by following with the area ratio at each peak of the carbon atom shown in *.It should be noted that, for each peak, when repeating with other carbon atoms in other structures, ratio can be obtained divided by the area portions based on these other carbon atoms.
(in structural formula (i) ~ (iv), R
1and R
2for hydrogen atom or methyl.)
Herein,
13the measuring method of C-NMR utilizes following condition to carry out.
" JNM-ECA500 " that [device category] Jeol Ltd. manufactures
[condition determination]
Sample solution concentration: 30% (w/v)
Measure solvent: DMSO-d6
Cumulative frequency: 4000 times
In the present invention, aforementioned structural formula (i) ~ (vi) if each end structure position to there is the ratio α as described above shown in structural formula (v)-glycol structure position be less than 5 % by mole, be particularly preferably less than 3 % by mole, for other end structure positions, α addition structure position such as shown in structural formula (i) is more than 70 % by mole, more specifically, α addition structure position shown in structural formula (i) formula is more than 70 % by mole, and the summation of the β addition structure position shown in the α addition structure position shown in this structural formula (i) and structural formula (ii) is when being the ratio becoming more than 84%, from the aspect of solidified nature and emulsifying property for preferably.In addition, when α β addition structure position shown in aforementioned structural formula (iii) is below 5 % by mole, from the aspect of emulsifying property for preferably, in aforementioned α addition structure further Michael addition there is the monocarboxylic acid of polymerizability unsaturated group and the Michael addition structure obtained and the structure position shown in aforementioned structural formula (iv) they are the ratio becoming less than 8 % by mole time, become good aspect for preferably from solidified nature.In addition, the epoxy group(ing) shown in aforementioned structural formula (vi) is unreacted and directly residual epoxy group(ing), and it exists ratio when being the ratio becoming less than 2 % by mole, especially less than 1 % by mole time be preferred.
Then, aforementioned epoxy resins is preferably in a part the compound with more than 2 epoxy group(ing), specifically, can enumerate: the bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, dihydroxyphenyl propane D type epoxy resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, A Hydrogenated Bisphenol A S type epoxy resin, Hydrogenated Bisphenol A D type epoxy resin, tetrabromo-bisphenol type epoxy resin; O-cresol phenolic epoxy varnish; Phenol novolak type epoxy resin, naphthol novolac type epoxy resin, bisphenol A novolac type epoxy resin, brominated phenol phenolic resin varnish type epoxy resin, alkylphenol phenolic resin varnish type epoxy resin, bisphenol S phenolic resin varnish type epoxy resin, containing phenolic resin varnish type epoxy resins such as methoxyl group phenolic resin varnish type epoxy resin, brominated phenol phenolic resin varnish type epoxy resins; And, phenol aralkyl type epoxy resin (epoxide of common name ZYLOCKresin), the diglycidylether of Resorcinol, the diglycidylether of quinhydrones, the 2 functional-type epoxy resin such as diglycidylether, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin of pyrocatechol; Triglycidyl group isocyanuric acid ester, triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, Dicycldpentadiene-phenol addition reaction-type epoxy resin, biphenyl modified novolac type epoxy resin (being connected to phenol nucleus with dimethylene and the epoxide of the polyphenol resin obtained), containing methoxyphenol aralkyl resin etc.In addition, aforementioned epoxy resins can be used alone, and also can mix two or more.
Wherein, bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin from the aspect of printing adaptability for preferably, for epoxy equivalent (weight) be in the scope of 170 ~ 500g/eq bisphenol-type epoxy resin, especially bisphenol A type epoxy resin time, the aspect excellent from emulsification property, the printing adaptability of excellence can be obtained when using as printing ink, particularly preferably.
On the other hand, monocarboxylic acid that react with above-mentioned epoxy resin, that have polymerizability unsaturated group such as can enumerate vinylformic acid, methacrylic acid, butenoic acid, particularly from the aspect of printing adaptability, preferred vinylformic acid, methacrylic acid, especially preferably vinylformic acid.
What use in the present invention as described above can by making epoxy resin and aforementionedly having the carboxylic acid reaction of polymerizability unsaturated group and manufacture containing polymerizability unsaturated group resin (A), specifically, when making it react under the existence of nitrogen atom basic catalyst, from easy aspect α-glycol amount being reduced to less than 5 % by mole for preferably.
Aforementioned nitrogen atom basic catalyst used herein is the basic cpd with nitrogen-atoms.As this nitrogen atom basic catalyst, such as can enumerate: n-butylamine, amylamine, hexyl amine, cyclo-hexylamine, octyl amine, the primary amine such as benzyl amine, diethylamide, dipropylamine, diisopropylamine, the straight-chain secondary amine such as dibutylamine, aziridine, azetidine, tetramethyleneimine, piperidines, azepan, the cyclic secondary amines such as Azocane and these alkyl replace the such secondary amine of body, Trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, 1, 4-diazabicyclo [2.2.2] octane, rubane and the such aliphatic tertiary amine of 3-quinoline core alcohol, the aromatic nitrile bases such as xylidine, and isoquinoline 99.9, pyridine, trimethylpyridine, the heterocyclic tertiary amines such as beta-picoline, imidazoles, purine, triazole, the secondary amidine such as guanidine, pyrimidine, triazine, 1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU) and 1, the nitrogen atom basic catalysts such as tertiary amidine such as 5-diazabicyclo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene (DBN).These nitrogen atom basic catalysts can be used alone and also can combinationally use two or more.
In these nitrogen atom basic catalysts, triethylamine or tetramethyl ammonium chloride from easy by the aspect that is reduced to less than 5% containing the α-glycol amount in polymerizability unsaturated group resin for preferably.
Herein, the consumption of aforementioned nitrogen atom basic catalyst is relative to material composition total mass 100 mass parts, when becoming the scope of 0.01 ~ 0.6 mass parts, particularly 0.03 ~ 0.5 mass parts, the especially ratio of 0.05 ~ 0.3 mass parts, from reduce generate become good aspect for preferably containing the α-glycol amount in polymerizability unsaturated group resin, emulsification property.
In addition, for manufacturing the above-mentioned method containing polymerizability unsaturated group resin (A), following method easy by be reduced to containing the α-glycol amount in polymerizability unsaturated group resin less than 5% in set out as preferably, described method is make epoxy resin and have the carboxylic acid of polymerizability unsaturated group under the existence of nitrogen atom basic catalyst, with the ratio that epoxy group(ing) and carboxyl are the scope of 0.9/1.0 ~ 1.0/0.9 (mol ratio), and relative to material composition gross weight 100 mass parts with 0.01 ~ 0.6 mass parts, preferably 0.03 ~ 0.5 mass parts, especially the ratio of 0.05 ~ 0.3 mass parts uses nitrogen atom basic catalyst, with the scope of temperature of reaction 80 ~ 125 DEG C, the preferably scope of 90 ~ 110 DEG C, it is made to react until epoxy equivalent (weight) becomes more than 8000g/eq or acid number becomes less than 2.0.
And then above-mentioned epoxy resin and the reaction of the carboxylic acid with polymerizability unsaturated group also can use the free radical polymerization monomer not containing the position with carboxyl and epoxy reaction to carry out in this reaction solvent as reaction solvent.
As the kind of the aforementioned free radical polymerization monomer not containing the position with carboxyl and epoxy reaction, such as can enumerate: NVP, acryloyl morpholine, (methyl) vinylformic acid Dicyclopentadiene (DCPD) ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylate, (methyl) acrylate, butoxy ethyl, (methyl) isobornyl acrylate, list (methyl) acrylate of Bisphenol F, single (methyl) acrylate such as list (methyl) acrylate of oxirane addition Bisphenol F, ethylene glycol bisthioglycolate (methyl) acrylate, dicyclopentenyl two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, dihydroxymethyl tristane diacrylate, tripropylene glycol two (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, oxirane addition 1, 6-hexylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, two (methyl) acrylate of hydroxyl trimethylacetic acid DOPCP, two (methyl) acrylate of dihydroxyphenyl propane, two (methyl) acrylate of Bisphenol F, two (methyl) acrylate of oxirane addition dihydroxyphenyl propane, two (methyl) acrylate such as two (methyl) acrylate of oxirane addition Bisphenol F, trimethylolpropane tris (methyl) acrylate, oxirane addition trimethylolpropane tris (methyl) acrylate, pentaerythritol triacrylate etc. three (methyl) acrylate, six acrylate etc. of Dipentaerythritol.
So obtain containing polymerizability unsaturated group resin (A) as described above preferably epoxy equivalent (weight) be in the scope that more than 8000g/eq or acid number are in less than 2.0.In addition, for containing polymerizability unsaturated group resin (A), when soltion viscosity in nonvolatile component 80 quality % solution when being dissolved in butylacetate is the scope of 0.5 ~ 30Pas, from the resistance to aspect flying ink and roller transitivity excellence when easily adjusting viscosity when forming printing ink and form printing ink for preferably, when being in the scope of 1.0 ~ 10.0Pas, become obvious aspect for particularly preferably from these effects.
Then, the polymerization starter (B) used in the present invention can be enumerated: cracking type Photoepolymerizationinitiater initiater and hydrogen-abstraction Photoepolymerizationinitiater initiater in molecule.As cracking type Photoepolymerizationinitiater initiater in molecule, such as can enumerate: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexyl-phenylketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl }-2-methyl-propan-1-ketone, 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone, 2, 2-diethoxy-1, the methyl phenyl ketone based compounds such as 2-diphenylethane-1-ketone, 1-[4-(thiophenyl)-, 2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, the bitter almond oil camphor based compounds such as carbazole based compound, bitter almond oil camphor, benzoin methyl ether, benzoin isopropyl ether such as the oxime compounds such as 1-(O-acetyl oxime), 3,6-two (2-methyl-2-morpholinyl propyl)-9-butyl carbazoles,
The aminoalkyl-phenones based compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(dimethylamino)-2-(4-methyl-benzyl)-1-(4-morpholino phenyl) butane-1-ketone, 2-methyl-2-morpholinyl ((4-methylthio group) phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone; Two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, TMDPO, two (2,6-Dimethoxybenzoyl)-2,4,4-acylphosphine oxide based compound such as trimethyl-pentyl phosphine oxide; Benzil, methyl benzoylformate etc.
On the other hand, as hydrogen-abstraction Photoepolymerizationinitiater initiater, such as can enumerate: benzophenone, o-benzoyl yl benzoic acid methyl esters-4-phenyl benzophenone, 4,4 '-dichloro benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 '-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3, the benzophenone based compounds such as 3 '-dimethyl-4-methoxy benzophenone; The thioxanthone based compounds such as ITX, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones; 4,4 '-bis-dimethylamino benzophenone, 4, the aminobenzophenone based compounds such as 4 '-bis-diethylamino benzophenone; And, 10-butyl-2-chloro-acridine ketone, 2-ethyl-anthraquinone, 9,10-phenanthrenequione, camphorquinone etc.These Photoepolymerizationinitiater initiaters can be used alone and also can combinationally use two or more.In these; from the aspect of solidified nature excellence; particularly preferably aminoalkyl-phenones based compound; in addition; use produce glow peak wavelength be the ultraviolet UV-LED light source of the scope of 350 ~ 420nm as active energy beam source time, combinationally use aminoalkyl-phenones based compound, acylphosphine oxide based compound and aminobenzophenone based compound from the aspect of solidified nature excellence for particularly preferably.
The consumption of these polymerization starters (B), relative to nonvolatile component 100 mass parts in Actinic-radiation curable composition of the present invention, as its total consumption, is preferably the scope of 1 ~ 20 mass parts.Namely, when total consumption of polymerization starter (B) is more than 1 mass parts, good solidified nature can be obtained, and when being below 20 mass parts, the problem that the physical property such as migration, solvent resistance, weathering resistance unreacted polymerization starter (B) can being avoided to remain in cause in cured article reduces.Better aspect is become, particularly relative to nonvolatile component 100 mass parts in Actinic-radiation curable composition of the present invention, when its total consumption is the scope of 3 ~ 15 mass parts more preferably from these balancing performances.
In addition, when irradiating the ultraviolet as active energy beam and form cured coating film, except aforementioned polymeric initiator (B), by utilizing photosensitizer, solidified nature can be improved further.Above-mentioned photosensitizer such as can be enumerated: the sulphur compounds etc. such as the urea classes such as the amine compound such as fatty amine, o-tolyl thiocarbamide, diethyldithiophosphoric acid sodium, all benzylisothiourea-p-toluenesulfonic esters.The consumption of these photosensitizers becomes good aspect from the effect that solidified nature improves, and relative to nonvolatile component 100 mass parts in Actinic-radiation curable composition of the present invention, as its total consumption, is preferably the scope of 1 ~ 20 mass parts.
Actinic-radiation curable composition of the present invention using describe in detail above containing polymerizability unsaturated group resin (A) and polymerization starter (B) as essential component, in the present invention, free radical polymerization monomer (C) can be combinationally used further.Above-mentioned free radical polymerization monomer (C) such as can be enumerated: N-caprolactam, NVP, N-vinylcarbazole, vinyl pyridine, N, N-dimethyl (methyl) acrylamide, acrylamide, acryloyl morpholine, amino-3, the 7-dimethyl monooctyl esters of (methyl) vinylformic acid 7-, isobutoxymethyl (methyl) acrylamide, tertiary octyl group (methyl) acrylamide, two acetone (methyl) acrylamide, (methyl) acrylate, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) 2-EHA, ethyl Diethylene Glycol (methyl) acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid Dicyclopentadiene (DCPD) ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid tetrachloro phenyl ester, (methyl) vinylformic acid 2-tetrachloro phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) tetrabromophenyl acrylate, (methyl) vinylformic acid 2-tetrabromo phenoxy ethyl, (methyl) vinylformic acid 2-Trichlorophenoxy ethyl ester, (methyl) tribromophenyl acrylate, (methyl) vinylformic acid 2-tribromophenoxy ethyl ester, (methyl) acrylate, (methyl) acrylate, butoxy ethyl, (methyl) Pentachlorophenyl Acrylate, (methyl) vinylformic acid pentabromo-phenyl ester, (methyl) vinylformic acid norbornene ester, methyl triethylene glycol (methyl) acrylate, (methyl) isobornyl acrylate, list (methyl) acrylate of Bisphenol F, list (methyl) acrylate of oxirane addition Bisphenol F, the various phosphorous acidic group vinyl systems monomers such as single { 2-(methyl) acryloyl-oxyethyl } phosphate ester acid, vinyl sulfonic acid, allyl sulphonic acid, 2-methallylsulfonic acid, 4-vinylbenzenesulfonic acid, 2-(methyl) acryloxy ethyl sulfonic acid, 3-(methyl) acryloxy propanesulfonic acid, 2-acrylamide-2-methyl propane sulfonic etc. are various containing sulfonic group ethene base system monomer, CH
2=CHCOO (CH
2)
3[Si (CH
3)
2o]
nsi (CH
3)
3, CH
2=C (CH
3) COOC
6h
4(Si (CH
3)
2o)
nsi (CH
3)
3, CH
2=C (CH
3) COO (CH
2)
3[Si (CH
3)
2o]
nsi (CH
3)
3, CH
2=C (CH
3) COO (CH
2)
3[Si (CH
3) (C
6h
5) O]
nsi (CH
3)
3, or CH
2=C (CH
3) COO (CH
2)
3[Si (C
6h
5)
2o]
nsi (CH
3)
3(n in wherein, various is set to the integer of 0 or 1 ~ 130.) etc. like that shown in general formula, various containing polysiloxane key monomer, γ-(methyl) acryloxypropyl Trimethoxy silane, γ-(methyl) acryloxypropyl triethoxyl silane, γ-(methyl) acryloxypropyl dimethoxysilane, γ-(methyl) acryloxypropyl diethoxy silane, γ-(methyl) acryloxypropyl three iso-propenyloxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl (three-'beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, vinyl trichloro silane or N-β-(N-vinylbenzylaminoethyl)-gamma-amino propyl trimethoxy silicane and its hydrochloride, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate etc. have (methyl) acrylate of hydroxyl and the 6-caprolactone affixture of these monomers, 2-dimethyl aminoethyl vinyl base ether, 2-diethylamino ethyl vinyl ether, 4-dimethrlaminobutyl vinyl ether, 4-diethylamino butyl vinyl ether, 6-dimethylamino hexyl vinyl ether etc. have the various vinyl ether of tertiary amine, the various vinyl ether with hydroxyl such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyl hexyl vinyl ether, or 2-hydroxyl-oxethyl allyl ethers, 4-hydroxybutoxy allyl ethers, the mono allyl ether of TriMethylolPropane(TMP) or the diallyl ether etc. of the diallyl ether of TriMethylolPropane(TMP), the mono allyl ether of tetramethylolmethane or tetramethylolmethane have the allyl ethers of hydroxyl and the 6-caprolactone affixture of these monomers, the vinyl ether such as methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, IVE, 2-ethylhexyl vinyl ether, cyclopentylethylene base ether, cyclohexyl vinyl ether, ethylene glycol bisthioglycolate (methyl) acrylate, dicyclopentenyl two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, tristane two (methyl) acrylate, dihydroxymethyl tristane diacrylate, tripropylene glycol two (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, two (methyl) acrylate of hydroxyl trimethylacetic acid DOPCP, two (methyl) acrylate of dihydroxyphenyl propane or F, two (methyl) acrylate of oxirane addition dihydroxyphenyl propane or F, toxilic acid, fumaric acid, methylene-succinic acid, 2 functional monomers such as the divinyl ester class of the various di-carboxylic acid such as the various unsaturated dibasic acid such as citraconic acid class: trimethylolpropane tris (methyl) acrylate, oxirane addition trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, oxirane addition tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, three (methyl) acrylate such as oxirane addition tetramethylolmethane four (methyl) acrylate, the 6-caprolactone affixture of five (methyl) acrylate of Dipentaerythritol, five (methyl) acrylate of oxirane addition Dipentaerythritol, six (methyl) acrylate of Dipentaerythritol, six (methyl) acrylate of oxirane addition Dipentaerythritol etc. and these monomers.
In these, from the aspect of the solidified nature excellence as printing ink, particularly preferably six (methyl) acrylate of five (methyl) acrylate of Dipentaerythritol, five (methyl) acrylate of oxirane addition Dipentaerythritol, six (methyl) acrylate of Dipentaerythritol or oxirane addition Dipentaerythritol.
Actinic-radiation curable composition of the present invention is particularly useful as active energy ray-curable printing ink, in above-mentioned situation, as other formulations of above-mentioned each composition, can use: the additives such as pigment, dyestuff, pigment extender, organic or inorganic filler, organic solvent, static inhibitor, defoamer, viscosity modifier, resistance to photostabilizer, weather stablizer, heat-resisting stabilizing agent, UV light absorber, antioxidant, flow agent, pigment dispersing agent, wax.
Actinic-radiation curable composition of the present invention and then active energy ray-curable printing ink can by after base material being carried out to printing, irradiate active energy beam and form cured coating film.This active energy beam can be enumerated: the ionization radial lines such as ultraviolet, electron beam, alpha-ray, β ray, gamma-rays.In these, from the aspect of solidified nature, particularly preferably ultraviolet.
As the active energy beam making Actinic-radiation curable composition of the present invention solidify, as described above, for ultraviolet, electron beam, alpha-ray, β ray, the ionization radial line that gamma-rays is such, as concrete energy source or solidification equipment, such as can enumerate: germicidal lamp, ultraviolet luminescent lamp, UV-LED, carbon arc, xenon lamp, manifolding high voltage mercury lamp, medium-pressure or high pressure mercury lamp, ultrahigh pressure mercury lamp, electrodeless lamp, metal halide lamp, using natural light etc. as the ultraviolet of light source, or utilize sweep type, the electron beam etc. of curtain type electron-beam accelerator.
In addition, as the pigment used in active energy ray-curable printing ink of the present invention, public painted pigment dyestuff can be enumerated, such as can enumerate " pigment dyestuff Ha Application De Block ッ Network (author: this Isao of Bridge, sale room: カ ラ ー オ Off ィ ス, first edition in 2006) " the middle printing ink pigment dyestuff etc. recorded, can use: insoluble azo pigment, insoluble azo colour, condensed azo-pigment, metal phthalocyanine pigment, metal-free phthalocyanine, quinacridone pigment, pyrene pigment, purple cyclic ketones pigment, isoindolenone pigments, isoindoline pigment, triazine dioxin pigment, thioindigo color, anthraquione pigmentss, quinophthalone pigments, metal complex pigment, diketo pyrrolo-pyrrole pigment(DPP pigment), charcoal blacks, and polycycle pigment etc.
In addition, the inorganic particles of pigment extender can be used as in active energy ray-curable printing ink of the present invention.As inorganic particles, can enumerate: the inorganic colored pigments such as titanium oxide, graphite, the flowers of zinc; The inorganic pigment extenders such as carbonic acid lime powder, precipitation threshold calcium carbonate, gypsum, clay (ChinaClay), silicon dioxide powder, diatomite, talcum, kaolin, white lake, barium sulfate, aluminum stearate, magnesiumcarbonate, barite powder, whetslate; Deng mineral dye, silicon, glass microballon etc.These inorganic particles, by using with the scope of 0.1 ~ 20 mass parts in ink, can obtain the mobility that can adjust ink, the effect preventing flying ink, prevent the infiltration to printing elements such as paper.
In addition, as the printing element being suitable for active energy ray-curable printing ink of the present invention.Can enumerate: the paper base material used in the shell of products catalogue, placard, leaflet, CD cover, email advertisement, pamphlet, makeup or beverage, medicine, toy, equipment etc. etc.; The film used in the various food packaging materials such as polypropylene film, polyethylene terephthalate (PET) film, aluminium foil, synthetic paper and all the time as printing element use various base materials.
In addition, as the printing process of active energy ray-curable printing ink of the present invention, such as, can enumerate: lithographic offset printing, letterpress, intaglio printing, intaglio plate offset printing, flexographic printing, silk screen printing etc.
The present invention the emulsification property of ink improve in, particularly to the space of a whole page continuously for feedwater lithographic offset printing in can preferably utilize.The continuous offset printing press for feedwater is sold by a large amount of printer manufacturers manufacture, as an example, can enumerate: Heidelberg Co., Ltd., KOMORICorporation, printing paper work Machinery Co., Ltd. of Mitsubishi Heavy Industries Ltd, ManrolandAG, RYOBI Co., Ltd., Co., Ltd. KBA etc., in addition, can use and utilize the sheet offset printing press of the printing of sheet form, use the offset rotary press of the printing of scroll state, all preferably can utilize the present invention in paper using supply mode arbitrarily.More specifically, can enumerate: the offset printing presses such as the DIAMONDseries that the Lithroneseries that Speedmastersystems, KOMORICorporation that Heidelberg Co., Ltd. manufactures manufacture, printing paper work Machinery Co., Ltd. of Mitsubishi Heavy Industries Ltd manufacture.
Embodiment
Below, the present invention is illustrated in greater detail according to embodiment.It should be noted that, the present invention is not limited to these embodiments.
[the glycol terminal group quantitative analysis method of epoxy acrylate]
Utilize
13c-NMR analyzes the glycol end base unit weight containing polymerizability unsaturated group resin (1) ~ (4) and (R1) ~ (R3) manufactured in embodiment 1 ~ 4 and comparative example 1 ~ 3.
Specifically, for respectively containing in the α addition structure shown in the end structure of polymerizability unsaturated group resin and following structural formula, β addition structure, α β addition structure, α glycol, aforementioned α addition structure further the Michael addition structure of Michael addition vinylformic acid and other * of residual epoxy base mark shown in carbon atom there is ratio, according to
13the peak area ratio of C-NMR figure calculates the mol ratio of each functional group, evaluates with their percentage.
It should be noted that, for the chemical shift of each carbon atom shown in the A ~ G in following structural formula (1) ~ (7) herein, using when being set to 39.5ppm as the peak of the DMSO-d6 measuring solvent as shown below.
The chemical shift of the carbon atom shown in A: 71.1ppm
The chemical shift of the carbon atom shown in B: 65.6ppm
The chemical shift of the carbon atom shown in C: 63.0ppm
The chemical shift of the carbon atom shown in D: 62.5ppm
The chemical shift of the carbon atom shown in E: 59.7ppm
The chemical shift of the carbon atom shown in F: 60.0ppm
The chemical shift of the carbon atom shown in G: 43.9ppm
In addition, the peak of the carbon atom (carbon atom shown in B) with * mark of the α addition structure of following structural formula (1) is overlapping with the carbon atom that the * of the structure position be present in the resin structure shown in following structural formula (6) marks (carbon atom shown in B), therefore, the ratio that exists of α addition structure uses the peak area deducting the carbon atom shown in A following structural formula (6) from the peak area of B and the value obtained.
(
13the condition determination of C-NMR)
" JNM-ECA500 " that [device category] Jeol Ltd. manufactures
[condition determination]
Sample solution concentration: 30% (w/v)
Measure solvent: DMSO-d6
Cumulative frequency: 4000 times
Embodiment 1
Liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent (weight) 188g/eq. that Dainippon Ink Chemicals manufactures is dropped in the four-hole boiling flask possessing stirrer, thermometer and prolong; Below, brief note makes " liquid BPA type epoxy resin ") 435.1 mass parts, vinylformic acid 163.6 mass parts and methoxyphenol (stopper; Below, brief note makes " MQ ") 0.1 mass parts, be warming up to 100 DEG C, then add triethylamine (catalyzer; Below, brief note makes " TEA ") 1.2 mass parts.Carry out reaction in 15 hours with 100 DEG C, thus obtain that epoxy equivalent (weight) is 18000g/eq., acid number is 0.4mgKOH/g, soltion viscosity (butylacetate nonvolatile component 80 Mass Solution) 1.8Pas containing polymerizability unsaturated group resin (1).Will based on measuring gained containing polymerizability unsaturated group resin (1)
13the ratio that exists at each end structure position of C-NMR is shown in table 1.
Embodiment 2
Liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent (weight) 188g/eq. that Dainippon Ink Chemicals manufactures is dropped in the four-hole boiling flask possessing stirrer, thermometer and prolong; Below, brief note makes " liquid BPA type epoxy resin ") 435.1 mass parts, vinylformic acid 163.6 mass parts and methoxyphenol (stopper; Below, brief note makes " MQ ") 0.1 mass parts, be warming up to 100 DEG C, then add tetramethyl ammonium chloride (catalyzer; Below, brief note makes " TMAC ") 1.2 mass parts.Carry out reaction in 15 hours with 100 DEG C, thus obtain that epoxy equivalent (weight) is 14000g/eq., acid number is 0.8mgKOH/g, soltion viscosity (butylacetate nonvolatile component 80 Mass Solution) 1.3Pas containing polymerizability unsaturated group resin (2).Will based on measuring gained containing polymerizability unsaturated group resin (2)
13the ratio that exists at each end structure position of C-NMR is shown in table 1.
Embodiment 3
Liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent (weight) 188g/eq. that Dainippon Ink Chemicals manufactures is dropped in the four-hole boiling flask possessing stirrer, thermometer and prolong; Below, brief note makes " liquid BPA type epoxy resin ") 435.1 mass parts, vinylformic acid 163.6 mass parts and methoxyphenol (stopper; Below, brief note makes " MQ ") 0.1 mass parts, be warming up to 100 DEG C, then add 2-ethyl-4-methylimidazole (catalyzer; Below, brief note makes " 2E4MZ ") 1.2 mass parts.Carry out reaction in 15 hours with 100 DEG C, thus obtain that epoxy equivalent (weight) is 24000g/eq., acid number is 0.3mgKOH/g, soltion viscosity (butylacetate nonvolatile component 80 Mass Solution) 1.4Pas containing polymerizability unsaturated group resin (3).Will based on measuring gained containing polymerizability unsaturated group resin (3)
13the ratio that exists at each end structure position of C-NMR is shown in table 1.
Embodiment 4
Phenol novolak type epoxy resin (" EPICLONN-660, epoxy equivalent (weight) 210g/eq. that Dainippon Ink Chemicals manufactures is dropped in the four-hole boiling flask possessing stirrer, thermometer and prolong; Below, brief note makes " PN type epoxy resin ") 448.4 mass parts, vinylformic acid 150.9 mass parts and methoxyphenol (stopper; Below, brief note makes " MQ ") 0.1 mass parts, be warming up to 100 DEG C, then add triethylamine (catalyzer; Below, brief note makes " TEA ".) 0.6 mass parts.Carry out reaction in 15 hours with 100 DEG C, thus obtain that epoxy equivalent (weight) is 18000g/eq., acid number is 0.4mgKOH/g, soltion viscosity (butylacetate nonvolatile component 80 Mass Solution) 14.5Pas containing polymerizability unsaturated group resin (4).Will based on measuring gained containing polymerizability unsaturated group resin (4)
13the ratio that exists at each end structure position of C-NMR is shown in table 1.
Comparative example 1
Liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent (weight) 188g/eq. that Dainippon Ink Chemicals manufactures is dropped in the four-hole boiling flask possessing stirrer, thermometer and prolong; Below, brief note makes " liquid BPA type epoxy resin ") 435.1 mass parts, vinylformic acid 163.6 mass parts and methoxyphenol (stopper; Below, brief note makes " MQ ".) 0.1 mass parts, be warming up to 100 DEG C, then add triphenylphosphine (catalyzer; Below, " TPP ") 1.2 mass parts made in brief note.Carry out reaction in 15 hours with 100 DEG C, thus obtain that epoxy equivalent (weight) is 20000g/eq., acid number is 0.5mgKOH/g, soltion viscosity (butylacetate nonvolatile component 80 Mass Solution) 1.8Pas containing polymerizability unsaturated group resin (R1).Will based on measuring gained containing polymerizability unsaturated group resin (R1)
13the ratio that exists at each end structure position of C-NMR is shown in table 2.
Comparative example 2
Liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent (weight) 188g/eq. that Dainippon Ink Chemicals manufactures is dropped in the four-hole boiling flask possessing stirrer, thermometer and prolong; Below, brief note makes " liquid BPA type epoxy resin ") 435.1 mass parts, vinylformic acid 163.6 mass parts and methoxyphenol (stopper; Below, brief note makes " MQ ".) 0.1 mass parts, be warming up to 130 DEG C, then add triethylamine (catalyzer; Below, brief note makes " TEA ") 1.2 mass parts.Carry out reaction in 15 hours with 130 DEG C, thus obtain that epoxy equivalent (weight) is 25000g/eq., acid number is 0.2mgKOH/g, soltion viscosity (butylacetate nonvolatile component 80 Mass Solution) 2.0Pas containing polymerizability unsaturated group resin (R2).Will based on measuring gained containing polymerizability unsaturated group resin (R2)
13the ratio that exists at each end structure position of C-NMR is shown in table 2.
Comparative example 3
Liquid bisphenol A type epoxy resin (" EPICLON850, epoxy equivalent (weight) 188g/eq. that Dainippon Ink Chemicals manufactures is dropped in the four-hole boiling flask possessing stirrer, thermometer and prolong; Below, brief note makes " liquid BPA type epoxy resin ") 435.1 mass parts, vinylformic acid 163.6 mass parts and methoxyphenol (stopper; Below, brief note makes " MQ ".) 0.1 mass parts, be warming up to 100 DEG C, then add triethylamine (catalyzer; Below, brief note makes " TEA ") 6.0 mass parts.Carry out reaction in 15 hours with 100 DEG C, thus obtain that epoxy equivalent (weight) is 20000g/eq., acid number is 0.2mgKOH/g, soltion viscosity (butylacetate nonvolatile component 80 Mass Solution) 1.2Pas containing polymerizability unsaturated group resin (R3).Will based on measuring gained containing polymerizability unsaturated group resin (R3)
13the ratio that exists at each end structure position of C-NMR is shown in table 2.
[preparation of the active energy ray-curable binding agent of emulsification Adaptability Evaluation]
In order to the effect that the emulsification adaptability in clearer and more definite expression the present invention improves, by containing in polymerizability unsaturated group resin (1) ~ (4) and each 83 mass parts of (R1) ~ (R3) above-mentioned the ethylene-oxide-modified tetramethylol methane tetraacrylate (SartomerCo.Ltd. added as active energy beam polymerizability acrylate monomer, " SR494 " that manufacture) 17 mass parts mixing, thus obtain active energy ray-curable binding agent (T1) ~ (T4) and (TR1) ~ (TR3) of emulsification Adaptability Evaluation.
[evaluation method of the emulsifying property of active energy ray-curable binding agent]
The emulsification Adaptability Evaluation of active energy ray-curable binding agent (T1) ~ (T4) prepared and (TR1) ~ (TR3) uses Ducted trier (Chuan Cun manages development and makes) to implement.
The sectional view of Ducted trier is shown in Fig. 1.Urceolus 3 is the metal of inner cylindrical shape that hollow out, that have bottom surface, and inside becomes the structure that can drop into and evaluate binding agent 7.After dropping into binding agent 7 (5 grams), the metal of cylindrical bar shape and inner core 2 as shown in Figure 1, insert until the bottom surface of close distance urceolus 3 is the distance of 1 millimeter.Afterwards, inner core is turned clockwise with 2000rpm, and urceolus also turns clockwise with 60rpm, poor by setting speed, applies to shear and stir binding agent 7.After stirring when through 3 minutes when, limit is continued to stir limit and directly over binding agent 7, is dripped distilled water with the speed of 0.5 (gram/minute), thus the distilled water of binding agent 7 and dropping carries out being uniformly mixed (emulsification) immediately.The dropping of distilled water continues 10 minutes, and the moment that the dripping quantity summation of distilled water reaches 5 grams terminates.
Ducted trier has the structure that urceolus 3 is rotated by urceolus drivingmotor 5, inner core 2 is rotated by inner core drivingmotor 1, and possessing the Water Tank with Temp.-controlled 4 of homo(io)thermism of binding agent 7 of urceolus 3 inside, the temperature of tap water 6 remains 30 DEG C usually.
Binding agent 7 (5 grams) and distilled water (5 grams) be uniformly mixed end after, weigh the weight (gram) of the residue distilled water (do not enter into binding agent and remaining water) being in inner core 2 inside.Thus, the gross weight Y of the distilled water entered in binding agent 7 is shown below,
The weight of Y (gram)=all drop into distilled water (5 grams)-residue distilled water
The emulsification rate Z of binding agent 7 such as formula shown,
Z (%)=Y ÷ (binding agent 7 (5 grams)+Y) × 100.
(herein, such as, the distilled water 5 grams of input all enters in binding agent, when residue distilled water is 0 gram, is calculated as Y=5 (gram), Z=50 (%).)
The numerical value of binding agent emulsification rate Z (%) is lower, and the characteristic suitably getting rid of emulsification moisture is more excellent, and the offset printing adaptability of following described ink is also more excellent, and the printing troubles such as Over emulsfication or the concentration reduction that caused by Over emulsfication not easily occur.According to following benchmark evaluation emulsification adaptability.
3: emulsification rate Z (%) is less than 25%, and emulsification adaptability is good.
2: emulsification rate Z (%) be more than 25% ~ be less than 35%, and emulsification adaptability is medium.
1: emulsification rate Z (%) is more than 35%, emulsification bad adaptability.
[preparation of active energy ray-curable printing ink]
Use mixing machine (single shaft dissolver), polymerizability unsaturated group resin (1) 34.5 mass parts is contained by what obtain in the above embodiments 1 with the state of compounding whole raw material (summation 100 mass parts), blue pigments (" HELIOGENBLUED7079 " that BASF Co., Ltd. manufactures, PigmentBlue15:3) 19 mass parts, as the dipentaerythritol acrylate (SartomerCo.Ltd. of active energy ray-curable acrylate monomer, " DPHA " that manufacture) 10 mass parts, with two (trishydroxymethyl) tetraacrylate (SartomerCo.Ltd., " SR355NS " that manufacture) 21.95 mass parts, with Viscoat 295 (" MIRAMERM-300 " that MIWON Co., Ltd. manufactures) 5 mass parts, as (" イ Off ィ ラ ー #5000PJ " hydrous magnesium silicate that Ishihara Sangyo Kaisha, Ltd. manufactures) 2 mass parts and the alkaline magnesium carbonate (NaikaiSaltIndustriesCo. of pigment extender, Ltd. " the magnesiumcarbonate TT " that manufacture) 0.5 mass parts, as (" S-381-N1 " polyolefin-wax that ShamrockInc. manufactures) 1 mass parts of wax, as (" Irgacure907 " 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone that BASF Co., Ltd. manufactures) 3.5 mass parts of Photoepolymerizationinitiater initiater, as (" EAB-SS " 4 that Daido Chemical Corp manufactures of light trigger, 4 '-bis-(diethylamino) benzophenone) 2.5 mass parts, (with " Q1301 " N-nitroso-group phenylhydroxylamine aluminium that Guang Chun medicine Co., Ltd. manufactures) 0.05 mass parts as stopper stirs, triple-roller mill is used to carry out mixing afterwards, thus obtain active energy ray-curable ink (I1).
Below, similarly polymerizability unsaturated group resin (2) ~ (4) and (R1) ~ (R3) are contained for other, also the above-mentioned raw materials of same mass parts is used, similarly manufacture, thus obtain active energy ray-curable ink (I2) ~ (I4) and (IR1) ~ (IR3).
[evaluation of solidified nature and the solvent resistance manufacture method of color development thing]
Use simple and easy color development machine (manufacture of RItester, Feng Rong Jinggong Co., Ltd), use black 0.10ml, in the rubber rollers that active energy ray-curable ink (I1) ~ (I4) so obtained and (IR1) ~ (IR4) is extended in RItester equably and metallic roll, on the surface of enamelled paper (Oji Paper manufacture " OKtopcoatplus57.5kg, A-SIZE "), throughout roughly 200cm
2the mode that is coated with equably with blue concentration 1.6 (measuring with the SpectroEye densitometer that X-Rite Co., Ltd. manufactures) of area ground carry out color development, make color development thing.It should be noted that, RItester refers to, the trier of color development ink on paper, film, can adjust transfer amount, the coining of ink.
[utilizing the curing of UV lamp source]
Carry out ultraviolet (UV) to the color development thing after ink coating to irradiate, black overlay film is solidified.Use water-cooled metal halide lamp (power 100W/cm1 lamp) and be equipped with the UV irradiating unit (EYEGRAPHICSCO. of endless belt conveyor, LTD. manufacture, be accompanied with cold mirror), color development thing is positioned on conveying belt, under prescribed condition shown below, makes it by (irradiation distance 11cm) immediately below lamp.Ultraviolet irradiation amount under using ultraviolet accumulated light system (UshioLtd., the UNIMETERUIT-150-A/ of manufacture is by ray machine UVD-C365) to measure each condition.
[evaluation method of active energy ray-curable ink: solidified nature]
For solidified nature, after just irradiating, pawl is utilized to abrade the presence or absence of the cut on method confirmation color development thing surface.While conveying belt speed (m/ minute) limit changing aforementioned UV irradiating unit is to color development thing irradiation ultraviolet radiation, there is no the fastest conveying belt speed (m/ minute) of cut even if describe to rub consumingly with pawl after hardening yet.Therefore, the numerical value of conveying belt speed is larger, and the solidified nature of ink is better.
[evaluation method of active energy ray-curable ink: solvent resistance]
For solvent resistance, after just irradiating, solvent rub method is utilized to confirm the presence or absence of the cut on print surface.With the conveying belt speed 50 (m/ minute) of aforementioned UV irradiating unit to color development thing irradiation ultraviolet radiation, make ink solidification.After hardening by the swab stick comprising ethanol, repeatedly rubbed by visual observation and evaluate the change of state after with the surface 30 times of black cured coating film, according to following benchmark evaluation solvent resistance.
3: unchanged
2: abrasion mark remains
1: black cured coating film disappears, and can confirm base material (paper using)
[offset printing method of active energy ray-curable ink]
For manufactured active energy ray-curable ink (I1) ~ (I4) and (IR1) ~ (IR3), evaluate offset printing adaptability.As UV irradiation equipment, use is equipped with EYEGRAPHICSCO., the ManrolandAG glue printing machine (RolandR700 printing press, width 40 inches of machines) of the water-cooled metal halide lamp (power 160W/cm, use 3 lamps) LTD. manufactured, implements offset printing with the print speed of 9000 per hour.Printing uses Oji Paper to manufacture OKtopcoatplus (57.5kg, A-SIZE).Fountain solution to space of a whole page supply uses the aqueous solution being mixed with tap water 98 mass parts and etching solution (FST-700, Dainippon Ink Chemicals manufacture) 2 mass parts.
[evaluation method of active energy ray-curable ink: printing adaptability]
As the evaluation method of offset printing ink printing adaptability, first, the water supply scale card of printing press is set as 40 (the standard water yields), the mode becoming the blue concentration 1.6 (measuring with the SpectroEye densitometer that X-Rite Co., Ltd. manufactures) of standard technology with print concentration operates ink supply key, at the moment of concentration stabilize fixing ink supply key.
Afterwards, under the condition keeping fixing ink supply key, water supply scale card is become 55 from 40, printing 300 under the condition increasing water supply amount, the blue concentration of the print after measuring 300.Under the state increasing water supply amount, the concentration of print reduces fewer, and emulsification adaptability is more excellent, can be evaluated as the ink of printing adaptability excellence.According to the printing adaptability of following benchmark evaluation active energy ray-curable ink.
3: the blue concentration of print is more than 1.5
2: the blue concentration of print is more than 1.4 ~ be less than 1.5
1: the blue concentration of print is less than 1.4
[table 1]
Table 1
[table 2]
Table 2
description of reference numerals
1: inner core drivingmotor
2: inner core
3: urceolus
4: Water Tank with Temp.-controlled
5: urceolus drivingmotor
6: tap water
7: evaluate binding agent
Claims (7)
1. an Actinic-radiation curable composition, is characterized in that, using containing polymerizability unsaturated group resin (A) and polymerization starter (B) as essential component,
Describedly to obtain for making epoxy resin and there is the monocarboxylic acid reaction of polymerizability unsaturated group containing polymerizability unsaturated group resin (A), and relative to resulting from or coming from the sum at end structure position of the glycidyl ether oxygen base in described epoxy resin, the ratio of α-glycol base exists
13the ratio of less than 5 % by mole is become in C-NMR measurement result.
2. Actinic-radiation curable composition according to claim 1, wherein, the end structure position resulted from or come from the glycidyl ether oxygen base in described epoxy resin (A) is for being selected from the group be made up of following structural formula (i) ~ (vi)
In structural formula (i) ~ (iv), R
1and R
2for hydrogen atom or methyl.
3. Actinic-radiation curable composition according to claim 1, wherein, epoxy resin (A) is bisphenol-type epoxy resin.
4. Actinic-radiation curable composition according to claim 1, wherein, described in there is polymerizability unsaturated group carboxylic acid be (methyl) vinylformic acid.
5. an active energy ray-curable printing ink, is characterized in that, containing the Actinic-radiation curable composition described in any one in Claims 1 to 4.
6. active energy ray-curable printing ink according to claim 5, it is offset printing ink.
7. a print, active energy ray-curable printing ink according to claim 5 carries out printing and obtains by it.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2013-150514 | 2013-07-19 | ||
| JP2013150514 | 2013-07-19 | ||
| PCT/JP2014/066979 WO2015008596A1 (en) | 2013-07-19 | 2014-06-26 | Active energy ray-curable composition, active energy ray-curable printing ink comprising same, and printed matter |
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| CN105408367A true CN105408367A (en) | 2016-03-16 |
| CN105408367B CN105408367B (en) | 2017-07-11 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250409A (en) * | 2016-12-28 | 2018-07-06 | 荒川化学工业株式会社 | Resin, activity energy-line solidifying type resin composition, solidfied material, active energy ray-curable printing ink and printed article |
| CN108485371A (en) * | 2018-04-17 | 2018-09-04 | 广州市恒远彩印有限公司 | The paper wrapper printing faces UV oil and preparation method thereof |
| CN108587306A (en) * | 2018-04-17 | 2018-09-28 | 广州市恒远彩印有限公司 | Blue ultraviolet cured offset printing ink and preparation method thereof |
| CN109082206A (en) * | 2018-07-24 | 2018-12-25 | 中山易必固新材料科技有限公司 | A kind of electron beam irradiation solid coatings and preparation method thereof with mirror effect |
| CN115279847A (en) * | 2020-03-26 | 2022-11-01 | 富士胶片株式会社 | Active energy ray-curable ink and image recording method |
| CN117362935A (en) * | 2023-10-30 | 2024-01-09 | 广东龙宇新材料有限公司 | Naphthol phenolic epoxy composition added with aziridine crosslinking agent and application thereof |
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| JP2017075222A (en) * | 2015-10-14 | 2017-04-20 | Ｄｉｃグラフィックス株式会社 | Uv-curable offset ink composition for laser marking |
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| CN108587306A (en) * | 2018-04-17 | 2018-09-28 | 广州市恒远彩印有限公司 | Blue ultraviolet cured offset printing ink and preparation method thereof |
| CN109082206A (en) * | 2018-07-24 | 2018-12-25 | 中山易必固新材料科技有限公司 | A kind of electron beam irradiation solid coatings and preparation method thereof with mirror effect |
| CN115279847A (en) * | 2020-03-26 | 2022-11-01 | 富士胶片株式会社 | Active energy ray-curable ink and image recording method |
| CN115279847B (en) * | 2020-03-26 | 2023-10-27 | 富士胶片株式会社 | Active energy ray-curable ink and image recording method |
| CN117362935A (en) * | 2023-10-30 | 2024-01-09 | 广东龙宇新材料有限公司 | Naphthol phenolic epoxy composition added with aziridine crosslinking agent and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI654244B (en) | 2019-03-21 |
| JP5866061B2 (en) | 2016-02-17 |
| CN105408367B (en) | 2017-07-11 |
| TW201510058A (en) | 2015-03-16 |
| WO2015008596A1 (en) | 2015-01-22 |
| JPWO2015008596A1 (en) | 2017-03-02 |
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