CN105408367B - Actinic-radiation curable composition, active energy ray-curable printer's ink and printed article using it - Google Patents
Actinic-radiation curable composition, active energy ray-curable printer's ink and printed article using it Download PDFInfo
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- CN105408367B CN105408367B CN201480041088.XA CN201480041088A CN105408367B CN 105408367 B CN105408367 B CN 105408367B CN 201480041088 A CN201480041088 A CN 201480041088A CN 105408367 B CN105408367 B CN 105408367B
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- ink
- unsaturated group
- epoxy resin
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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
There is provided and embodied during for printer's ink high solidification and there is the Actinic-radiation curable composition of excellent emulsification adaptability and hectographic printing adaptability, have both the active energy ray-curable printer's ink and its printed article of excellent curability, emulsibility, hectographic printing adaptability.Specifically, the Actinic-radiation curable composition is used as essential component using the resin of unsaturated group containing polymerism (A) and polymerization initiator (B), the resin of unsaturated group containing polymerism (A) be make epoxy resin and with polymerism unsaturated group monocarboxylic acid reaction obtained from the resin of unsaturated group containing polymerism, and relative to result from or come from glycidol ether epoxide end structure position sum, the ratio of α glycol bases exists13Turn into 5 moles of below % ratio in C NMR measurement results.
Description
Technical field
It is related to the Actinic-radiation curable composition useful as the raw material of active energy ray-curable ink etc..
And then, it is directed to use with the active energy ray-curable printer's ink and printed article of said composition.
Background technology
Actinic-radiation curable composition is because the thermal history to coated base is few, hardness of film, scratch resistance excellent
Advantage and the various plastic basis materials protective agent of hard paint, paper etc. of electrical article of being in, mobile phone etc., printer's ink binding agent,
Solder resist etc. is used in various fields.Wherein, to epoxy acrylic obtained by epoxy resin addition acrylic or methacrylic acid
Ester resin is widely used (referring for example to special as the adaptation to base material, material excellent in adhesion in various fields
Sharp document 1.).
However, during using above-mentioned epoxy acrylate as printer's ink binding agent, making especially as hectographic printing ink
Used time, there is required emulsification bad adaptability.That is, Mo Heshui is simultaneously continuously supplied to the space of a whole page, utilizes Mo Yushui's
Repulsive interaction and carry out in the hectographic printing of image formation, require ink high emulsification adaptability, as a result aforementioned epoxy acrylate
Hydrophily is strong, the appropriate characteristic for releasing emulsification moisture is poor, therefore, ink excessively emulsification during printing, producing printing concentration reduces etc.
The situation of printing trouble is more.On the other hand, as the UV ink of the excellent active energy ray curable of emulsification property, it is known to group
Close and use as the rosin modified phenolic resin of varnish and the technology of active energy ray curable monomer (referring for example to patent text
Offer 2).However, foregoing rosin modified phenolic resin does not have the polymerism to active energy beam, accordingly, there exist Miboin body
The problem of curability is reduced.
Thus, being used as the printer's ink of active energy ray curable, it is impossible to obtain embodiment high solidification and height can be obtained
The printer's ink for emulsifying adaptability is present situation.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 61-218620 publications
Patent document 2：No. 4734490 publications of Japanese Patent No.
The content of the invention
Problems to be solved by the invention
Therefore, high solidification is embodied when the problem to be solved in the present invention is there is provided for printer's ink and with excellent
Emulsification adaptability and hectographic printing adaptability Actinic-radiation curable composition, have both excellent curability, emulsibility,
The active energy ray-curable printer's ink and its printed article of hectographic printing adaptability.
The solution used to solve the problem
The present inventor etc. further investigate repeatedly in order to solve the above problems, and as a result find：By for epoxy resin is used
The resin of unsaturated group containing polymerism obtained from monocarboxylic acid (B) with polymerism unsaturated group is modified, and α-glycol
The total ratio at the end structure position of the fiduciary point resin exists13Adjustment turns into 5 moles of below % ratio in C-NMR measurement results
Rate, so as to embody excellent curability, and the emulsification property of printer's ink in itself obtains tremendous improvement, can obtain good
Printing characteristic, so as to complete the present invention.
That is, the present invention provides a kind of Actinic-radiation curable composition, it is characterised in that with unsaturated containing polymerism
Group resin (A) and polymerization initiator (B) are as essential component, and the resin of unsaturated group containing polymerism (A) is to make epoxy
Obtained from resin and monocarboxylic acid reaction with polymerism unsaturated group, and relative to resulting from or come from foregoing ring
The sum at the end structure position of the glycidol ether epoxide in oxygen tree fat, the ratio of α-glycol base exists13In C-NMR measurement results
Ratio as 5 moles of below %.
The present invention and then a kind of active energy ray-curable printer's ink of offer, it is characterised in that contain foregoing active energy
Measure ray-curable composition.
The present invention and then a kind of printed article of offer, it is printed using foregoing active energy ray-curable printer's ink
Obtained from.
The effect of invention
According to the present invention it is possible to provide embodied during for printer's ink high solidification and with excellent emulsification adaptability and
The Actinic-radiation curable composition of hectographic printing adaptability, have both excellent curability, emulsibility, hectographic printing adapt to
Property active energy ray-curable printer's ink and its printed article.
Brief description of the drawings
Fig. 1 is the sectional view of the Ducted testing machines (Chuan Cun reason developments are made) used in emulsification Adaptability Evaluation experiment.
Embodiment
The present invention active energy ray-curable composition be characterised by, for make epoxy resin and with polymerism not
α glycol knots in the resin of unsaturated group containing polymerism obtained from the monocarboxylic acid reaction of saturated group, its end structure position
The presence ratio at structure position is 5 moles of below %.
Herein, in the resin of unsaturated group containing polymerism, result from or come from the glycidyl ether oxygen in epoxy resin
The end structure position of base refers to, passes through the epoxy radicals in raw material epoxy resin and the monocarboxylic acid with polymerism unsaturated group
Reaction and the various end structure positions generated or unreacted and the epoxy radicals that directly remains, be following structures specifically
Various end structures shown in formula (i)~(vi),
(in structural formula (i)~(iv), R1And R2For hydrogen atom or methyl.).
In the present invention, it can utilize13In the sum for the end structure that C-NMR is determined, by by aforementioned structural formula (v) Suo Shi
The containing ratio adjustment of α-glycol structure position turn into 5 moles of below % ratio, so as to contain polymerism unsaturated group using this
The curability of the printer's ink of group's resin is good, and embodies excellent emulsification property.When foregoing containing ratio is 3 moles of below %, make
Used for printer's ink in the case of carrying out hectographic printing, become especially excellent aspect from printing characteristic, particularly preferably.
It should be noted that in the present invention, without complete containing above-mentioned various end structures (aforementioned structural formula (i)~(vi))
On the basis of portion, the sum of the end structure selected in from them, as long as the containing ratio of foregoing α-glycol structure position rubs for 5
You are below %.
Herein, aforementioned structural formula (i)~(vi) presence ratio can be utilized as described above13C-NMR is measured, tool
For body, can as it is following with * shown in carbon atom each peak area ratio export.It should be noted that for each peak,
With in other structures other carbon atoms repeat when, can with divided by based on other carbon atoms area portions and obtain ratio.
(in structural formula (i)~(iv), R1And R2For hydrogen atom or methyl.)
Herein,13C-NMR assay method is carried out using following condition.
" JNM-ECA500 " of [device category] Jeol Ltd.'s manufacture
[condition determination]
Sample solution concentration：30% (w/v)
Determine solvent：DMSO-d6
Cumulative frequency：4000 times
In the present invention, aforementioned structural formula (i)~(vi) if each end structure position presence ratio as described above
α-glycol structure position shown in structural formula (v) is 5 moles of below %, particularly preferably 3 moles below %, for other
End structure position, such as α additions structure position shown in structural formula (i) is 70 moles of more than %, more specifically, structural formula
(i) the α additions structure position shown in formula is the α additions structure position and structure shown in 70 moles of more than % and the structural formula (i)
When the summation of β addition structure positions shown in formula (ii) is the ratio for being changed into more than 84%, in terms of curability and emulsibility
Set out to be preferred.In addition, when the α β additions structure position shown in aforementioned structural formula (iii) is 5 moles of below %, from emulsibility
Aspect is set out to be preferred, and further Michael's addition has the monocarboxylic acid of polymerism unsaturated group in foregoing α additions structure
Obtained from Michael's addition structure be that structure position shown in aforementioned structural formula (iv) is the ratio for being changed into 8 moles of below %
When, become good aspect from curability to be preferred.In addition, the epoxy radicals shown in aforementioned structural formula (vi) is unreacted
The epoxy radicals directly remained, there is ratio in it when being the ratio for being changed into 2 moles of below %, be during especially for 1 mole of below %
It is preferred that.
Then, aforementioned epoxy resins are preferably the compound with more than 2 epoxy radicals in a molecule, specifically, can
To enumerate：Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A D-ring oxygen tree fat, hydrogenation
Bisphenol A type epoxy resin, A Hydrogenated Bisphenol A F types epoxy resin, A Hydrogenated Bisphenol A S types epoxy resin, hydrogenated bisphenol A D-ring oxygen tree fat,
The bisphenol-type epoxy resins such as tetrabromobisphenol A type epoxy resin；O-cresol phenolic epoxy varnish；Phenol novolak type ring
Oxygen tree fat, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, brominated phenol nobolak type epoxy
Resin, alkylphenol phenolic resin varnish type epoxy resin, bisphenol S phenolic resin varnish type epoxy resin, the ring of phenolic varnish type containing methoxyl group
The phenolic resin varnish type epoxy resins such as oxygen tree fat, brominated phenol phenolic resin varnish type epoxy resin；And, phenol aralkyl type asphalt mixtures modified by epoxy resin
Fat (common name ZYLOCK resin epoxides), the diglycidyl ether of resorcinol, the diglycidyl ether of quinhydrones, adjacent benzene
The 2 functional-type epoxy resin such as diglycidyl ether, biphenyl type epoxy resin, the tetramethyl biphenyl type epoxy resin of diphenol；Three contractings
Water glyceryl 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 with dimethylene (obtained from being connected to phenol nucleus
The epoxides of polynary phenol resin), aralkyl resin containing metoxyphenol etc..In addition, aforementioned epoxy resins can be used alone,
Two or more can also be mixed.
Wherein, bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin are preferred from printing adaptability aspect, are
Epoxide equivalent be in 170~500g/eq scope bisphenol-type epoxy resin, especially bisphenol A type epoxy resin when, from emulsification
Excellent, as printer's ink using when can obtain excellent printing adaptability for the use of set out, particularly preferably.
On the other hand, reacted with the above-mentioned epoxy resin, monocarboxylic acid with polymerism unsaturated group can for example be lifted
Go out acrylic acid, methacrylic acid, butenoic acid, particularly from printing adaptability aspect, preferably acrylic acid, metering system
Acid, particularly preferred acrylic acid.
The resin of unsaturated group containing polymerism (A) used in the present invention as described above can by make epoxy resin and
The foregoing monocarboxylic acid with polymerism unsaturated group reacts and manufactured, specifically, in depositing for nitrogen atom base catalyst
When under reacting it, from α-glycol amount easily is reduced into 5 moles of below % aspect to be preferred.
Foregoing nitrogen atom base catalyst used herein is the alkali compounds with nitrogen-atoms.It is used as the nitrogenous original
Sub- base catalyst, for example, can enumerate：N-butylamine, amylamine, hexyl amine, cyclo-hexylamine, octyl amine, benzyl amine etc. primary
Amine, the straight-chain secondary amine, aziridine, azetidine, pyrroles such as diethylamide, dipropylamine, diisopropylamine, dibutylamine
Secondary amine, Trimethylamine, three second as the cyclic secondary amines such as alkane, piperidines, azepan, Azocane and these alkyl substitution body
Base amine, tripropylamine, tri-butylamine, triethylenediamine, 1,4- diazabicyclos [2.2.2] octane, quinuclidine and 3- quinoline cores
Aliphatic tertiary amine as alcohol, the aromatic nitrile base such as dimethylaniline, and isoquinolin, pyridine, trimethylpyridine, beta-picoline
Deng heterocyclic tertiary amines, the secondary amidine such as imidazoles, purine, triazole, guanidine, pyrimidine, triazine, 1, the carbon -7- alkene of 8- diazabicyclos [5.4.0] 11
And the nitrogen atom base catalyst such as the tertiary amidine such as 1,5- diazabicyclos [4.3.0] nonyl- 5- alkene (DBN) (DBU).These nitrogenous originals
Sub- base catalyst, which can be used alone, can also be applied in combination two or more.
In these nitrogen atom base catalysts, triethylamine or tetramethyl ammonium chloride are unsaturated from will easily contain polymerism
The aspect that α-glycol amount in group resin is reduced to less than 5% is set out to be preferred.
Herein, the consumption of foregoing nitrogen atom base catalyst turns into relative to the mass parts of material composition gross mass 100
0.01~0.6 mass parts, particularly 0.03~0.5 mass parts, especially the scope of the ratio of 0.05~0.3 mass parts when, from
Reducing α-glycol amount in the resin of unsaturated group containing polymerism of generation, emulsification property becomes good aspect and sets out to be excellent
Choosing.
In addition, the method for manufacturing the above-mentioned resin of unsaturated group containing polymerism (A), following method will easily contain poly-
The aspect that α-glycol amount in conjunction property unsaturated group resin is reduced to less than 5% is set out to be preferred, and methods described is makes epoxy
Resin and monocarboxylic acid with polymerism unsaturated group are in the presence of nitrogen atom base catalyst, with epoxy radicals and carboxyl
For the ratio of 0.9/1.0~1.0/0.9 (mol ratio) scope, and relative to the mass parts of material composition gross weight 100 with 0.01
The ratio of~0.6 mass parts, preferably 0.03~0.5 mass parts, especially 0.05~0.3 mass parts uses nitrogen atom base catalysis
Agent, with the scope of 80~125 DEG C of reaction temperature, preferably 90~110 DEG C of scope, makes its reaction until epoxide equivalent is changed into
More than 8000g/eq or acid number are changed into less than 2.0.
And then, the reaction of above-mentioned epoxy resin and the monocarboxylic acid with polymerism unsaturated group, which can also be used, not to be contained
Carried out with carboxyl and the free radical polymerization monomer at the position of epoxy reaction as reaction dissolvent in the reaction dissolvent.
As the species of the foregoing free radical polymerization monomer for not containing the position with carboxyl and epoxy reaction, for example may be used
To enumerate：NVP, acryloyl morpholine, (methyl) acrylic acid bicyclopentadiene ester, (methyl) acrylic acid two
Cyclopentene epoxide ethyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid phenoxy group
Ethyl ester, (methyl) acrylate, butoxy ethyl, (methyl) isobornyl acrylate, list (methyl) acrylate of Bisphenol F, epoxy
Single (methyl) acrylate such as list (methyl) acrylate of alkane addition Bisphenol F；Ethylene glycol two (methyl) acrylate, two rings penta
Alkenyl two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, dihydroxy first
Base tristane diacrylate, tripropylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, 1,6-
Hexylene glycol two (methyl) acrylate, alkylene oxide addition 1,6-HD two (methyl) acrylate, polyethylene glycol two (methyl)
Acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, hydroxyl trimethylacetic acid neopentyl glycol
Two (methyl) acrylate of ester, two (methyl) acrylate of bisphenol-A, two (methyl) acrylate of Bisphenol F, alkylene oxide add
Two (methyl) acrylic acid such as two (methyl) acrylate of two (methyl) acrylate, alkylene oxide addition Bisphenol F into bisphenol-A
Ester；Trimethylolpropane tris (methyl) acrylate, alkylene oxide addition trimethylolpropane tris (methyl) acrylate, Ji Wusi
Alcohol triacrylate etc. three (methyl) acrylate；Six acrylate of dipentaerythritol etc..
Preferred epoxide equivalent is in 8000g/eq to the so obtained resin of unsaturated group containing polymerism (A) as described above
Above or acid number be in less than 2.0 scope.In addition, for the resin of unsaturated group containing polymerism (A), being dissolved in butyl acetate
When the mass % solution of nonvolatile component 80 in solution viscosity be 0.5~30Pas scope when, from formed printer's ink when hold
Easily adjustment viscosity and the excellent aspect of resistance to winged ink and roller metastatic when forming printer's ink is set out to be preferred, in 1.0~
During 10.0Pas scope, it is particularly preferred to become obvious aspect from these effects.
Then, the polymerization initiator (B) used in the present invention can be enumerated：Intramolecular cracking type Photoepolymerizationinitiater initiater and take by force
Hydrogen Photoepolymerizationinitiater initiater.As intramolecular cracking type Photoepolymerizationinitiater initiater, for example, it can enumerate：Diethoxy acetophenone, 2-
Hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzil dimethyl ketal, 1- (4- isopropyl phenyls) -2- hydroxy-2-methyls third
Alkane -1- ketone, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone, 1- hydroxycyclohexyl-phenylketones, 2- hydroxyls -1-
{ 4- [4- (2- hydroxy-2-methyls-propiono)-benzyl]-phenyl } -2- methyl-propan -1- ketone, 2,2- dimethoxys -1,2- two
The acetophenone based compounds such as diphenylphosphino ethane -1- ketone, 2,2- diethoxy -1,2- diphenylethane -1- ketone；1- [4- (benzene sulphur
Base) -, 2- (O- benzoyls oxime)], 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -, 1- (O- acetyl oxime)
It is even Deng carbazole based compound, benzoin, benzene such as oxime compound, double (2- methyl -2- the morpholinyl propyls) -9- butyl carbazoles of 3,6-
The benzoin based compound such as relation by marriage methyl ether, benzoin isopropyl ether；
2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) butane -1- ketone, 2- (dimethylamino) -2- (4- first
Base benzyl) -1- (4- morpholino phenyls) butane -1- ketone, 2- methyl -2- morpholinyls ((4- methyl mercaptos) phenyl) propane -1- ketone, 2-
The aminoalkyl-phenones based compounds such as benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone；Double (2,4,6- front threes
Base benzoyl)-phenyl phosphine oxide, 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, double (2,6- dimethoxybenzoyls
Base) the acylphosphine oxide based compound such as -2,4,4- trimethyl-pentyl phosphine oxides；Benzil, methyl benzoylformate etc..
On the other hand, as hydrogen-abstraction Photoepolymerizationinitiater initiater, for example, it can enumerate：Benzophenone, o-benzoyl Ji Benjia
Sour methyl esters -4- phenyl benzophenones, 4,4 '-dichloro benzophenone, dihydroxy benaophenonel, -4 '-methyl of 4- benzoyls-hexichol
Base thioether, acrylated benzophenone, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3 '-dimethyl -4-
The benzophenone based compound such as methoxy benzophenone；ITX, 2,4- dimethyl thioxanthones, 2,4- diethyl thiophenes
The thioxanthones based compounds such as ton ketone, the clopenthixal ketones of 2,4- bis-；4,4 '-bis- dimethylamino benzophenones, 4,4 '-bis- diethyl aminos
The aminobenzophenone based compound such as base benzophenone；And, 10- butyl -2- chloro-acridines ketone, 2- EAQs, 9,10- are luxuriant and rich with fragrance
Quinone, camphorquinone etc..These Photoepolymerizationinitiater initiaters, which can be used alone, can also be applied in combination two or more.In these, from curability
Excellent aspect is set out, particularly preferred aminoalkyl-phenones based compound, in addition, using produce glow peak wavelength be 350~
When the UV-LED light sources of the ultraviolet of 420nm scope are as active energy beam source, aminoalkyl-phenones system is applied in combination
Compound, acylphosphine oxide based compound and aminobenzophenone based compound are especially excellent from the excellent aspect of curability
Choosing.
The consumption of these polymerization initiators (B) is not relative to waving in the Actinic-radiation curable composition of the present invention
The mass parts of composition 100 are sent out, its total consumption, the preferably scope of 1~20 mass parts is used as.That is, total consumption of polymerization initiator (B)
During to be more than 1 mass parts, good curability can be obtained, and during for below 20 mass parts, can be avoided unreacted poly-
Close the problem of physical property such as migration, solvent resistance, against weather that initiator (B) is remained in resulted in solidfied material are reduced.From this
A little balancing performances become better aspect and set out, especially with respect to the Actinic-radiation curable composition of the present invention
In the mass parts of nonvolatile component 100, its total consumption be 3~15 mass parts scope when more preferably.
In addition, when irradiation forms cured coating film as the ultraviolet of active energy beam, except aforementioned polymeric initiator
(B) outside, by using photosensitizer, curability can further be improved.Above-mentioned photosensitizer can for example be enumerated：Aliphatic
The urea classes such as the amines such as amine, o-tolyl thiocarbamide, diethyldithioposphoric acid sodium, equal benzylisothiourea-to toluene sulphur
Sulphur compounds such as acid esters etc..The consumption of these photosensitizers becomes good aspect from the effect that curability is improved, relatively
The mass parts of nonvolatile component 100 in the Actinic-radiation curable composition of the present invention, as its total consumption, be preferably
The scope of 1~20 mass parts.
The Actinic-radiation curable composition of the present invention is with the resin of unsaturated group containing polymerism (A) described in detail above
With polymerization initiator (B) as essential component, in the present invention, it can be further combined using free radical polymerization monomer (C).On
Stating free radical polymerization monomer (C) can for example enumerate：N- caprolactams, NVP, N- vinyl
Carbazole, vinylpyridine, N, N- dimethyl (methyl) acrylamide, acrylamide, acryloyl morpholine, (methyl) acrylic acid 7-
Amino -3,7- dimethyl monooctyl ester, isobutoxymethyl (methyl) acrylamide, t-octyl (methyl) acrylamide, two acetone (first
Base) acrylamide, (methyl) acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) propylene
Sour 2- Octyl Nitrites, ethyl diethylene glycol (methyl) acrylate, (methyl) lauryl acrylate, the ring penta of (methyl) acrylic acid two
Diene ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid tetrachlorobenzene
Ester, (methyl) acrylic acid 2- tetrachloros phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) tetrabromophenyl acrylate, (first
Base) acrylic acid 2- tetrabromos phenoxy ethyl, (methyl) acrylic acid 2- Trichlorophenoxies ethyl ester, (methyl) tribromophenyl acrylate,
(methyl) acrylic acid 2- tribromophenoxies ethyl ester, (methyl) acrylate, (methyl) acrylate, butoxy ethyl,
(methyl) Pentachlorophenyl Acrylate, (methyl) acrylic acid pentabromo- phenyl ester, (methyl) acrylic acid norbornene ester, methyl triethylene glycol (first
Base) acrylate, (methyl) isobornyl acrylate, list (methyl) acrylate of Bisphenol F, the list of alkylene oxide addition Bisphenol F
(methyl) acrylate；The various phosphorous acidic group vinyl systems such as single { 2- (methyl) acryloyl-oxyethyl } phosphate ester acid are single
Body；Vinyl sulfonic acid, allyl sulphonic acid, 2- methallylsulfonic acids, 4- vinylbenzenesulfonic acids, 2- (methyl) acryloxy second
The various base system of ethene containing the sulfonic group lists such as sulfonic acid, 3- (methyl) acryloxies propane sulfonic acid, 2- acrylamide-2-methyl propane sulfonics
Body；CH2=CHCOO (CH2)3[Si(CH3)2O]nSi(CH3)3、CH2=C (CH3)COOC6H4〔Si(CH3)2O)nSi(CH3)3、CH2
=C (CH3)COO(CH2)3[Si(CH3)2O]nSi(CH3)3、CH2=C (CH3)COO(CH2)3[Si(CH3)(C6H5)O]nSi
(CH3)3Or CH2=C (CH3)COO(CH2)3[Si(C6H5)2O]nSi(CH3)3(n in wherein, various is set to 0 or 1~130
Integer.) etc. like that shown in formula, the various monomers of key containing polysiloxanes；γ-(methyl) acryloxypropyl trimethoxy silicon
Alkane, γ-(methyl) acryloxypropyl triethoxysilane, γ-(methyl) acryloxypropyl dimethoxy silicon
Alkane, γ-(methyl) acryloxypropyl diethoxy silane, γ-isopropyl alkene oxygen of (methyl) acryloxypropyl three
Base silane, vinyltrimethoxy silane, VTES, vinyl (three-'beta '-methoxy ethyoxyl) silane, second
Alkenyl triacetoxysilane, vinyl trichlorosilane or N- β-(N- vinylbenzylaminoethyls)-gamma-amino propyl group front three
TMOS and its hydrochloride；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, polyethyleneglycol
(methyl) acrylate, polypropylene glycol list (methyl) acrylate etc. have (methyl) acrylate and these monomers of hydroxyl
6-caprolactone addition product；2- dimethyl aminoethyl vinyl bases ether, 2- diethylaminos ethyl vinyl ether, 4- dimethylaminos
Base butyl vinyl ether, 4- diethylaminos butyl vinyl ether, 6- dimethylamino hexyl vinyl ethers etc. have tertiary amine
Various vinyl ethers；The various tools such as 2- hydroxyethyl vinyl ethers, 4- hydroxybutyl vinyl ethers, 6- hydroxyl hexyl vinyl ethers
There is the vinyl ethers of hydroxyl；Or 2- hydroxyl-oxethyls allyl ether, 4- hydroxybutoxies allyl ether, the list of trimethylolpropane
The diallyl of the diallyl ether of allyl ether or trimethylolpropane, the mono allyl ether of pentaerythrite or pentaerythrite
Ether etc. has the allyl ether of hydroxyl and the 6-caprolactone addition product of these monomers；Methyl vinyl ether, ethyl vinyl ether,
N-propyl vinyl ether, n-butyl vinyl ether, IVE, 2- ethylhexyl vinyl ethers, cyclopentylethylene base
The vinyl ethers such as ether, cyclohexyl vinyl ether；Ethylene glycol two (methyl) acrylate, dicyclopentenyl two (methyl) acrylic acid
Ester, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, tristane two (methyl) acrylic acid
Ester, dihydroxymethyl tristane diacrylate, tripropylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) propylene
Acid esters, 1,6-HD two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) propylene
Acid esters, neopentyl glycol two (methyl) acrylate, two (methyl) acrylate, bisphenol-A or the F of hydroxyl trimethylacetic acid DOPCP
Two (methyl) acrylate, alkylene oxide addition bisphenol-A or F two (methyl) acrylate；Maleic acid, fumaric acid, itaconic acid,
2 functional monomers such as the divinyl esters of various dicarboxylic acids such as the various unsaturated dibasic acid classes such as citraconic acid：Trihydroxy methyl third
Alkane three (methyl) acrylate, alkylene oxide addition trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) third
Olefin(e) acid ester, alkylene oxide addition pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, alkylene oxide addition
(methyl) acrylate of pentaerythrite four (methyl) acrylate etc. three；Five (methyl) acrylate of dipentaerythritol, epoxy
Five (methyl) acrylate of alkane addition dipentaerythritol, six (methyl) acrylate of dipentaerythritol, alkylene oxide addition two
The 6-caprolactone addition product of six (methyl) acrylate of pentaerythrite etc. and these monomers.
In these, from the aspect that the curability as printer's ink is excellent, five (first of particularly preferred dipentaerythritol
Base) acrylate, five (methyl) acrylate of alkylene oxide addition dipentaerythritol, six (methyl) acrylic acid of dipentaerythritol
Six (methyl) acrylate of ester or alkylene oxide addition dipentaerythritol.
The Actinic-radiation curable composition of the present invention is particularly useful as active energy ray-curable printer's ink,
In the case of above-mentioned, as other blends of above-mentioned each composition, it can use：Pigment, dyestuff, extender pigment, organic or inorganic
Filler, organic solvent, antistatic additive, defoamer, viscosity modifier, resistance to light stabilizer, weatherability stabilizer, heat-resisting stabilizing agent,
The additives such as ultra-violet absorber, antioxidant, levelling agent, pigment dispersing agent, wax.
The Actinic-radiation curable composition and then active energy ray-curable printer's ink of the present invention can pass through
After being printed to base material, irradiate active energy beam and form cured coating film.The active energy beam can be enumerated：It is ultraviolet
The ionization radial lines such as line, electron beam, alpha ray, β rays, gamma-rays.It is particularly preferably purple from curability aspect in these
Outside line.
As the active energy beam of Actinic-radiation curable composition solidification of the invention is made, as described above,
The ionization radial line as ultraviolet, electron beam, alpha ray, β rays, gamma-rays, is filled as specific energy source or solidification
Put, for example, can enumerate：Bactericidal lamp, ultraviolet fluorescent lamp, UV-LED, carbon arc, xenon lamp, manifolding high-pressure sodium lamp, middle pressure or
High-pressure sodium lamp, ultrahigh pressure mercury lamp, electrodeless lamp, metal halide lamp, using natural light etc. as the ultraviolet of light source or using sweeping
Retouch type, electron beam of curtain type electron-beam accelerator etc..
In addition, as the pigment used in active energy ray-curable printer's ink of the invention, known public affairs can be enumerated
Coloring organic pigment, for example, can enumerate " organic pigment Ha Application De Block ッ Network (authors：Bridge this Isao, sale room：カラー
オ Off ィ ス, first edition in 2006) " described in printer's ink organic pigment etc., can use：Insoluble azo pigment, insoluble idol
Nitrogen pigment, condensed azo pigment, metal phthalocyanine pigment, metal-free phthalocyanine, quinacridone pigment, pyrene pigment, purple cyclic ketones face
Material, isoindolenone pigments, isoindoline pigment, triazine dioxin pigments, thioindigo color, anthraquione pigmentss, quinophthalone pigments, metal
Complex Pigments, diketo-pyrrolo pyrrole pigments, charcoal blacks and polycycle pigment etc..
In addition, can be used as the inorganic micro- of extender pigment in the active energy ray-curable printer's ink of the present invention
Grain.As inorganic particles, it can enumerate：The inorganic colored pigments such as titanium oxide, graphite, the flowers of zinc；Carbonic acid pulverized limestone, precipitability carbonic acid
Calcium, gypsum, clay (ChinaClay), silicon dioxide powder, diatomite, talcum, kaolin, alumina white, barium sulfate, aluminum stearate,
The inorganic extender pigments such as magnesium carbonate, barite powder, whetslate；Deng inorganic pigment, silicon, glass microballoon etc..These inorganic particles lead to
Cross and used in ink with the scope of 0.1~20 mass parts, result in can adjust ink mobility, prevent fly ink, prevent to
The effect of the infiltration of the printing elements such as paper.
In addition, being used as the printing element of the active energy ray-curable printer's ink suitable for the present invention.It can enumerate：Product
In shell of catalogue, poster, leaflet, CD sets, email advertisement, pamphlet, cosmetics or beverage, medicine, toy, equipment etc. etc.
The paper base material used；Make in the various food packaging materials such as polypropylene film, polyethylene terephthalate (PET) film
Film, aluminium foil, synthetic paper and the various base materials used all the time as printing element.
In addition, the printing process of the active energy ray-curable printer's ink as the present invention, such as can enumerate：Lithographic plate
Hectographic printing, letterpress, intaglio printing, intaglio plate hectographic printing, flexible version printing, silk-screen printing etc..
The present invention prints in terms of the emulsification property raising of ink, particularly in the lithographic offset that water is continuously fed to the space of a whole page
Can be preferably by brush.The offset press of continuous supply water is manufactured by a large amount of printer manufacturers to be sold, can as one
To enumerate：Heidelberg Co., Ltd., KOMORI Corporation, printing paper work Machinery Co., Ltd. of Mitsubishi Heavy Industries Ltd,
Manroland AG, RYOBI Co., Ltd., Co., Ltd. KBA etc., further, it is possible to use utilizing the printing of piece form
Sheet offset press, using scroll state printing offset rotary press, any with can be with paper supply mode
Preferably by the present invention.More specifically, it can enumerate：The Speedmaster of Heidelberg Co., Ltd. manufacture
The Lithrone series of systems, KOMORI Corporation manufactures, printing paper work Machinery Co., Ltd. of Mitsubishi Heavy Industries Ltd
The offset presses such as the DIAMOND series of manufacture.
Embodiment
Hereinafter, the present invention is described in more detail according to embodiment.It should be noted that the present invention is not limited to these implementations
Example.
[analysis method of the glycol end base unit weight of epoxy acrylate]
Utilize13C-NMR analyzes the resin of unsaturated group containing polymerism (1) manufactured in embodiment 1~4 and comparative example 1~3
~(4) and (R1)~(R3) glycol end base unit weight.
Specifically, the end structure for respectively unsaturated group containing polymerism resin is that α shown in following structural formula adds
The further Michael's addition acrylic acid into structure, β additions structure, α β additions structure, α glycol, foregoing α additions structure
The presence ratio of carbon atom shown in other * marks of Michael's addition structure and residual epoxy base, according to13C-NMR figures
Peak area ratio calculates the mol ratio of each functional group, is evaluated with their percentage.
It should be noted that for the chemical potential of each carbon atom shown in A~G in following structural formula herein (1)~(7)
Move, using as the peak for the DMSO-d6 for determining solvent be set to 39.5ppm when as shown below.
The chemical shift of carbon atom shown in A：71.1ppm
The chemical shift of carbon atom shown in B：65.6ppm
The chemical shift of carbon atom shown in C：63.0ppm
The chemical shift of carbon atom shown in D：62.5ppm
The chemical shift of carbon atom shown in E：59.7ppm
The chemical shift of carbon atom shown in F：60.0ppm
The chemical shift of carbon atom shown in G：43.9ppm
In addition, the peak with the * carbon atoms (carbon atom shown in B) marked of the α addition structures of following structural formula (1)
(carbon shown in B is former for the carbon atom that the * of structure position with being present in the resin structure shown in following structural formula (6) is marked
Son) it is overlapping, therefore, the presence ratio of α addition structures uses the carbon subtracted from B peak area shown in the A in following structural formula (6)
It is worth obtained from the peak area of atom.
(13C-NMR condition determination)
" JNM-ECA500 " of [device category] Jeol Ltd.'s manufacture
[condition determination]
Sample solution concentration：30% (w/v)
Determine solvent：DMSO-d6
Cumulative frequency：4000 times
Embodiment 1
(DIC plants of liquid bisphenol A types epoxy resin is put into the four-hole boiling flask for possessing mixer, thermometer and condenser pipe
" EPICLON850, the epoxide equivalent 188g/eq. of formula commercial firm manufacture；Hereinafter, brief note makees " liquid BPA types epoxy resin ") 435.1
Mass parts, the mass parts of acrylic acid 163.6 and metoxyphenol (polymerization inhibitor；Hereinafter, brief note makees " MQ ") 0.1 mass parts, it is warming up to
100 DEG C, then add triethylamine (catalyst；Hereinafter, brief note makees " TEA ") 1.2 mass parts.15 hours are carried out with 100 DEG C instead
Should, so that it is that 18000g/eq., acid number are 0.4mgKOH/g, solution viscosity (butyl acetate nonvolatile component to obtain epoxide equivalent
80 Mass Solutions) 1.8Pas the resin of unsaturated group containing polymerism (1).Will be based on measure gained unsaturated group containing polymerism
Group's resin (1)13The presence ratio at C-NMR each end structure position is shown in table 1.
Embodiment 2
(DIC plants of liquid bisphenol A types epoxy resin is put into the four-hole boiling flask for possessing mixer, thermometer and condenser pipe
" EPICLON850, the epoxide equivalent 188g/eq. of formula commercial firm manufacture；Hereinafter, brief note makees " liquid BPA types epoxy resin ") 435.1
Mass parts, the mass parts of acrylic acid 163.6 and metoxyphenol (polymerization inhibitor；Hereinafter, brief note makees " MQ ") 0.1 mass parts, it is warming up to
100 DEG C, then add tetramethyl ammonium chloride (catalyst；Hereinafter, brief note makees " TMAC ") 1.2 mass parts.It is small that 15 are carried out with 100 DEG C
Shi Fanying, thus obtain epoxide equivalent be 14000g/eq., acid number be 0.8mgKOH/g, (butyl acetate is non-volatile for solution viscosity
The Mass Solution of composition 80) 1.3Pas the resin of unsaturated group containing polymerism (2).Will be based on the insatiable hunger containing polymerism of measure gained
With group resin (2)13The presence ratio at C-NMR each end structure position is shown in table 1.
Embodiment 3
(DIC plants of liquid bisphenol A types epoxy resin is put into the four-hole boiling flask for possessing mixer, thermometer and condenser pipe
" EPICLON850, the epoxide equivalent 188g/eq. of formula commercial firm manufacture；Hereinafter, brief note makees " liquid BPA types epoxy resin ") 435.1
Mass parts, the mass parts of acrylic acid 163.6 and metoxyphenol (polymerization inhibitor；Hereinafter, brief note makees " MQ ") 0.1 mass parts, it is warming up to
100 DEG C, then add 2-ethyl-4-methylimidazole (catalyst；Hereinafter, brief note makees " 2E4MZ ") 1.2 mass parts.Entered with 100 DEG C
Row 15 hours reacts, so that it is that 24000g/eq., acid number are 0.3mgKOH/g, solution viscosity (butyl acetate to obtain epoxide equivalent
The Mass Solution of nonvolatile component 80) 1.4Pas the resin of unsaturated group containing polymerism (3).Polymerization will be contained based on gained is determined
Property unsaturated group resin (3)13The presence ratio at C-NMR each end structure position is shown in table 1.
Embodiment 4
Phenol novolak type epoxy resin (DIC is put into the four-hole boiling flask for possessing mixer, thermometer and condenser pipe
" EPICLON N-660, the epoxide equivalent 210g/eq. of Co., Ltd.'s manufacture；Hereinafter, brief note makees " PN types epoxy resin ") 448.4
Mass parts, the mass parts of acrylic acid 150.9 and metoxyphenol (polymerization inhibitor；Hereinafter, brief note makees " MQ ") 0.1 mass parts, it is warming up to
100 DEG C, then add triethylamine (catalyst；Hereinafter, brief note makees " TEA ".) 0.6 mass parts.15 hours are carried out with 100 DEG C instead
Should, so that it is that 18000g/eq., acid number are 0.4mgKOH/g, solution viscosity (butyl acetate nonvolatile component to obtain epoxide equivalent
80 Mass Solutions) 14.5Pas the resin of unsaturated group containing polymerism (4).Will be unsaturated containing polymerism based on gained is determined
Group resin (4)13The presence ratio at C-NMR each end structure position is shown in table 1.
Comparative example 1
(DIC plants of liquid bisphenol A types epoxy resin is put into the four-hole boiling flask for possessing mixer, thermometer and condenser pipe
" EPICLON 850, the epoxide equivalent 188g/eq. of formula commercial firm manufacture；Hereinafter, brief note makees " liquid BPA types epoxy resin ")
435.1 mass parts, the mass parts of acrylic acid 163.6 and metoxyphenol (polymerization inhibitor；Hereinafter, brief note makees " MQ ".) 0.1 mass parts,
100 DEG C are warming up to, triphenylphosphine (catalyst is then added；Hereinafter, brief note makees the " mass parts of TPP ") 1.2.15 are carried out with 100 DEG C
Hour reaction, thus obtain epoxide equivalent be 20000g/eq., acid number be 0.5mgKOH/g, solution viscosity (do not wave by butyl acetate
Send out composition 80 Mass Solution) the 1.8Pas resin of unsaturated group containing polymerism (R1).Polymerism will be contained based on gained is determined
Unsaturated group resin (R1)13The presence ratio at C-NMR each end structure position is shown in table 2.
Comparative example 2
(DIC plants of liquid bisphenol A types epoxy resin is put into the four-hole boiling flask for possessing mixer, thermometer and condenser pipe
" EPICLON 850, the epoxide equivalent 188g/eq. of formula commercial firm manufacture；Hereinafter, brief note makees " liquid BPA types epoxy resin ")
435.1 mass parts, the mass parts of acrylic acid 163.6 and metoxyphenol (polymerization inhibitor；Hereinafter, brief note makees " MQ ".) 0.1 mass parts,
130 DEG C are warming up to, triethylamine (catalyst is then added；Hereinafter, brief note makees " TEA ") 1.2 mass parts.15 are carried out with 130 DEG C
Hour reaction, thus obtain epoxide equivalent be 25000g/eq., acid number be 0.2mgKOH/g, solution viscosity (do not wave by butyl acetate
Send out composition 80 Mass Solution) the 2.0Pas resin of unsaturated group containing polymerism (R2).Polymerism will be contained based on gained is determined
Unsaturated group resin (R2)13The presence ratio at C-NMR each end structure position is shown in table 2.
Comparative example 3
(DIC plants of liquid bisphenol A types epoxy resin is put into the four-hole boiling flask for possessing mixer, thermometer and condenser pipe
" EPICLON850, the epoxide equivalent 188g/eq. of formula commercial firm manufacture；Hereinafter, brief note makees " liquid BPA types epoxy resin ") 435.1
Mass parts, the mass parts of acrylic acid 163.6 and metoxyphenol (polymerization inhibitor；Hereinafter, brief note makees " MQ ".) 0.1 mass parts, it is warming up to
100 DEG C, then add triethylamine (catalyst；Hereinafter, brief note makees " TEA ") 6.0 mass parts.15 hours are carried out with 100 DEG C instead
Should, so that it is that 20000g/eq., acid number are 0.2mgKOH/g, solution viscosity (butyl acetate nonvolatile component to obtain epoxide equivalent
80 Mass Solutions) 1.2Pas the resin of unsaturated group containing polymerism (R3).Will be unsaturated containing polymerism based on gained is determined
Group resin (R3)13The presence ratio at C-NMR each end structure position is shown in table 2.
[preparation of the active energy ray-curable binding agent of emulsification Adaptability Evaluation]
For the effect that the more specific emulsification adaptability represented in the present invention is improved, by above-mentioned insatiable hunger containing polymerism
Added with group resin (1)~(4) and each 83 mass parts of (R1)~(R3) as active energy beam polymerism acrylate
Ethylene-oxide-modified tetramethylol methane tetraacrylate (Sartomer Co.Ltd., " SR494 " of manufacture) 17 mass parts of monomer
And mix so that obtain emulsify Adaptability Evaluation active energy ray-curable binding agent (T1)~(T4) and (TR1)~
(TR3)。
[evaluation method of the emulsibility of active energy ray-curable binding agent]
Active energy ray-curable binding agent (T1)~(T4) prepared and (TR1)~(TR3) emulsification adaptability
Evaluate using Ducted testing machines (Chuan Cun reason developments are made) to implement.
The section of Ducted testing machines is illustrated in Fig. 1.Outer barrel 3 is internal cylindric gold hollow out, with bottom surface
Category, inside, which turns into, can put into the structure for evaluating binding agent 7.Put into after binding agent 7 (5 grams), the metal of cylindrical bar shape is inner cylinder 2
As shown in figure 1, insertion is until close is 1 millimeter of distance apart from the bottom surface of outer barrel 3.Afterwards, make inner cylinder clockwise with 2000rpm
Rotation, outer barrel is also turned clockwise with 60rpm, poor by setting speed, and binding agent 7 is applied and shears and is stirred.Stirring
Afterwards at the time of by 3 minutes, it is added dropwise and is distilled to the surface of binding agent 7 with the speed of 0.5 (gram/minute) when continuing to stir
Water, so that binding agent 7 and the distilled water being added dropwise are stirred mixing (emulsification) immediately.The dropwise addition of distilled water continues 10 minutes, steams
The dripping quantity summation of distilled water terminates at the time of reaching 5 grams.
There is Ducted testing machines outer barrel 3 to be rotated by outer barrel drive motor 5, inner cylinder 2 drives electricity by inner cylinder
The structure that motivation 1 rotates, and possess the constant Water Tank with Temp.-controlled 4 of the temperature of binding agent 7 inside outer barrel 3, the temperature of running water 6
It is generally maintained at 30 DEG C.
After the stirring mixing of binding agent 7 (5 grams) and distilled water (5 grams) terminates, the remaining distillation inside inner cylinder 2 is weighed
The weight (gram) of water (not entering into binding agent and remaining water).Thus, the gross weight of the distilled water entered in binding agent 7
Y is shown below,
The weight of Y (gram)=whole input distilled water (5 grams)-remaining distilled water
The emulsification rate Z of binding agent 7 as shown in formula,
Z (%)=Y ÷ (binding agent 7 (5 grams)+Y) × 100.
(herein, for example, 5 grams of the distilled water of input is fully entered in binding agent, when remaining distilled water is 0 gram, it is calculated as Y
=5 (grams), Z=50 (%).)
Binding agent emulsification rate Z (%) numerical value is lower, and the characteristic for suitably excluding emulsification moisture is more excellent, following described
The hectographic printing adaptability of ink is also more excellent, is not susceptible to Over emulsfication or by the printing trouble such as concentration reduction caused by Over emulsfication.
Adaptability is emulsified according to following benchmark evaluations.
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%, emulsification adaptability it is medium.
1：Emulsification rate Z (%) is more than 35%, emulsifies bad adaptability.
[preparation of active energy ray-curable printer's ink]
Using mixer (single shaft dissolvers), to be compounded the states of whole raw materials (mass parts of summation 100) by above-mentioned reality
Applying the mass parts of the resin of unsaturated group containing polymerism (1) 34.5 obtained in example 1, blue pigment, (BASF Co., Ltd. manufactures
“HELIOGEN BLUE D7079”、Pigment Blue15：3) 19 mass parts, be used as active energy ray-curable acrylic acid
Dipentaerythritol acrylate (Sartomer Co.Ltd., " DPHA " of manufacture) 10 mass parts of ester monomer and two (three hydroxyls
Methyl) tetraacrylate (Sartomer Co.Ltd., " SR355NS " of manufacture) 21.95 mass parts and trihydroxy methyl third
Alkane triacrylate (MIWON Co., Ltd. manufacture " MIRAMER M-300 ") 5 mass parts, as extender pigment (Song Cun is produced
The manufacture of industry Co., Ltd. " イ Off ィ ラ ー #5000PJ " hydrous magnesium silicates) 2 mass parts and basic magnesium carbonate (Naikai Salt
Industries Co., Ltd. manufacture " magnesium carbonate TT ") 0.5 mass parts, the (" S- of Shamrock Inc. manufactures as wax
381-N1 " polyolefin-waxes) 1 mass parts, as Photoepolymerizationinitiater initiater (BASF Co., Ltd. manufacture " Irgacure907 " 2-
Methyl isophthalic acid-[4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone) 3.5 mass parts, (Datong District's chemical conversion industry as light trigger
" EAB-SS " 4,4 '-bis- (diethylaminos) benzophenone of Co., Ltd.'s manufacture) 2.5 mass parts, (and the light as polymerization inhibitor
" Q1301 " N- nitroso phenylhydroxylamines aluminium of Chun Yao Co., Ltd. manufacture) 0.05 mass parts are stirred, afterwards using three rollers
Mill is kneaded, so that it is black (I1) to obtain active energy ray-curable.
Hereinafter, similarly for other resin of unsaturated group containing polymerism (2)~(4) and (R1)~(R3), also use
The above-mentioned raw materials of same mass parts, are similarly manufactured, thus obtain active energy ray-curable ink (I2)~(I4) and
(IR1)~(IR3).
[the evaluation manufacture method of color development thing of curability and solvent resistance]
Using simple color development machine (manufacture of RItester, Feng Rong Jinggong Co., Ltd), using black 0.10ml, will so it obtain
Active energy ray-curable ink (I1)~(I4) and (IR1)~(IR4) be equably extended in RI tester rubber rollers and
In metallic roll, in the table of art paper (Oji Paper manufacture " OK topcoat plus 57.5kg, A-SIZE ")
On face, throughout substantially 200cm2Area with blue concentration 1.6 (with X-Rite Co., Ltd. manufacture SpectroEye densimeters
Measuring) mode that is equably coated with carries out color development, makes color development thing.It should be noted that RI tester refer to, paper,
The testing machine of color development ink on film, can adjust transfer amount, the coining of ink.
[utilizing the curing of UV lamp light source]
Ultraviolet (UV) irradiation is carried out to the color development thing after ink coating, solidifies black overlay film.Use water-cooled metal halide
Lamp (power 100W/cm1 lamps) and be equipped with ribbon conveyer UV irradiation units it is (EYE GRAPHICS CO., LTD. manufacture, attached
With cold mirror), color development thing is positioned on conveyer belt, the underface of lamp is passed under rated condition as shown below
(irradiation distance 11cm).Using ultraviolet accumulated light system (Ushio Ltd., the UNIMETER UIT-150-A/ of manufacture by
Ray machine UVD-C365) come the ultraviolet irradiation amount under the conditions of determining respectively.
[the evaluation method of active energy ray-curable ink：Curability]
For curability, the presence or absence of the cut on method confirmation color development thing surface is abraded using pawl after just irradiating.Side changes
Is used after hardening even if describing to color development thing irradiation ultraviolet radiation by pawl for conveying tape speed (m/ minutes) side of foregoing UV irradiation units
Consumingly rub the also most fast conveying tape speed (m/ minutes) without cut.Therefore, the numerical value of conveying tape speed is bigger, black
Curability is better.
[the evaluation method of active energy ray-curable ink：Solvent resistance]
For solvent resistance, the presence or absence of the cut on printed article surface is confirmed using solvent rub method after just irradiating.With
The conveying tape speed 50 (m/ minutes) of foregoing UV irradiation units makes black solidification to color development thing irradiation ultraviolet radiation.After hardening with bag
Swab stick containing ethanol, observes the state change behind the surface 30 times of friction evaluations ink cured coating film repeatedly by visual observation, according to
Following benchmark evaluation solvent resistances.
3：It is unchanged
2：Abrasion mark is remained
1：Black cured coating film disappears, and can confirm that base material (using paper)
[offset printing method of active energy ray-curable ink]
For manufactured active energy ray-curable ink (I1)~(I4) and (IR1)~(IR3), hectographic printing is evaluated
Adaptability.As ultraviolet lamp, using being equipped with EYE GRAPHICS CO., the water-cooled metal halide of LTD. manufactures
Manroland AG glues printing machine (Roland R700 printing machines, the width 40 of lamp (power 160W/cm, use 3 lamps)
Inch machine), hectographic printing is implemented with the print speed printing speed of 9000 per hour.Printing is manufactured using Oji Paper
OKtopcoat plus(57.5kg、A-SIZE).The fountain solution supplied to the space of a whole page is using being mixed with the mass parts of running water 98 and erosion
Carve the aqueous solution of liquid (FST-700, Dainippon Ink Chemicals's manufacture) 2 mass parts.
[the evaluation method of active energy ray-curable ink：Printing adaptability]
As the evaluation method of offset printing ink printing adaptability, first, the water supply dial of printing machine is set as 40 (marks
Quasi- water), being changed into the blue concentration 1.6 of standard technology with printed article concentration, (SpectroEye manufactured with X-Rite Co., Ltd. is dense
Degree meter is measured) mode operate ink supply key, ink supply key is fixed at the time of concentration is stable.
Afterwards, under conditions of fixed ink supply key is kept, water is supplied into dial and is changed into 55 from 40, in increase water supply
300 are printed under conditions of amount, the blue concentration of the printed article after 300 is determined.The printed article in the state of increase water quantity delivered
Concentration reduction it is fewer, emulsification adaptability it is more excellent, the excellent ink of printing adaptability can be evaluated as.According to following benchmark evaluations
The printing adaptability of active energy ray-curable ink.
3：The blue concentration of printed article is more than 1.5
2：The blue concentration of printed article be more than 1.4~be less than 1.5
1：The blue concentration of printed article is less than 1.4
[table 1]
Table 1
[table 2]
Table 2
Description of reference numerals
1：Inner cylinder drive motor
2：Inner cylinder
3：Outer barrel
4：Water Tank with Temp.-controlled
5：Outer barrel drive motor
6：Running water
7：Evaluate binding agent
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.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013150514 | 2013-07-19 | ||
| JP2013-150514 | 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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| CN105408367B true CN105408367B (en) | 2017-07-11 |
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| JP (1) | JP5866061B2 (en) |
| CN (1) | CN105408367B (en) |
| TW (1) | TWI654244B (en) |
| WO (1) | WO2015008596A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| JP6996284B2 (en) * | 2016-12-28 | 2022-01-17 | 荒川化学工業株式会社 | Resin and its manufacturing method, active energy ray-curable resin composition, cured product, active energy ray-curable printing ink, and printed matter. |
| 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 |
| WO2021192653A1 (en) * | 2020-03-26 | 2021-09-30 | 富士フイルム株式会社 | Active energy beam-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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010003759A1 (en) * | 1997-11-28 | 2001-06-14 | Kuniaki Sato | Photo curable resin composition and photosensitive element |
| CN1509324A (en) * | 2001-05-16 | 2004-06-30 | ��Ԩ��ѧ��ҵ��ʽ���� | Curing vesin composition and sealants and end-sealing materials for displays |
| CN101784578A (en) * | 2007-08-21 | 2010-07-21 | 日本化药株式会社 | Reactive carboxylate compound, active-energy-ray-curable resin composition utilizing the same, and use of the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61218620A (en) * | 1985-03-26 | 1986-09-29 | Toshiba Corp | Production of acrylic acid and/or methacrylic acid modified epoxy resin |
| JP3496668B2 (en) * | 1997-11-28 | 2004-02-16 | 日立化成工業株式会社 | Photocurable resin composition and photosensitive element using the same |
| JP4798413B2 (en) * | 2000-12-26 | 2011-10-19 | ナガセケムテックス株式会社 | Water-soluble curable epoxy (meth) acrylate and its production and use |
| JP2006124698A (en) * | 2001-05-16 | 2006-05-18 | Sekisui Chem Co Ltd | Curing resin composition, and sealant and end-sealing material for display element |
| JP4734490B2 (en) * | 2003-06-03 | 2011-07-27 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable dry lithographic printing ink composition, printing method and printed matter thereof |
| JP2007010796A (en) * | 2005-06-28 | 2007-01-18 | Tokyo Ohka Kogyo Co Ltd | Pigment-dispersed radiation-sensitive resin composition and colored pattern forming method |
| JP2010270186A (en) * | 2009-05-20 | 2010-12-02 | National Printing Bureau | Ink composition |
| JP2013108093A (en) * | 2013-02-25 | 2013-06-06 | Nippon Kayaku Co Ltd | Reactive carboxylate compound, active energy ray-curable resin composition using the same, and application thereof |
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2014
- 2014-06-26 WO PCT/JP2014/066979 patent/WO2015008596A1/en active Application Filing
- 2014-06-26 JP JP2015509659A patent/JP5866061B2/en active Active
- 2014-06-26 CN CN201480041088.XA patent/CN105408367B/en not_active Expired - Fee Related
- 2014-07-11 TW TW103124033A patent/TWI654244B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010003759A1 (en) * | 1997-11-28 | 2001-06-14 | Kuniaki Sato | Photo curable resin composition and photosensitive element |
| CN1509324A (en) * | 2001-05-16 | 2004-06-30 | ��Ԩ��ѧ��ҵ��ʽ���� | Curing vesin composition and sealants and end-sealing materials for displays |
| CN101784578A (en) * | 2007-08-21 | 2010-07-21 | 日本化药株式会社 | Reactive carboxylate compound, active-energy-ray-curable resin composition utilizing the same, and use of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI654244B (en) | 2019-03-21 |
| WO2015008596A1 (en) | 2015-01-22 |
| JP5866061B2 (en) | 2016-02-17 |
| CN105408367A (en) | 2016-03-16 |
| JPWO2015008596A1 (en) | 2017-03-02 |
| TW201510058A (en) | 2015-03-16 |
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