CN1944548B - Printing ink using ultraviolet cured resin composition as active ingradient - Google Patents
Printing ink using ultraviolet cured resin composition as active ingradient Download PDFInfo
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- CN1944548B CN1944548B CN 200610087122 CN200610087122A CN1944548B CN 1944548 B CN1944548 B CN 1944548B CN 200610087122 CN200610087122 CN 200610087122 CN 200610087122 A CN200610087122 A CN 200610087122A CN 1944548 B CN1944548 B CN 1944548B
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Abstract
The present invention relates to one kind of printing ink, and the printing ink has ultraviolet cured resin composition as the effective component. The ultraviolet cured resin composition contains glyceryl monomethacrylate and/or glyceryl dimethacrylate as light reactive diluent, and may be used in printing, spraying or adhering polypropylene, polyethylene and other polyolefin, ethylene-vinyl alcohol copolymer and other un-adhesive plastic material. In addition, it may be used in printing, spraying or adhering polycarbonate, polyester, paper, metal and other adhesive material.
Description
Technical field
The present invention relates to can be used as the ultraviolet-curing resin composition of printing-ink, be specifically related to the ultraviolet-curing resin composition is the printing ink of effective constituent, wherein composition also has the binding property of appropriateness for not containing the combination that chlorine is objectionable impurities to difficult binding property plastic materials such as polypropylene (polypropylene), polyethylene polyolefine such as (polyethylene) (polyolefin) or ethylene-vinyl alcohol copolymers.
The invention still further relates to ultraviolet-curing resin composition.
Background technology
At present, polypropylene (PP), polyethylene polyolefin-based resins such as (PE) are used in a large number in fields such as auto parts, electric parts, material of construction, packaging materials for food.And polypropylene itself be the material that has fewer environmental impacts, so its use field enlarges day by day owing to do not contain objectionable impurities such as chlorine system.
Yet polyolefin-based resins is not owing to have structural functional group, and be crystallinity and nonpolar, and therefore, printing-ink, coating, the tackiness agent of combination exist paint adhesion poor usually, implements printing, sprays problem such as difficulty.For this polyolefin-based resins is implemented printing etc.
In patent documentation 1 (TOHKEMY 2005-139305 communique), proposed to contain the ultraviolet-curing resin composition of chlorinatedpolyolefins (chlorinated polyolefin) as adhesive resin.
Yet it is the material chlorinatedpolyolefins that above-mentioned traditional UV curable resin composition contains chlorine, is the combination useful to environment hardly.
Summary of the invention
The present invention proposes in view of this conventional situation, its purpose is to provide the ultraviolet-curing resin composition as novel printing printing ink, and wherein composition also can form difficult binding property plastic materials such as polyolefine such as polypropylene, polyethylene or ethylene-vinyl alcohol copolymers and have appropriate fusible printing film.
The object of the invention also is to provide the ultraviolet-curing resin composition as printing ink, wherein composition be do not contain chlorine be objectionable impurities to the useful combination of environment, simultaneously can satisfy aforementioned adhesion.
In view of above-mentioned conventional situation, the present inventor is research with keen determination repeatedly, the result learns: contain the composition glycerin monomethyl acrylic ester useful to environment (Glycerol monomethacrylate) by making, glycerine dimethacrylate (Glycerol dimethacrylate) is as the ultraviolet-curing resin composition of photoreactivity thinner, even do not contain chlorinatedpolyolefins etc., also can be to polyethylene, plastic materials such as polyolefine such as polypropylene or ethylene-vinyl alcohol copolymer form has appropriate fusible printing film, coating film, binder films etc. have finally been finished the present invention.
Promptly, ultraviolet-curing resin composition of the present invention is characterised in that: contain Photoepolymerizationinitiater initiater and photoreactivity thinner at least, wherein contain any one or two kinds of as above-mentioned photoreactivity thinner of glycerin monomethyl acrylic ester and glycerine dimethacrylate.
Specifically it is characterized in that: for being used as printing-ink, coating, the ultraviolet-curing resin composition of tackiness agent, for following composition (still, do not comprise chlorine based polymer and monomer) ultraviolet curing resin, comprise that 1-99% weight is as photoreactivity thinner (Reactive Diluents, glycerin monomethyl acrylic ester Monomer) and glycerine dimethacrylate any one or two kinds of, 1-15% weight Photoepolymerizationinitiater initiater (photoinitiator), other photoreactivity thinners of 0-90% weight, 0-90% weight polyreactive oligomers (Olygomer), the 0-70% weight polymer, 0-15% weight photosensitizers (photosensitizer), 0-20% weight additive, 0-65% weight pigment.
The used glycerin monomethyl acrylic ester of the present invention (Glycerol monomethacrylate) can be exemplified below and state glycerin monomethyl acrylic ester shown in the general formula (1).Commercially available product can be given an example as " BLEMMER-GLM " of NOF Corp.
General formula (1)
The used glycerine dimethacrylate of the present invention (Glycerol dimethacrylate) can be exemplified below and state glycerine dimethacrylate shown in the general formula (2).Commercially available product can be given an example as " BLEMMER-GMR-H " of NOF Corp.
General formula (2)
The used Photoepolymerizationinitiater initiater of the present invention, can give an example as: arone class Photoepolymerizationinitiater initiater is (for example: the benzyldimethylketal class, acetophenones (acetophenon type), benzoin ethers, benzophenone (benzophenone type), the oximinoketone class, the alkylamino benzophenone, the benzyl class, the bitter almond oil camphor class, benzoylbenzoic acid ester class, α-acyl oxime ester class etc.), sulfur-bearing be Photoepolymerizationinitiater initiater (for example: sulfide-based, thioxanthene ketone (thioxanton type) etc.), other can be used for the various Photoepolymerizationinitiater initiaters of ultraviolet-curing resin composition.
Among the present invention, Photoepolymerizationinitiater initiater can contain independent more than a kind or 2 kinds and use.
Among the present invention, Photoepolymerizationinitiater initiater can contain with the combination of photosensitizers such as amine.Photosensitizers specifically can be given an example as trolamine (trietanolamine), 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, methyl (replacing) diethanolamine (ethyl diethanol amine) etc.
Further; concrete Photoepolymerizationinitiater initiater can give an example as: 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone (2; 2-Dimethoxy-1; 2-diphenylethane-1-on); 1-hydroxy-cyclohexyl benzophenone (1-Hydroxy-cyclohexyl-phenylketone); benzophenone (Benzophenone); 2; 2-dimethoxy-2-phenyl methyl phenyl ketone; 2; 4-diethyl thioxanthone (2; 2-Diethylthio xthanthone); isopropyl thioxanthone (Osopropyl thioxthanthone); 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide (2; 4; 6-Trimethlbenzoyl diphenylphosphine oxide); the aminomethyl phenyl oxoethanoic acid; two-2; 4; (Bis (2 for 6-trimethylbenzoyl phenyl phosphine oxide; 4; 6-trimethylbenzoyl)-phenylphosphineoxide); 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 (2-Benzyl-2-dimethylamaion-1-(4-morphorinophenyl) butanone-1); 4-phenoxy group dichloroacetophenone; two (2; 6-dimethoxy benzoyl)-2; 4; (Bis (2 for 4-trimethylammonium-amyl group phosphine oxide; 4; 6-trimethylbenzoyl)-phenylphosphineoxide); the 4-tertiary butyl-dichloroacetophenone; the 4-tertiary butyl-Trichloroacetophenon; diethoxy acetophenone; 2-hydroxy-2-methyl-1-phenylpropyl alcohol alkane-1-ketone (2-Hydroxy-2-methyl-1-phenyl-propane-1-on); 2-hydroxyl-3-acryloyl-oxy propyl methyl acid esters; the 2-hydroxyethyl meth acrylate; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone (1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one); 1-(4-dodecylphenyl)-2-methylpropane-1-ketone; 1-[4-(2-hydroxy ethoxy) phenyl]-2-hydroxy-2-methyl-propane-1-ketone (1-[4-(2-Hydroxyethoxy) phenyl]-2-hydroxy-2-methyl-l-propane-1-on); 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone (2-methyl-1[4-(methylthio) phenyl]-2-morphorinopropane-1-on); benzyl (Benzil); bitter almond oil camphor (Benzoin); benzoin methyl ether (Benzoine methyl ether); bitter almond oil camphor ethyl ether (Benzoine ethylether); bitter almond oil camphor isopropyl ether (Benzoine isopropylether); bitter almond oil camphor isobutyl ether (Benzine isobutyl ether); benzyldimethylketal (Benzildimethyl ketal); the benzoyl phenylformic acid; benzoyl methyl benzoate (Methyl-o-benzoylbenzoate); 4-phenyl benzophenone (4-Phenylbenzophenone); dihydroxy benaophenonel; propylene acidylate benzophenone (Acrylated benzophenon); 3; 3 '-dimethyl-4-methoxy benzophenone; 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone (3; 3 '; 4; 4 '-Tetra-(t-butylperoxrcarbonyl) benzophenone); 9; the 10-phenanthrenequione; camphorquinone; dibenzosuberone; 2-ethyl-anthraquinone (2-ethyl antherquinone); 4 '; 4 "-diethyl isophthaloyl benzene; α-acyl oxime ester; 4-benzoyl-4 '-methyldiphenyl sulfide (4-Benzoyl-4 '-methyldiphenyl sulphide); thioxanthone; 2-clopenthixal ketone (2-Chloro thioxthanthone); 2-methyl thioxanthone; 2; 4-dimethyl thioxanthone (2; 4-Diethylthioxantone); 2; 4-two clopenthixal ketones; 2,4-di-isopropyl thioxanthone; acylphosphine oxide etc.
Ultraviolet-curing resin composition of the present invention can contain any or two kinds as the above-mentioned glycerin monomethyl acrylic ester of photoreactivity thinner and glycerine dimethacrylate, further also can contain other photoreactivity thinner.
Other photoreactivity thinners can be given an example as: aliphatic series (methyl) acrylate, ester ring type system (methyl) acrylate, aromatics system (methyl) acrylate, ether system (methyl) acrylate, ethene base system monomer, (methyl) acrylic amide etc.Wherein (methyl) acrylate refers to contain at least a kind of of acrylate, an acrylate.
Further, concrete other photoreactivity thinners, can give an example as vinylformic acid Lauryl Ester (Laurylacrylate), vinylformic acid stearyl (Stearyl acrylate), vinylformic acid cyclohexyl ester (Cyclohexylacrylate), isooctyl acrylate ester (Isooctyl acrylate), the different tetradecyl ester of vinylformic acid (Isotetradecyl acrylate), vinylformic acid isooctadecane base ester (Isosteary acrylate), isobornyl acrylate (Isobonyl acylate), oxyethyl group-glycol ether acrylate (Ethoxy diethyleneglycolacrylate), 2-ethylhexyl-Trivalin SF acrylate (2-Ethylhexyl carbytol acrylate), neopentyl glycol phenylformic acid acrylate (Neopentylglycol benzoate acrylate), Nonylphenoxy polyethylene glycol acrylate (Nonyl phenoxy polyethyleneglycol acrylate), ECH modification phenoxy group acrylate (Phenoxy acrylate, modified ECH), phenoxyethyl acrylate (Phenoxy ethyl acrylate), to cumylphenol oxyethane modification acrylate, tristane dimethanol acrylate (Tricyclodecane dimethanol acrylate), caprolactam (Vinylcaprolactam), acryloyl morpholine (Acryloyl morpholine), 1,6-hexanediyl ester (1,6-Hexanediol diacrylate), 2-hydroxyl-3-propionyloxy propyl methyl acid esters (2-Hydroxy-3-acryloyloxy propyl methacrylate), 1,9-nonanediol diacrylate (1,9-Nonannediol diacrylate), dihydroxymethyl two cyclopentyl diacrylates (Dimethyroldicyclopentane diacrylate), neopentylglycol diacrylate (Neopentylglycoldiacrylate), neopentyl glycol poly(propylene oxide) modification diacrylate, polyethyleneglycol diacrylate (Polyethyleneglycol diacrylate), dipentaerythritol acrylate (DPHA, Dipentaerythritol hexaacrylate), polytetramethylene glycol diacrylate (Polytetramethyleneglycol), 2-butyl-2-ethyl-1, ammediol diacrylate (2-Buthyl-2-ethyl-1.3-propanediol diacrylate), Viscoat 295 (Trimethylolpropane triacrylate), TriMethylolPropane(TMP) oxyethane modification triacrylate (Trimethylolpropane triacrylate, modified EO), 2-hydroxyethyl meth acrylate (2-Hydroxyethyl methacrylate), 2-hydroxyl 3-phenoxy propyl acrylate (2-Hydroxy 3-phenoxy propyl acrylate), vinylformic acid 2-ethylhexyl-glycol ether ester (2-Ethyl hexyl diglycol acrylate), vinylformic acid methoxy poly (ethylene glycol) ester (Methoxypolyethyleneglycol acrylate), the two third glycosides alcohol esters (Methoxydipropyleneglycol acrylate) of vinylformic acid methoxyl group, vinylformic acid phenoxy group macrogol ester (Phenoxypolyethyleneglycol acrycol acrylate), the acrylate of nonylphenol EO adduct (Arcylate of ethyleneoxide modifited nonylphenol), tetrahydrofurfuryl acrylate (Tetrahdro furfueyl acrylate), vinylformic acid 2-hydroxy methacrylate (2-Hydroxyethyl acrylate), vinylformic acid 2-hydroxy propyl ester (2-Hydroxypropyl acrylate), vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester (2-Hydroxy 3-phencxy propyl acrylate), succsinic acid 2-acryloxy ethyl ester (2-Acryloyloxy ethyl succinnate), hexahydrophthalic acid 2-acryloxy ethyl ester (2-Acryloyloxyethyl hexahydro phthalate), phthalic acid 2-acryloxy ethyl-2-hydroxy methacrylate (2-Acryloloxy ethyl 2-hydoxy ethyl phthalate), diacrylate triethyleneglycol ester (Trithyleneglycol diacrylate), diacrylate 3-methyl isophthalic acid, 5-pentadiol ester (3-Methyl-1.5-pentanediol diacrylate), dihydroxyl methyl tristane diacrylate (Dimethylol tricycle decane diacrylate), the diacrylate of the PO adduct of dihydroxyphenyl propane (Diacrylate of ethylene oxide modified bisphenol A) etc.
Ultraviolet-curing resin composition of the present invention except that aforesaid combination, further can contain polyreactive oligomers
Polyreactive oligomers, can give an example as: carbamate is that oligopolymer (Urethane acrylateoligomer), polyethers are that oligopolymer, epoxy are that oligopolymer (Epoxy acrylate oligomer), polyester are oligopolymer (Polyether acrylate oligomer), acrylic ester oligopolymer (Oligoetheracrylate oligomer) etc.
Further, carbamate is an oligopolymer, specifically can give an example as the Ebecryl 230 of DAICEL-CYTECCOMPANY LTD, Ebecryl 244, Ebecryl 245, Ebecryl 270, Ebecryl 284, Ebecryl 285, Ebecryl 4830, Ebecryl 4835, Ebecryl 4858, Ebecryl1290, Ebecryl 2210, Ebecryl 215, Ebecryl 4827, Ebecryl 4849, Ebecryl 6700, Ebecryl 204, Ebecryl 8804, Ebecryl 8800-20R, Ebecryl 204; The AH-600 of Kyoeisha Chemical Co., Ltd., AT-600, UA-306H; The Beamset502H of Arakawa Chemical Industries, Ltd., Beamset504H, Beamset505A-6, Beamset550B, Beamset575; Actilane200, Actilane200TP20, Actilane210TP30, Actilane230HD30, Actilane250HD25, Actilane250TP25, Actilane270, Actilane280, Actilane290, Actilane165, Actilance167, the Actilane170 of Akcros Chemicals company; SartomerCompany, the CN929 of Inc. company, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN983E80, CN964, CN965, CN980, CN981; Toagosei Co., Ltd (Toagosei Co., AronixM-1100 Ltd.), M1200, AronixM-1600; KAYARAD UX-2201, the KAYARADUX-2301 of Nippon Kayaku K. K, KAYARAD UX-3204, KAYARAD UX-3301, KAYARAD UX-4101, KAYARAD UX-7101 etc.
Polyethers is the concrete example of oligopolymer, can give an example as the P084F of BASF AG, LR-8894 etc.
Epoxy is the concrete example of oligopolymer, can give an example as Actilane300, Actilane310, Actilane320, Actilane320DA25, Actilane340, the Actilane330 of Akcros Chemicals company; The Ebecryl 600 of DAICEL-CYTECCOMPANY LTD, Ebecryl 3500, Ebecryl 3600, Ebecryl 3700-20H, EB Ebecryl 3702; Sartomer Company, the CN104 of Inc., CN111, CN115, CN151 etc.
Polyester is the concrete example of oligopolymer, can give an example as the Beamset700 of Arakawa Chemical Industries, Ltd., Beamset710, Beamset720, Beamset730, Beamset750; The Ebecryl 770 of DAICEL-CYTEC COMPANY LTD, Ebecryl 81, Ebecryl 830; The AronixM-6100 of Toagosei Co., Ltd, AronixM-6200, AronixM-7100 etc.
The concrete example of acrylic ester oligopolymer can be given an example as the Ebecryl 1701 of DAICEL-CYTEC COMPANYLTD, Ebecryl 767.
Ultraviolet-curing resin composition of the present invention except that aforesaid combination, further can contain polymkeric substance.
Polymkeric substance can use the polymkeric substance that is dissolved in ultraviolet-curing resin composition of the present invention.For example can use: thermoplastic acrylic resin, vinyl chloride copolymer, Resins, epoxy, derivatived cellulose etc.
In the ultraviolet-curing resin composition of the present invention, can appropriateness cooperate stablizers such as UV light absorber, oxidation inhibitor, the poly-agent of thermal resistance in case of necessity; Correction agent, defoamer, thickening material, anti-sludging agent, pigment dispersing agent, static inhibitor, preventing atomization agent etc. are surfactant-based; Various additives such as wax, slip(ping)agent, near infrared ray absorption.Further, also can make microparticulate such as tinting pigment or filler pigment.
In addition, in order to improve coating or printing, or adjust the viscosity or cured film (printing film, the coating film etc.) thickness of ultraviolet-curing resin composition, also can dose the non-polymerization organic solvent or add synthetic resins plastic material.
Organic solvent can be given an example as ester classes such as lower alcohols, ketone, ethers, cellosolve class, n-butyl acetate, single acetic acid glycol ether ester, halogenated hydrocarbon, hydro carbons etc.And, when the PC (polycarbonate resin) of lining poor solvent resistance, preferred lower alcohol, cellosolve class, ester class and their mixture.
The pigment that can further add in case of necessity in the used ultraviolet-curing resin composition of the present invention can be given an example as pigment dyestuff or mineral dyes such as the filler pigments of record in 1970 year of: the coating raw material handbook version (Japanese coating industry can be compiled), white pigments, mineral black, gray paint, red pigment, brown pigments, veridian, blue pigments, violet pigment, metal powder pigment, high-visibility pigment, pearl pigment; Further can give an example as plastic pigment etc.
Above-mentioned pigment dyestuff can be given an example as various insoluble azo colours (non laked azopigments), as: diarylide yellow (Benzidine Yellow G), the Chinese husky yellow (HansaYellow), C lake red CAN'T 4R (Permanent Red 4R) etc.; Solubility azo pigment (Azo laked Pigments) is as Lake red C (Lake Red C), carmine 6B (Brilliant Carmine 6B), purplish red 10 (Bordeaux Lake 10) etc.; Various (copper) phthalocyanine (phthalocyanine pigments) series pigments is as phthalocyanine blue (Phthalocyanine Blue), phthalocyanine green (Phthalocyanine Green) etc.; Various chloride dyeing are formed sediment, if Dan Mingsedian (Rhodamine Lake), methyl violet color lake (Methyl VioletLake) etc.; Various mordanting dye series pigments are as quinoline color lake, strong green grass or young crops (Fast Sky blue) etc.; The various dyestuff series pigments of building are as anthraquione pigmentss (anthraquinone pigments), thioindigo series pigments (thioindigo pigments), ペ リ ノ Application series pigments (perinone pigments); Various quinoline bifurcation pyridine series pigments are as red B of the expensive look of aquatic foods (Cinquasia Red B) etc.; Various dioxazine pigments are as dioxazine violet (dioxazine Violet) etc.; Various polycondensation azo pigment are as Cromophtal etc.; Nigrosine (Pigment black 1) etc.
Above-mentioned mineral dye can be given an example as various chromic salt, as: chrome yellow (Chrome Yellow), zinc chromate (Basic ZincPotassium Chromate), molybdate orange (Molybdate Orange) etc.; Various ferrocyanic acid compounds, as: Prussian blue (Iron Blue) etc.; Various metal oxides, as: titanium dioxide (Titanium Dioxide), zinc white (Zinc Oxide), titan yellow (Nickel AntimonyTitanium Yellow Rutile), ferric oxide (Synthetic Iron Oxide Black), red iron oxide (Synthetic Iron Oxide Red), chromoxide green (Chromium Oxide Green) etc.; Various sulfide or selenide are as cadmium yellow (Cadmium yellow), cadmium red (Cadmium red), zunsober (Chinese vermilion) etc.; Various vitriol, as: barium sulfate, lead sulfate etc.; Various silicate are as Calucium Silicate powder, ultramarine (Ultramarine Blue) etc.; Various carbonate, as: lime carbonate, magnesiumcarbonate etc.; Various phosphoric acid salt, as: cobalt violet (Cobalt Violet), manganese violet (Manganese Violet); Various metallic powdery pigments are as aluminium powder, bronze, silver powder, copper powder, bronze powder, brass powder etc.; The flaky pigment of above-mentioned metal, mica sheet pigment; Metallic pigment or pearly pigment, as: the mica sheet pigment (Metal oxide coated Mica pigments) of covering metal oxide form, mica shape iron oxide pigment (Micaceous iron oxide pigments) etc.; Graphite, carbon black etc.
Filler pigment,, the silicon-dioxide white of can giving an example, moisture fine particle silica (white carbon black), super-fine powder anhydride silica (aerosil), silica sand (quartz sand), talcum, precipitation threshold magnesiumcarbonate, bentonite (bentonute), clay (China Clay), kaolin (Hydrated AluminiumSilicate), loess (Ochre) etc. as: precipitation threshold barium sulfate (Precipitaed Barium sulfate), chalk, precipitated chalk, Calcium hydrogen carbonate, Mirabilitum crystallina, aluminium.
Ultraviolet-curing resin composition of the present invention can contain photoreactivity thinner---glycerin monomethyl acrylic ester and/or the glycerine dimethacrylate of 1-99% weight as necessary composition.Preferably containing of this photoreactivity thinner is proportional for 1-45% weight.
The Formulation Example of ultraviolet-curing resin composition of the present invention, as shown in table 1 below.
[table 1]
| Material | Containing in ultraviolet-curing resin composition proportional (% weight) |
| Glycerin monomethyl acrylic ester and/or glycerine dimethacrylate | 1-99 |
| Other photoreactivity thinners | 0-90 |
| Polyreactive oligomers | 0-90 |
| Polymkeric substance | 0-70 |
| Photoepolymerizationinitiater initiater | 1-15 |
| Material | Containing in ultraviolet-curing resin composition proportional (% weight) |
| Photosensitizers | 0-15 |
| Additive | 0-20 |
| Tinting pigment, filler pigment | 0-65 |
| Add up to | 100 |
Ultraviolet-curing resin composition of the present invention can be used for silk screen printing or other general printing inks, coating, tackiness agent etc.
Ultraviolet-curing resin composition of the present invention for difficult binding property plastic materials such as polyolefine such as polypropylene, polyethylene or ethylene-vinyl alcohol copolymers, can be implemented printing or spraying or bonding.And, also can implement printing or spraying or bonding to plastic materials such as polycarbonate, polyester or highly adhesive materials such as paper, metal.
The method that ultraviolet-curing resin composition of the present invention is coated on above-mentioned material does not have particular determination, for example can use: coating methods such as intaglio plate coating method, rolling method, curtain coating method, spraying coating method; Print process such as woodburytype, silk screen print method.
Ultraviolet-curing resin composition of the present invention carries out uviolizing by after coating on the material, can form cured coating film.And, further by on this cured coating film, being coated with repeatedly and solidifying, can carry out the coating of multilayer shape lamination.
Difficult binding property plastic material such as polyolefine such as polypropylene, polyethylene or ethylene-vinyl alcohol copolymer is implemented printing or spraying or when bonding, preferably this plastic material implemented pre-treatments such as flame treating or corona treatment.
Ultraviolet-curing resin composition of the present invention, as described above, be combined to form owing to contain at least as any of the glycerin monomethyl acrylic ester of photoreactivity thinner and glycerine dimethacrylate, therefore good to plastic material stickiness such as polyolefine such as polypropylene, polyethylene or ethylene-vinyl alcohol copolymers, can implement good printing, spraying, gluing etc. to above-mentioned difficult adhesive material.Therefore, can be widely used as printing-ink, coating, tackiness agent etc.
In addition, because not contain chlorine be that adhesive resin can obtain above-mentioned effect, therefore, waste recovery or recycle when waiting does not have the danger of objectionable impurities generation, has many effects such as exceedingly useful as the new ultra-violet line curable resin composition of environment-friendly type.
Embodiment
Below, the embodiment of the invention is described.
At first, preparation is as the following prescription sample 1-3 of ultraviolet-curing resin composition of the present invention.
(sample 1)
Photoreactivity thinner glycerin monomethyl acrylic ester: 95% weight
Photoepolymerizationinitiater initiater 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone: 5% weight
(sample 2)
Photoreactivity thinner glycerine dimethacrylate: 95% weight
Photoepolymerizationinitiater initiater 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone: 5% weight
(sample 3)
Photoreactivity thinner glycerin monomethyl acrylic ester: 47.5% weight
Photoreactivity thinner glycerine dimethacrylate: 47.5% weight
Photoepolymerizationinitiater initiater 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone: 5% weight
Next, prepare polypropylene (PP) plate, polyethylene (PE) plate as the thickness 2.0mm of test materials, each material surface is implemented pre-treatment, make wetting tension: polypropylene board is that 40mN/m, polyethylene board are 46mN/m.
, use said sample 1-3, on the surface of each test materials, use 380 order silk screen versions, implement printing, obtain test and use print,, make cured coating film (printing epithelium) these print irradiation ultraviolet radiations by silk screen print method thereafter.
Placement is after 24 hours down in 20 ℃ for each cured coating film, and " the checker adhesive tape method " stipulated among the employing JIS K 54008.5.2 carried out the stickiness test to it, and all samples, Total Test material all can obtain the evaluation of " 10 ".
Below,, further describe as the situation of printing for ultraviolet-curing resin composition of the present invention based on specific embodiment with the outer curable ink of purple line.
For printing ink of the present invention, coat specified amount on the printing material after, make its curing by uviolizing, can on this material, form the printing epithelium (cured coating film).
The printing material that is used to form the printing epithelium is not particularly limited, and can give an example as difficult binding property plastic materials such as polyolefine such as polypropylene, polyethylene or ethylene-vinyl alcohol copolymers; Highly adhesive materials such as plastic material such as polycarbonate, polyester or paper, metal etc.
The method of the printing ink that coating is originally given an example on above-mentioned materials is not particularly limited, and for example can adopt: print processes such as woodburytype, silk screen print method.
When on difficult binding property plastic materials such as polyolefine such as polypropylene, polyethylene or ethylene-vinyl alcohol copolymer, implementing printing,, preferably implement pre-treatments such as flame treating or corona treatment on the face being printed of this plastic material in order to improve printing epithelium stickiness etc.
When implementing above-mentioned pre-treatment, " wetting tension test method " according to regulation among the JIS K 6768 measured, implement flame treating or corona treatment, make to be printed the face wetting tension: polypropylene material is that 40mN/m is above, polythene material is that 46mN/m is above, the ethylene-vinyl alcohol copolymer material is more than the 46mN/m.
Preferred wetting tension: polypropylene material is that 48mN/m is above, polythene material is that 54mN/m is above, the ethylene-vinyl alcohol copolymer material is more than the 54mN/m.
Below, embodiment and comparative example are described.
(embodiment 1-9)
As ultraviolet-curing resin composition of the present invention, prescription (unit: printing ink % weight) shown in the embodiment 1-9 among the preparation following table 2-4.
Prepare polypropylene board, polyethylene board, ethylene-vinyl alcohol copolymer plate as the thickness 1.5mm of printing material, implement pre-treatment, make above-mentioned materials be printed the face wetting tension: polypropylene board is that 40mN/m, polyethylene board are that 46mN/m, ethylene-vinyl alcohol copolymer material are 46mN/m., adopt 460 order silk screen plates,, the printing ink of each embodiment is printed in each printing material moral is printed face, obtain print by silk screen print method thereafter.
Make above-mentioned print under the metal halide lamp of 80W/cm1 lamp, cross travelling belt No. 1 time, carry out uviolizing, make cured coating film (printing epithelium) with the speed of 5m/min.
Placement is after 24 hours down in 20 ℃ for each cured coating film, and " the checker adhesive tape method " stipulated among the employing JIS K54008.5.2 carries out the stickiness test, and the result as shown in Table.
(comparative example 1-9)
As record in the table, the printing ink prescription of preparation comparative example 1-9 (unit: % weight), carry out same stickiness test with the foregoing description.The result as shown in Table.
[table 2]
[table 3]
[table 4]
From above result as can be known: contain at least as any ultraviolet curable ink that is combined to form of the glycerin monomethyl acrylic ester of photoreactivity thinner and glycerine dimethacrylate good bonding to difficult adhesive materials such as polyolefine such as PP, PE or ethylene-vinyl alcohol copolymers.
Relative therewith, as can be known: do not contain glycerin monomethyl acrylic ester and glycerine dimethacrylate any, only contain the comparative example of other photoreactivity thinner, to above-mentioned difficult adhesive material poor adhesion.
More than the printing-ink that contains ultraviolet-curing resin composition of the present invention is explained, it will be understood by those skilled in the art that, ultraviolet-curing resin composition of the present invention can add in coating and the tackiness agent equally and uses, and its bond properties to materials such as polypropylene, polyethylene and ethylene-vinyl alcohol copolymers can be proved from the foregoing description.
More than, the example example of ultraviolet-curing resin composition of the present invention is illustrated; But the present invention is not limited to these embodiment, and also there is the possibility of all changes in the technological thought category of much less putting down in writing in each claim.
Claims (6)
1. printing-ink, with the ultraviolet-curing resin composition is effective constituent, described composition is by 1-99% weight any one or two kinds of as the glycerin monomethyl acrylic ester of photoreactivity thinner and glycerine dimethacrylate, 1-15% weight Photoepolymerizationinitiater initiater, other photoreactivity thinners of 0-90% weight, 0-90% weight polyreactive oligomers, the 0-70% weight polymer, 0-15% weight photosensitizers, 0-20% weight additive and 0-65% weight pigment are formed, wherein said Photoepolymerizationinitiater initiater is selected from arone class Photoepolymerizationinitiater initiater and sulfur-bearing is any one or two kinds of of Photoepolymerizationinitiater initiater, it is oligopolymer that described polyreactive oligomers is selected from carbamate, polyethers is an oligopolymer, epoxy is an oligopolymer, polyester is oligopolymer and acrylic ester oligopolymer, and described polymkeric substance is selected from the thermoplastic acrylic resin, vinyl chloride copolymer, Resins, epoxy and derivatived cellulose.
2. the described printing-ink of claim 1, it is characterized in that described other photoreactivity thinners are selected from the vinylformic acid Lauryl Ester, the vinylformic acid stearyl, the vinylformic acid cyclohexyl ester, the isooctyl acrylate ester, the different tetradecyl ester of vinylformic acid, vinylformic acid isooctadecane base ester, isobornyl acrylate, oxyethyl group-glycol ether acrylate, 2-ethylhexyl-Trivalin SF acrylate, neopentyl glycol phenylformic acid acrylate, the Nonylphenoxy polyethylene glycol acrylate, ECH modification phenoxy group acrylate, phenoxyethyl acrylate, to cumylphenol oxyethane modification acrylate, tristane dimethanol acrylate, caprolactam, acryloyl morpholine, 1, the 6-hexanediyl ester, 2-hydroxyl-3-propionyloxy propyl methyl acid esters, 1,9-nonanediol diacrylate, dihydroxymethyl two cyclopentyl diacrylates, neopentylglycol diacrylate, neopentyl glycol poly(propylene oxide) modification diacrylate, polyethyleneglycol diacrylate, dipentaerythritol acrylate, the polytetramethylene glycol diacrylate, 2-butyl-2-ethyl-1, the ammediol diacrylate, Viscoat 295, TriMethylolPropane(TMP) oxyethane modification triacrylate, 2-hydroxyethyl meth acrylate and 2-hydroxyl 3-phenoxy propyl acrylate, vinylformic acid 2-ethylhexyl-glycol ether ester, vinylformic acid methoxy poly (ethylene glycol) ester, the two third glycosides alcohol esters of vinylformic acid methoxyl group, vinylformic acid phenoxy group macrogol ester, the acrylate of nonylphenol EO adduct, tetrahydrofurfuryl acrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, succsinic acid 2-acryloxy ethyl ester, hexahydrophthalic acid 2-acryloxy ethyl ester, phthalic acid 2-acryloxy ethyl-2-hydroxy methacrylate, the diacrylate triethyleneglycol ester, diacrylate 3-methyl isophthalic acid, the 5-pentadiol ester, dihydroxyl methyl tristane diacrylate, the diacrylate of the PO adduct of dihydroxyphenyl propane.
3. a printing forming composition is used the described printing-ink of claim 1, implements printing and form on the plastic material that is formed by polyolefine or ethylene-vinyl alcohol copolymer.
4. ultraviolet-curing resin composition, wherein said composition is by 1-99% weight any one or two kinds of as the glycerin monomethyl acrylic ester of photoreactivity thinner and glycerine dimethacrylate, 1-15% weight Photoepolymerizationinitiater initiater, other photoreactivity thinners of 0-90% weight, 0-90% weight polyreactive oligomers, the 0-70% weight polymer, 0-15% weight photosensitizers, 0-20% weight additive and 0-65% weight pigment are formed, wherein said Photoepolymerizationinitiater initiater is selected from arone class Photoepolymerizationinitiater initiater and sulfur-bearing is any one or two kinds of of Photoepolymerizationinitiater initiater, it is oligopolymer that described polyreactive oligomers is selected from carbamate, polyethers is an oligopolymer, epoxy is an oligopolymer, polyester is oligopolymer and acrylic ester oligopolymer, and described polymkeric substance is selected from the thermoplastic acrylic resin, vinyl chloride copolymer, Resins, epoxy and derivatived cellulose.
5. the coating that contains the described ultraviolet-curing resin composition of claim 4.
6. the tackiness agent that contains the described ultraviolet-curing resin composition of claim 4.
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| JP4665050B2 (en) * | 2008-01-15 | 2011-04-06 | 株式会社きもと | Curable composition, cured product and laminate |
| CN101831208B (en) * | 2009-03-13 | 2013-01-09 | 恒昌涂料（惠阳）有限公司 | Photocureable coating for digital electronic products |
| JP5609321B2 (en) * | 2010-06-30 | 2014-10-22 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable ink composition |
| EP2836369B1 (en) * | 2012-04-12 | 2019-02-27 | Hewlett-Packard Development Company, L.P. | Media composition |
| JP5994393B2 (en) * | 2012-05-31 | 2016-09-21 | 株式会社リコー | Photopolymerizable inkjet ink, ink cartridge, inkjet printing apparatus |
| CN102841503B (en) * | 2012-09-18 | 2013-12-04 | 江苏科技大学 | Photolithographic electronic silver paste composition for touch screen and preparation thereof |
| JP6299275B2 (en) * | 2013-05-15 | 2018-03-28 | 株式会社リコー | Photopolymerizable inkjet ink, ink cartridge, coated material |
| JP6757522B2 (en) * | 2013-05-15 | 2020-09-23 | 株式会社リコー | Photopolymerizable curable composition, composition set, cured product and method for producing cured product |
| US20160257818A1 (en) * | 2015-03-06 | 2016-09-08 | Daisuke Mezaki | Layered product and method for producing same, and layered product producing apparatus |
| JP6938168B2 (en) * | 2017-02-28 | 2021-09-22 | デクセリアルズ株式会社 | Method for producing a laminate and a photocurable resin composition |
| WO2018163942A1 (en) * | 2017-03-07 | 2018-09-13 | 東レ株式会社 | Actinic-ray-curable ink for lithographic printing and method for producing printed matter using same |
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