CN104220478A - Active energy ray-curable composition, active energy ray-curable coating material using same, and active energy ray-curable printing ink using same - Google Patents
Active energy ray-curable composition, active energy ray-curable coating material using same, and active energy ray-curable printing ink using same Download PDFInfo
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- CN104220478A CN104220478A CN201380015498.2A CN201380015498A CN104220478A CN 104220478 A CN104220478 A CN 104220478A CN 201380015498 A CN201380015498 A CN 201380015498A CN 104220478 A CN104220478 A CN 104220478A
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- Prior art keywords
- active energy
- energy ray
- curable composition
- actinic
- printing ink
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- 235000012222 talc Nutrition 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Epoxy Resins (AREA)
Abstract
Provided is an active energy ray-curable composition which is characterized by being obtained by reacting (A) a polyfunctional acrylate, (B) an aromatic dicarboxylic acid and (C) an aromatic epoxy resin, and then reacting the obtained reactant with (D) a carboxylic acid having a polymerizable unsaturated group. In cases where this active energy ray-curable composition is used in a coating material such as a hard coat agent, this active energy ray-curable composition is capable of providing a cured film of the coating material with high scratch resistance. Consequently, this active energy ray-curable composition is suitable as a material for a hard coat agent that forms a protective film on the surface of an article. In cases where this active energy ray-curable composition is used in a printing ink, this active energy ray-curable composition is capable of providing the ink with high anti-misting properties and is also capable of providing a cured film of the printing ink with high adhesion to a base and high solvent resistance. Consequently, this active energy ray-curable composition is suitable as a binder for various printing inks such as a lithographic printing ink and a gravure printing ink.
Description
Technical field
Relate to the raw material as coating, ink etc. and useful Actinic-radiation curable composition.And then, relate to the active energy ray-curable coating and active energy ray-curable printing ink that use said composition.
Background technology
Actinic-radiation curable composition because the thermal history applied coated base is few, hardness of film and the such advantage of excellent scratch resistance, therefore use in the various field such as outer paint (over coating agent), printing ink binding agent, solder resist of the hard paint of various plastic basis materials, paper etc. of household appliances, mobile phone etc.Wherein, to the Epocryl of epoxy resin addition acrylic or methacrylic acid as the adaptation to base material, material excellent in adhesion and being used frequently in various field (such as with reference to patent documentation 1.)。
But when Epocryl is in the past used as the plastic basis material of such as household appliances, mobile phone etc. with hard paint, wiping the chance of drawing hard coating surface with finger as the touch panel of smart mobile phone increases, and therefore its surface needs higher scuff resistance.In addition, when Epocryl is used as printing ink binding agent, there is the problem that emulsification adaptability is poor or printing ink anti-fog properties (anti-misting property) is poor needed for printing ink.In order to solve this problem, have: combinationally use the method for the resin of the printing adaptability excellences such as rosin series resin, diallyl phthalate resin (such as with reference to patent documentation 2.), but this combinationally uses also, and there are the following problems: printing ink reduces the adaptation of polypropylene, nylon film, or reduces based on the solidified nature of active energy beam.
So, seeking following Actinic-radiation curable composition, namely, when it is for hard paint, high scuff resistance can be given to its cured coating film, during for printing ink, can give high anti-fog properties to this ink, can to the imparting of its cured coating film to the high adhesion of base material and high solvent resistance.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 61-218620 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2010-241866 publication
Summary of the invention
the problem that invention will solve
The problem that the present invention will solve is, can give when being provided for the coating such as hard paint excellent scuff resistance, for can give during printing ink excellent anti-fog properties, to the adaptation of base material and the Actinic-radiation curable composition of solvent resistance.In addition, the active energy ray-curable coating using this Actinic-radiation curable composition and active energy ray-curable printing ink is provided.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research repeatedly in order to solve above-mentioned problem, found that, react by making polyfunctional acrylic ester and aromatic dicarboxylic acid and aromatic epoxy resin, then make gained reaction product carry out reacting with the carboxylic acid with polymerizability unsaturated group and the Actinic-radiation curable composition that obtains when for coating such as hard paints, high scuff resistance can be given to its cured coating film, when for printing ink, can give high anti-fog properties to this ink, can to the imparting of its cured coating film to the high adhesion of base material and high solvent resistance, thus complete the present invention.
Namely, the present invention relates to Actinic-radiation curable composition, the active energy ray-curable coating using said composition and active energy ray-curable printing ink, the feature of described Actinic-radiation curable composition is, it is by making polyfunctional acrylic ester (A) react with aromatic dicarboxylic acid (B) and aromatic epoxy resin (C), then makes gained reaction product carry out reacting obtaining with the carboxylic acid (D) with polymerizability unsaturated group.
the effect of invention
Actinic-radiation curable composition of the present invention, when for coating such as hard paints, can give high scuff resistance to its cured coating film, therefore as the housing at household appliances such as televisor, refrigerator, washing machine, air-conditionings; The housing of the electronicss such as computer, smart mobile phone, mobile phone, digital camera, game machine; The interior material of the various vehicle such as automobile, train; The various building materials such as decorative sheet; Carpenter's materials such as furniture, artificial/synthetic leather; The material of the hard paint of the surface formation protective membrane of the article such as FRP bathing pool is useful.
In addition, Actinic-radiation curable composition of the present invention is when for printing ink, can give high anti-fog properties to this ink, can to the imparting of its cured coating film to the high adhesion of base material and high solvent resistance, the binding agent therefore as various printing inks such as lithographic plate ink, intaglio inks is useful.
Embodiment
Active energy ray-curable aqueous resin combination of the present invention is by making polyfunctional acrylic ester (A) react with aromatic dicarboxylic acid (B) and aromatic epoxy resin (C), then makes gained reaction product carry out reacting obtaining with the carboxylic acid (D) with polymerizability unsaturated group.
Aforementioned polyfunctional acrylic ester (A) is the compound with more than 2 acryls, and the quantity of acryl is preferably 3.As the compound with 3 acryls, Viscoat 295, ethylene-oxide-modified Viscoat 295 and glycerine propoxylate etc. can be listed.Among these polyfunctional acrylic esters (A), be preferably ethylene-oxide-modified Viscoat 295.In addition, these polyfunctional acrylic esters (A) can be used alone also can combinationally use two or more.
Aforementioned fragrance race dicarboxylic acid (B) is for having the dicarboxylic acid of aromatic nucleus.As this aromatic dicarboxylic acid (B), include, for example out phthalic acid, m-phthalic acid, terephthalic acid etc.In addition, as aromatic dicarboxylic acid (B), the acid anhydride of the aromatic dicarboxylic acid of Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride and so on can also be used.Among these aromatic dicarboxylic acids (B), from the reactivity height of the epoxy group(ing) had with aforementioned fragrance race epoxy resin, be preferably m-phthalic acid.In addition, these aromatic dicarboxylic acids (B) can be used alone also can combinationally use two or more.
Aforementioned fragrance race epoxy resin (C) is for having the epoxy resin of aromatic nucleus.As this aromatic epoxy resin (C), include, for example out the bisphenol-type epoxy resins such as tetramethyl-bisphenol-type epoxy resin; The bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin; Dicyclopentadiene-modified aromatic series difunctional epoxy resin; Dihydroxy naphthlene class is carried out the dihydroxy naphthlene type epoxy resin of epoxidation; The glycidyl ester type resin of aromatic binary carboxylic acid; The difunctional epoxy resin derived by xylenol, naphthalene aralkyl epoxy resin; By the dicyclopentadiene-modified epoxy resin of these aromatic series difunctional epoxy resin; By ester modified epoxy resin etc. acrylic modified for these aromatic series difunctional epoxy resin binary.Among these aromatic epoxy resins (C); from the reactivity height of the acryl of the secondary hydroxyl generated by making epoxy ring-opening with the reaction of aforementioned fragrance race dicarboxylic acid (B) and aforementioned polyfunctional acrylic ester (A), be preferably bisphenol A type epoxy resin.In addition, these aromatic epoxy resins (C) can be used alone also can combinationally use two or more.
Aforementioned carboxylic acid (D) is the carboxylic acid with polymerizability unsaturated group.As this carboxylic acid (D), include, for example out vinylformic acid, methacrylic acid etc.Among these carboxylic acids (D), from the solidified nature well of irradiating based on active energy beam, be preferably vinylformic acid.In addition, these carboxylic acids (D) can be used alone also can combinationally use two or more.
Actinic-radiation curable composition of the present invention can be manufactured by following two operations.
[the 1st operation]
Polyfunctional acrylic ester (A) and aromatic dicarboxylic acid (B) and aromatic epoxy resin (C) is made to carry out the operation of reacting.
[the 2nd operation]
The reaction product obtained in the 1st operation and the carboxylic acid (D) with polymerizability unsaturated group is made to carry out the operation of reacting.
In the 1st above-mentioned operation; the carboxyl of aromatic dicarboxylic acid (B) and the epoxy group(ing) of aromatic epoxy resin (C) be bonding by the opening of epoxy group(ing), and the acryl of consequent secondary hydroxyl and polyfunctional acrylic ester (A) is reacted by Michael reaction.Therefore, can think that gained reaction product has aforementioned fragrance race dicarboxylic acid (B) and aforementioned fragrance race epoxy resin (C) and react the structure that the polymer chain generated undertakies by aforementioned polyfunctional acrylic ester (A) being cross-linked.In addition, can think such as use ethylene-oxide-modified pentaerythritol triacrylate at polyfunctional acrylic ester (A), the carrying out of reaction when aromatic dicarboxylic acid (B) uses m-phthalic acid, aromatic epoxy resin (C) uses bisphenol A type epoxy resin be as following (reaction formula 1).It should be noted that, write a Chinese character in simplified form the segment that aforementioned fragrance race dicarboxylic acid (B) after Michael reaction reacts with aforementioned fragrance race epoxy resin (C).
(in formula, n, x, y and z represent the repeating unit in bracket respectively.)
About the consumption of aforementioned fragrance race epoxy resin (C) in above-mentioned 1st operation, relative to the carboxyl 1 mole that aforementioned fragrance race dicarboxylic acid (B) has, the epoxy group(ing) that aforementioned fragrance race epoxy resin (C) has preferably reach 1 ~ 5 scope, more preferably reach 1.1 ~ 3 scope, further preferably reach 1.5 ~ 3 scope.Use by the epoxy group(ing) that makes aromatic epoxy resin (C) have is excessive, the reaction product obtained in the 1st operation can have epoxy group(ing).
In addition, the consumption of the aforementioned polyfunctional acrylic ester (A) in above-mentioned 1st operation, relative to total amount 100 mass parts of aforementioned fragrance race dicarboxylic acid (B) with aforementioned fragrance race epoxy resin (C), is preferably the scope of 20 ~ 300 mass parts, is more preferably the scope of scope, more preferably 80 ~ 120 mass parts of 50 ~ 200 mass parts.
In addition, above-mentioned 1st operation is preferably carried out under the existence of catalyzer (E), as this catalyzer (E), can list triphenylphosphine, glyoxal ethyline, trimethyl ammonium chloride etc.Among these catalyzer (E), calm reaction easy to control is set out, and is preferably triphenylphosphine.In addition, these catalyzer (E) can be used alone also can combinationally use two or more.
And then above-mentioned 1st operation is preferably carried out under the existence of stopper (F), as this stopper (F), the nitrous base system stoppers such as nitroso-group phenylhydroxylamine ammonium salt can be listed; The quinone system stoppers such as Resorcinol, MEHQ (hydroquinone monomethyl ether), benzoquinones; Bitter diazanyl (the diphenylpicrylhydrazyl of N, N-phenylbenzene; DPPH), the radical scavenger such as trityl group, butylhydroxy toluene; Benzotriazole system antioxidant etc.Among these stoppers (F), from the solvability height in resin, be preferably MEHQ.In addition, these stoppers (F) can be used alone also can combinationally use two or more.
In addition, about the temperature of reaction in above-mentioned 1st operation, from epoxy addition reaction and addition reaction meeting propelling well, be preferably the scope of 100 ~ 140 DEG C, be more preferably the scope of 110 ~ 130 DEG C.
The epoxy equivalent (weight) of the reaction product obtained by above-mentioned 1st operation is preferably the scope of 100 ~ 2000g/eq., is more preferably the scope of scope, the more preferably 100 ~ 300g/eq. of 100 ~ 500g/eq..In addition, about acid number, the scope being preferably 0.1 ~ 3.0, the scope of the scope being more preferably 0.1 ~ 2.0, more preferably 0.1 ~ 1.0.
On the other hand, in above-mentioned 2nd operation, the carboxyl that the epoxy group(ing) had by making the reaction product obtained in the 1st operation and vinylformic acid etc. have the carboxylic acid (D) of polymerizability unsaturated group reacts, and imports polymerizability unsaturated group in the reaction product that can obtain in the 1st operation.About this reaction, the reaction product such as, obtained in the 1st operation be material shown in above-mentioned (reaction formula 1) and carboxylic acid (D) uses vinylformic acid time, can as shown in following (reaction formula 2).
(in formula, x, y and z represent the repeating unit in bracket respectively.)
In addition, about the reaction product obtained in the 1st operation and the reaction of carboxylic acid (D) with polymerizability unsaturated group, the Above-mentioned catalytic agent (E) and stopper (F) that illustrate in the 1st operation also can be used in as required.
About the epoxy equivalent (weight) of the Actinic-radiation curable composition of the present invention obtained via above-mentioned 1st operation and the 2nd operation, become well from the stability of composition, be preferably the scope of 5000 ~ 50000g/eq., be more preferably the scope of scope, the more preferably 14000 ~ 50000g/eq. of 10000 ~ 50000g/eq..In addition, about acid number, from the view point of the stability of composition, the scope being preferably 0.5 ~ 10, the scope of the scope being more preferably 0.5 ~ 5, more preferably 0.5 ~ 3.
In addition, polyfunctional acrylic ester (A ') can also be added in Actinic-radiation curable composition of the present invention further.When adding this polyfunctional acrylic ester (A '), adding when above-mentioned 2nd operation or adding after the 2nd operation.As polyfunctional acrylic ester (A '), the material identical with polyfunctional acrylic ester (A) can be used, identical or different with polyfunctional acrylic ester (A), be preferably ethylene-oxide-modified Viscoat 295.In addition, these polyfunctional acrylic esters (A ') can be used alone also can combinationally use two or more.
Active energy ray-curable coating of the present invention contains Actinic-radiation curable composition of the present invention, as other formulation, the additives such as pigment, dyestuff, pigment extender, organic or inorganic filler, active energy ray-curable monomer, active energy ray-curable oligopolymer, organic solvent, static inhibitor, defoamer, viscosity modifier, resistance to photostabilizer, weathering stabilizers, heat-resisting stabilizing agent, UV light absorber, antioxidant, flow agent, pigment dispersing agent can be used.
Active energy ray-curable coating of the present invention, by irradiating active energy beam after coating base material, can make cured coating film.This active energy beam refers to the ionization radial lines such as ultraviolet, electron beam, alpha-ray, β ray, gamma-rays.When making cured coating film as active energy beam irradiation ultraviolet radiation, preferably, in active energy ray-curable aqueous coating of the present invention, add Photoepolymerizationinitiater initiater (G) and improve solidified nature.In addition, if needed, photosensitizers can also be added further to improve solidified nature.On the other hand, when using the ionization radial line of electron beam, alpha-ray, β ray, gamma-rays and so on, even if do not use Photoepolymerizationinitiater initiater, photosensitizers also can promptly solidify, therefore without the need to specially adding Photoepolymerizationinitiater initiater (G), photosensitizers.
As foregoing photo-polymerization initiator (G), cracking type Photoepolymerizationinitiater initiater and hydrogen-abstraction Photoepolymerizationinitiater initiater in molecule can be listed.As cracking type Photoepolymerizationinitiater initiater in molecule, include, for example out the methyl phenyl ketone based compounds such as 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-hydroxy-cyclohexyl-benzophenone, 2-methyl-2-morpholino (4-methylthio group phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone; The bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, benzoin iso-propylether; The acylphosphine oxide based compounds such as 2,4,6-Three methyl Benzene acyloin diphenyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide; Benzil, methyl phenyl glyoxylate ester (methyl phenyl glyoxylate) etc.
On the other hand, as hydrogen-abstraction Photoepolymerizationinitiater initiater, include, for example out benzophenone, o-benzoyl yl benzoic acid methyl 4-phenyl benzophenone, 4,4 '-dichloro benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 '-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4 '-four (t-butyl peroxy 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; Michler's keton, 4, the aminobenzophenone based compounds such as 4 '-diethylamino benzophenone; 10-butyl-2-chloro-acridine ketone, 2-ethyl-anthraquinone, 9,10-phenanthrenequione, camphorquinone (camphorquinone) etc.These Photoepolymerizationinitiater initiaters (G) may be used alone, can also be used in combination two or more.
In addition, as foregoing photo sensitizers, include, for example out the amine such as fatty amine, aromatic amine; The ureas such as o-tolyl thiocarbamide; The sulphur compounds etc. such as diethyldithiophosphoric acid sodium, s-benzylisothiourea p-toluenesulfonic esters.
About the consumption of these Photoepolymerizationinitiater initiaters and photosensitizers, relative to nonvolatile component 100 mass parts in active energy ray-curable coating of the present invention, be preferably 0.05 ~ 20 mass parts respectively, be more preferably 0.5 ~ 10 quality %.
In addition, active energy ray-curable coating of the present invention can use as the coating for the various article of application.As can the article of application active energy ray-curable coating of the present invention, the housing of the household appliances such as televisor, refrigerator, washing machine, air-conditioning can be listed; The housing of the electronicss such as computer, smart mobile phone, mobile phone, digital camera, game machine; The interior material of the various vehicle such as automobile, train; The various building materials such as decorative sheet; Carpenter's materials such as furniture, artificial/synthetic leather; FRP bathing pool etc.
In addition, as the coating process of active energy ray-curable coating of the present invention, different because of purposes, include, for example out the method for gravure coater, roller coating machine, comma coater, knife coater, Kohler coater, curtain coater, kiss roll coater, spray coating machine, wheeled coating machine, spin coater, dip-coating, silk screen printing, spraying, applicator, bar coater etc.
As the active energy beam making active energy ray-curable paint solidification of the present invention, as implied above, there is the ionization radial line of ultraviolet, electron beam, alpha-ray, β ray, gamma-rays and so on, as concrete energy source or solidification equipment, include, for example out the ultraviolet using germicidal lamp, ultraviolet luminescent lamp, carbon arc, xenon lamp, duplicating high voltage mercury lamp, medium-pressure or high pressure mercury lamp, ultrahigh pressure mercury lamp, electrodeless lamp, metal halide lamp, natural light etc. as light source; Or, the electron beam etc. produced by sweep type, curtain type electron-beam accelerator.
Active energy ray-curable printing ink of the present invention contains Actinic-radiation curable composition of the present invention, and in addition, compounding have the formulation being suitable for various mode of printing.Such as, when lithographic printing brush ink, the additives such as pigment, dyestuff, pigment extender, paraffin, polyolefin-wax, organic solvent, pigment dispersing agent can be used.
In addition, when active energy ray-curable printing ink of the present invention, compounding Photoepolymerizationinitiater initiater, photosensitizers as required, its compounding amount is also identical with the situation of coating.And then the active energy beam used during solidification and the device for irradiating it also can use identical active energy beam and device.
In addition, active energy ray-curable printing ink of the present invention can use as the ink for printing various printed thing.As this printed thing, the paper base material that goods catalogue, brochure, cosmetic package etc. use can be listed; The film etc. that the various food packaging materials such as polypropylene film, polyethylene terephthalate (PET) film use.
In addition, as the printing process of active energy ray-curable printing ink of the present invention, include, for example out lithography, intaglio printing, intaglio offset printing, flexographic printing etc.
Embodiment
Below, specific embodiment is listed to illustrate in greater detail the present invention.It should be noted that, the acid number of products therefrom measures according to JIS test method K0070-1992, and epoxy equivalent (weight) measures according to JIS test method K7236:2001.
(embodiment 1)
Ethylene-oxide-modified Viscoat 295 is dropped into (hereinafter referred to as " EOTMPTA " in the four-hole boiling flask possessing stirrer, thermometer and prolong.) 177.5 mass parts, (" DER331 ", epoxy equivalent (weight) that DOW Chemical Amada Co., Ltd. manufactures are 185g/eq. to bisphenol A type epoxy resin; Hereinafter referred to as " Bis-A type epoxy resin ".) 145 mass parts, terephthalic acid is (hereinafter referred to as " TPA ".) 32 mass parts, butylated hydroxytoluene (stopper; Hereinafter referred to as " BHT ".) 1.8 mass parts and MEHQ (stopper; Hereinafter referred to as " MQ ".) 0.2 mass parts, after being warming up to 120 DEG C, add triphenylphosphine (catalyzer; Hereinafter referred to as " TPP ".) 2.7 mass parts.Reaction 5 hours is continued with 120 DEG C, the time point of 1050g/eq. is reached at the epoxy equivalent (weight) of reaction soln, drop into vinylformic acid 24 mass parts, EOTMPTA105 mass parts and TPP1.2 mass parts, then carry out the reaction of 2 hours further with 120 DEG C, thus obtain epoxy equivalent (weight) be 15000g/eq. and acid number be 3.4 Actinic-radiation curable composition (1).
(embodiment 2)
EOTMPTA177.5 mass parts, Bis-A type epoxy resin 145 mass parts, m-phthalic acid is dropped into (hereinafter referred to as " IPA " in the four-hole boiling flask possessing stirrer, thermometer and prolong.) 32 mass parts, BHT1.8 mass parts and MQ0.2 mass parts, after being warming up to 120 DEG C, add TPP2.7 mass parts.Reaction 5 hours is continued with 120 DEG C, the time point of 1050g/eq. is reached at the epoxy equivalent (weight) of reaction soln, drop into vinylformic acid 25 mass parts, EOTMPTA105 mass parts and TPP1.2 mass parts, then carry out the reaction of 2 hours further with 120 DEG C, thus obtain epoxy equivalent (weight) be 16000g/eq. and acid number be 2.1 Actinic-radiation curable composition (2).
(embodiment 3)
EOTMPTA177.5 mass parts, Bis-A type epoxy resin 149.5 mass parts, IPA21 mass parts, BHT1.8 mass parts and MQ0.2 mass parts is dropped in the four-hole boiling flask possessing stirrer, thermometer and prolong, after being warming up to 120 DEG C, add TPP2.7 mass parts.Reaction 5 hours is continued with 120 DEG C, the time point of 1050g/eq. is reached at the epoxy equivalent (weight) of reaction soln, drop into vinylformic acid 28 mass parts, EOTMPTA105 mass parts and TPP1.2 mass parts, then carry out the reaction of 2 hours further with 120 DEG C, thus obtain epoxy equivalent (weight) be 15500g/eq. and acid number be 1.5 Actinic-radiation curable composition (3).
(embodiment 4)
Viscoat 295 is dropped into (hereinafter referred to as " TMPTA " in the four-hole boiling flask possessing stirrer, thermometer and prolong.) 177.5 mass parts, Bis-A type epoxy resin 145 mass parts, IPA32 mass parts, BHT1.8 mass parts and MQ0.2 mass parts, after being warming up to 120 DEG C, add TPP2.7 mass parts.Reaction 5 hours is continued with 120 DEG C, the time point of 1050g/eq. is reached at the epoxy equivalent (weight) of reaction soln, drop into vinylformic acid 25 mass parts, EOTMPTA105 mass parts and TPP1.2 mass parts, then carry out the reaction of 2 hours further with 120 DEG C, thus obtain epoxy equivalent (weight) be 15100g/eq. and acid number be 2.5 Actinic-radiation curable composition (4).
(embodiment 5)
Glycerine propoxylate is dropped into (hereinafter referred to as " GPTA " in the four-hole boiling flask possessing stirrer, thermometer and prolong.) 177.5 mass parts, Bis-A type epoxy resin 145 mass parts, IPA32 mass parts, BHT1.8 mass parts and MQ0.2 mass parts, after being warming up to 120 DEG C, add TPP2.7 mass parts.Reaction 5 hours is continued with 120 DEG C, the time point of 1050g/eq. is reached at the epoxy equivalent (weight) of reaction soln, drop into vinylformic acid 24 mass parts, EOTMPTA105 mass parts and TPP1.2 mass parts, then carry out the reaction of 2 hours further with 120 DEG C, thus obtain epoxy equivalent (weight) be 16000g/eq. and acid number be 2.2 Actinic-radiation curable composition (5).
The raw material of the Actinic-radiation curable composition obtained in above-described embodiment 1 ~ 5 (1) ~ (5) composition, epoxy equivalent (weight) and acid number are summarized in table 1.
[table 1]
(comparative example 1)
In the four-hole boiling flask possessing stirrer, thermometer and prolong, drop into Bis-A type epoxy resin 145 mass parts, vinylformic acid 56 mass parts, BHT1.8 mass parts and MQ0.2 mass parts, after being warming up to 120 DEG C, add TPP1.2 mass parts.Then, carry out the reaction of 5 hours with 120 DEG C, thus obtain epoxy equivalent (weight) be 15000g/eq. and acid number be 1.0 Actinic-radiation curable composition (R1).
(embodiment 6)
[preparation of active energy ray-curable coating]
By Actinic-radiation curable composition (1) 100 mass parts, the Photoepolymerizationinitiater initiater (" IRGACURE184 " that BASF JAPAN LTD. manufactures that obtain in above-described embodiment 1; 1-hydroxy-cyclohexyl-benzophenone) 4 mass parts and N-BUTYL ACETATE 20 mass parts mixing, obtain active energy ray-curable coating (1).Then, for the cured coating film of gained active energy ray-curable coating (1), the evaluation of following scuff resistance is carried out.
[evaluation of scuff resistance]
Use applicator to be coated on sheet glass (thickness is for 2mm) by the mode that active energy ray-curable coating (1) obtained above reaches 10 μm with dry film thickness, after solvent seasoning, use the high voltage mercury lamp of 80W/cm, with 0.8J/cm
2ultraviolet irradiation amount make it solidify, obtain the evaluation film of scuff resistance.Then, (load is 500g/cm to utilize the wear testing machine being provided with Steel Wool (Nippon Steel Wool Co., Ltd. manufactures " Bonsuta No.0000 ") in the circular clamp of diameter for 27mm
2), 100 times are carried out to the surface of gained evaluation film and comes and goes abrasion.With haze meter (" NDH5000 " that Japanese electricity Se Industrial Co., Ltd manufactures), the film after test is measured, evaluate scuff resistance by gained haze value according to following benchmark.
Zero: haze value is less than 5.
△: haze value is more than 5 and less than 10.
×: haze value is more than 10.
(embodiment 7 ~ 10 and comparative example 2)
Replace except the Actinic-radiation curable composition (1) of use in embodiment 6 except using Actinic-radiation curable composition (2) ~ (5) that obtain in embodiment 2 ~ 5 and comparative example 1 and (R1), similarly operate, prepare active energy ray-curable coating (2) ~ (5) and (R1), obtain cured coating film, carry out the evaluation of scuff resistance.
The evaluation result of the active energy ray-curable system component obtained in above-described embodiment 6 ~ 10 and comparative example 2 and scuff resistance is summarized in table 2.
[table 2]
Known: it is very little that the cured coating film employing the active energy ray-curable coating of the embodiment 6 ~ 10 of Actinic-radiation curable composition of the present invention utilizes Steel Wool to carry out the haze value after abrasion, is 1 ~ 2%, has high scuff resistance.
On the other hand, the active energy ray-curable coating of comparative example 2 is the example of the Actinic-radiation curable composition employing polyfunctional acrylic ester (A) and the aromatic dicarboxylic acid (B) not using the present invention used, known its utilizes Steel Wool to carry out the haze value after abrasion up to 11%, and scuff resistance is poor.
(embodiment 11)
[preparation of active energy ray-curable printing ink]
By Actinic-radiation curable composition (1) 23 mass parts, red pigment (Pigment red 57-1) 19 mass parts, yellow ultramarine (pigment yellow 13) 3 mass parts, the straight-chain polyester acrylate (" Ebecryl657 " that USB chemical company manufactures that obtain in above-described embodiment 1; Hereinafter referred to as " PEsA ".) 25 mass parts, TMPTA13 mass parts, talcum 8 mass parts, polyethylene wax 5 mass parts, Photoepolymerizationinitiater initiater (BASF JAPAN LTD. manufacture " IRGACURE907 ", 2-methyl-2-morpholino (4-methylthio group phenyl) propane-1-ketone; Hereinafter referred to as " Photoepolymerizationinitiater initiater (1) ".) 2 mass parts, Photoepolymerizationinitiater initiater (4,4 '-diethylamino benzophenone; Hereinafter referred to as " Photoepolymerizationinitiater initiater (2) ".) 2 mass parts mixing after, carry out mixing with triple-roller mill, obtain active energy ray-curable printing ink (1).Then, for gained active energy ray-curable printing ink (1), evaluate following anti-fog properties, in addition, for the cured coating film of active energy ray-curable printing ink (1), carry out the evaluation of following adaptation and solvent resistance.
[anti-fog properties evaluation]
Use inkometer (Thwing-Albert Instrument Company, " Model101 ") with 1200rpm, the condition of 32 DEG C, active energy ray-curable printing ink (1) obtained above is carried out to the circulation of the ink of 1 minute, the state (the mist amount of generation) hazed by visual observation, carrys out evaluating anti-fogging property according to following benchmark.
5: do not produce mist.
4: the mist producing denier.
3: slightly produce mist.
2: produce mist.
1: acutely produce mist.
[evaluation of adaptation]
The corona treatment PET film using bar coater #4 active energy ray-curable printing ink (1) obtained above to be coated the pet film (East paj Co., Ltd. as base material to manufacture; Thickness is 50 μm), use the high voltage mercury lamp of 80W/cm with 0.8J/cm
2ultraviolet irradiation amount make it solidify, obtain the evaluation film of adaptation.At the surface mount scotch tape of gained evaluation film, by the visual observation state that film is peeled off from base material when peeling off rapidly, evaluate adaptation according to following benchmark.
◎: film is not peeled off from base material completely.
Zero: do not peel off from base material, but in film, cohesive failure occurs, a part for film is peeled off.
△ a: part for film is peeled off from base material.
×: part whole stripping from base material of pasting scotch tape.
[evaluation of solvent resistance]
Use bar coater #4 to be coated with active energy ray-curable printing ink (1) obtained above, use the high voltage mercury lamp of 80W/cm with 0.8J/cm
2ultraviolet irradiation amount make it solidify, obtain the evaluation film of solvent resistance.By visual observation with the felt containing ethanol to the state of the film coated surface after the surface wipes 10 times of gained evaluation film, evaluate solvent resistance according to following benchmark.
Zero: unchanged.
△: residual wiping vestige.
×: ink disappears, and can confirm base material.
(embodiment 12 ~ 15 and comparative example 3)
Replace except the Actinic-radiation curable composition (1) of use in embodiment 11 except using Actinic-radiation curable composition (2) ~ (5) that obtain in embodiment 2 ~ 5 and comparative example 1 and (R1), similarly operate, prepare active energy ray-curable printing ink (2) ~ (5) and (R1).Use gained active energy ray-curable printing ink, carry out the evaluation of anti-fog properties, adaptation and solvent resistance similarly to Example 11.
(comparative example 4)
Except using in comparative example 1 Actinic-radiation curable composition (R1) 10 mass parts that obtains and rosin modified phenolic resin (" Beckasite F-7305 " that DIC Corporation manufactures) 13 mass parts to replace except Actinic-radiation curable composition (1) 23 mass parts that uses in embodiment 11, similarly operate, prepare active energy ray-curable printing ink (R2).Use gained active energy ray-curable printing ink, carry out the evaluation of adaptation, anti-fog properties and solvent resistance similarly to Example 11.
The evaluation result of the composition of the active energy ray-curable printing ink obtained in above-described embodiment 11 ~ 15, comparative example 3 and 4 and anti-fog properties, adaptation and solvent resistance is summarized in table 3.
[table 3]
Known: the anti-fog properties excellence employing the active energy ray-curable printing ink of the embodiment 11 ~ 15 of Actinic-radiation curable composition of the present invention.In addition we know: the cured coating film of active energy ray-curable printing ink of the present invention has very high adaptation to pet film, and has high solvent resistance.
On the other hand, the active energy ray-curable printing ink of comparative example 3 is the use of the example of the Actinic-radiation curable composition of polyfunctional acrylic ester (A) and the aromatic dicarboxylic acid (B) not using the present invention used, the mist amount of this active energy ray-curable printing ink known is very many, its anti-fog properties existing problems.In addition we know: the adaptation of cured coating film to pet film of this printing ink is poor, and solvent resistance is insufficient.
The active energy ray-curable printing ink of comparative example 4 is the example Actinic-radiation curable composition of the polyfunctional acrylic ester not using the present invention used (A) and aromatic dicarboxylic acid (B) and Gum Rosin combinationally used, known: when this active energy ray-curable printing ink is compared with comparative example 3, mist amount can be suppressed, but the adaptation of the cured coating film of this printing ink to pet film is poor, and does not have solvent resistance completely.
Claims (7)
1. an Actinic-radiation curable composition, it is characterized in that, it is by making polyfunctional acrylic ester (A) react with aromatic dicarboxylic acid (B) and aromatic epoxy resin (C), then makes gained reaction product carry out reacting obtaining with the carboxylic acid (D) with polymerizability unsaturated group.
2. Actinic-radiation curable composition according to claim 1, wherein, described polyfunctional acrylic ester (A) is for being selected from least a kind of polyfunctional acrylic ester in the group that is made up of Viscoat 295, ethylene-oxide-modified Viscoat 295 and glycerine propoxylate.
3. Actinic-radiation curable composition according to claim 1 and 2, wherein, described aromatic dicarboxylic acid (B) is for being selected from least a kind of aromatic dicarboxylic acid in the group that is made up of phthalic acid, m-phthalic acid and terephthalic acid.
4. the Actinic-radiation curable composition according to any one of claims 1 to 3, wherein, described aromatic epoxy resin (C) is bisphenol A type epoxy resin.
5. the Actinic-radiation curable composition according to any one of Claims 1 to 4, wherein, described in there is polymerizability unsaturated group carboxylic acid (D) be vinylformic acid.
6. an active energy ray-curable coating, is characterized in that, it contains the Actinic-radiation curable composition according to any one of Claims 1 to 5.
7. an active energy ray-curable printing ink, is characterized in that, it contains the Actinic-radiation curable composition according to any one of Claims 1 to 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-062043 | 2012-03-19 | ||
| JP2012062043 | 2012-03-19 | ||
| PCT/JP2013/057057 WO2013141117A1 (en) | 2012-03-19 | 2013-03-13 | Active energy ray-curable composition, active energy ray-curable coating material using same, and active energy ray-curable printing ink using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104220478A true CN104220478A (en) | 2014-12-17 |
| CN104220478B CN104220478B (en) | 2016-03-02 |
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| CN201380015498.2A Expired - Fee Related CN104220478B (en) | 2012-03-19 | 2013-03-13 | Actinic-radiation curable composition, the active energy ray-curable coating using it and active energy ray-curable printing ink |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5495087B2 (en) |
| CN (1) | CN104220478B (en) |
| IN (1) | IN2014DN08494A (en) |
| TW (1) | TWI557143B (en) |
| WO (1) | WO2013141117A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968001A (en) * | 2015-03-13 | 2016-09-28 | 日本化药株式会社 | Carboxyl-containing reactive compound, hardened resin composition using same, and hardened substance |
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6196877B2 (en) * | 2013-10-21 | 2017-09-13 | サカタインクス株式会社 | Active energy ray-curable offset printing ink composition and printing method using the composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1678655A (en) * | 2002-08-05 | 2005-10-05 | 昭和高分子株式会社 | Polycarboxylic acid resin, polycarboxylic acid resin composition, and cured article obtained therefrom |
| JP2010241866A (en) * | 2009-04-01 | 2010-10-28 | Tokyo Printing Ink Mfg Co Ltd | Lithographic ink and printed matter printed using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216016A (en) * | 1988-07-01 | 1990-01-19 | Showa Highpolymer Co Ltd | Manufacture of molded form |
| JP4935967B2 (en) * | 2005-07-27 | 2012-05-23 | Ｄｉｃ株式会社 | Method for producing branched polyether resin composition and method for producing acid pendant type branched polyether resin composition |
| KR100883047B1 (en) * | 2006-07-10 | 2009-02-11 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable/thermosetting resin composition, cured product thereof and printed wiring board |
-
2013
- 2013-03-13 WO PCT/JP2013/057057 patent/WO2013141117A1/en active Application Filing
- 2013-03-13 JP JP2013546113A patent/JP5495087B2/en not_active Expired - Fee Related
- 2013-03-13 CN CN201380015498.2A patent/CN104220478B/en not_active Expired - Fee Related
- 2013-03-13 IN IN8494DEN2014 patent/IN2014DN08494A/en unknown
- 2013-03-18 TW TW102109556A patent/TWI557143B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1678655A (en) * | 2002-08-05 | 2005-10-05 | 昭和高分子株式会社 | Polycarboxylic acid resin, polycarboxylic acid resin composition, and cured article obtained therefrom |
| JP2010241866A (en) * | 2009-04-01 | 2010-10-28 | Tokyo Printing Ink Mfg Co Ltd | Lithographic ink and printed matter printed using the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968001A (en) * | 2015-03-13 | 2016-09-28 | 日本化药株式会社 | Carboxyl-containing reactive compound, hardened resin composition using same, and hardened substance |
| CN105968001B (en) * | 2015-03-13 | 2020-05-08 | 日本化药株式会社 | Carboxyl group-containing reactive compound, curable resin composition using same, and cured product |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI557143B (en) | 2016-11-11 |
| IN2014DN08494A (en) | 2015-05-08 |
| CN104220478B (en) | 2016-03-02 |
| TW201343690A (en) | 2013-11-01 |
| WO2013141117A1 (en) | 2013-09-26 |
| JP5495087B2 (en) | 2014-05-21 |
| JPWO2013141117A1 (en) | 2015-08-03 |
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