CN101235235A - Ultraviolet solidifying type ink and decoration printed matter using the same - Google Patents
Ultraviolet solidifying type ink and decoration printed matter using the same Download PDFInfo
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- CN101235235A CN101235235A CN 200710003266 CN200710003266A CN101235235A CN 101235235 A CN101235235 A CN 101235235A CN 200710003266 CN200710003266 CN 200710003266 CN 200710003266 A CN200710003266 A CN 200710003266A CN 101235235 A CN101235235 A CN 101235235A
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Abstract
The invention relate to ultraviolet curing ink, which uses any one or two of 43-83 parts by weight of chloride polyester acrylic ester, 10-50 parts by weight of acryloyl morpholine and 0-35 parts by weight of light responsiveness thinner and conglomerate oligomer as main components. The ink can be conducted with printing on the surface of various materials, and has excellent adhesiveness.
Description
Technical field
The present invention relates to ultraviolet curable ink, decoration printed matter and decorated resin moulding product.
Background technology
In recent years, because problems such as environmental problem, printing productive rate replace solvent type ink, ultraviolet curable ink is widely used.Ultraviolet curable ink (uv printing ink) is to cause photochemical reaction with ultraviolet energy, is that unit is solid-state from liquid curing with the second, carries out the printing ink that epithelium forms.The main component of printing ink is optical polymerism resin, Photoepolymerizationinitiater initiater, tinting material and auxiliary agent, does not comprise organic solvent in principle.Ultraviolet curable ink in the past has open in Japanese kokai publication sho 63-117023, Japanese kokai publication hei 2-202563, Japanese kokai publication hei 6-184484 or TOHKEMY 2003-145573 etc.
But the binding property of ultraviolet curable ink in the past and specific plastics limits to some extent, and we expect to obtain printing material and be not limited, and has a multifarious ultraviolet curable ink as the solvent type ink that bounding force is widely arranged.
For example, propose among the Japanese kokai publication sho 63-117023, printing ink for the material that is used for polyvinyl chloride, polycarbonate, polymethacrylate resin, by any one or two kinds and acryloyl morpholine (ア Network リ ロ イ Le モ Le ホ リ Application with urethane acrylate (Port リ ウ レ Application ア Network リ レ one ト) and urethane methacrylate (Port リ ウ レ Application メ Network リ レ one ト), acryloyl morpholine) uses together, then can solve viscosity along with problems such as time increases.In Japanese kokai publication hei 6-184484, propose, for the printing ink that is used for polycarbonate, vinylchlorid, propenyl, processing PET, metallize panel material, by with polycaprolactone urethane origoester acrylate (ウ レ Application ア Network リ レ one ト オ リ go マ one) and caprolactam (PVC ニ Le カ プ ロ ラ Network system) and vinylformic acid phenoxy ethyl (Off エ ノ キ シ エ チ Le ア Network リ レ one ト) serve as must composition the ultraviolet curable ink constituent can solve problems such as overlapping printing, post-treatment type.
The conventional art of above-mentioned document record can not be widely used in more plastic material, and on binding property room for improvement is arranged still.
Summary of the invention
The purpose of this invention is to provide for wider plastic material provides binding property good printing ink.Particularly for the also operable printing ink of impossible polyolefin material and other materials (for example, polycarbonate, propenyl, vinylchlorid, processing PET) in the past.
The present invention relates to ultraviolet curable ink, polyester chloride acrylic ester (salt elementization Port リ エ ス テ Le ア Network リ レ one ト that contains 43～83 weight parts, chlorinated polyester acrylate), the acryloyl morpholine of 10～50 weight parts (ア Network リ ロ イ Le モ Le ホ リ Application, acryloyl morpholine), also add Photoepolymerizationinitiater initiater.
According to the present invention, provide and use above-mentioned printing ink, with the silk screen of 100～460 meshcounts plastic material is implemented the decoration printed matter that decorating printing forms.
According to the present invention, provide for polyolefine, polycarbonate, propenyl, vinylchlorid, the good printing ink of processing PET binding property.
Ultraviolet curable ink of the present invention, the main component that comprises are polyester chloride acrylic ester and acryloyl morpholine; Any one or two kinds that further preferably comprise photoresponse thinner and polyreactive oligomers, and add Photoepolymerizationinitiater initiater.
Composition irradiation ultraviolet radiation or the electron rays promptly developed ultra-violet solidified printing ink in the 1940's carry out the polymeric technology.Also developed the optical polymerism resin of acrylic ester and methacrylate ester.These optical polymerism resins are classified as oligopolymer and photoreactivity thinner.
The photoreactivity thinner uses the polyester acrylate class of high boiling monomer class and low degree of adhesion.The photoreactivity thinner has a significant impact solidified nature, binding property except the ink viscosity adjustment is used, and is very important to its selection.
Photoepolymerizationinitiater initiater: by ultraviolet energy generation free radical, the reactive group of it and monomer or oligopolymer reacts and initiated polymerization.In order to promote the initiation reaction of Photoepolymerizationinitiater initiater, sometimes also with the auxiliary agent that is called as sensitizing agent.The sensitizing agent of this moment is not by UV-activated, but plays the effect that the fill-in light polymerization starter carries out initiation reaction.
Below, each composition is described respectively.
Polyester chloride acrylic ester (salt elementization Port リ エ ス テ Le ア Network リ レ one ト used in the present invention, chlorinated polyester acrylate) can be at synthesizing chlorinated polyester (salt elementization Port リ エ ス テ Le, chlorinated polyester) after, combining of the terminal hydroxyl of vinylformic acid and its obtained by esterification.City's article for sale for example has: Ebecryl 436, the Ebecryl 438 of ダ イ セ Le サ イ テ Star Network Co., Ltd. (DAICEL-CYTEC CompanyLTD.), Ebecryl 446 etc.
Acryloyl morpholine used in the present invention (acryloylmorpholine) represent with following chemical structural formula (I) by ア Network リ ロ イ Le モ Le ホ リ Application.City's article for sale for example has: " ACMO " of Kohjin Co., Ltd..
Formula (I)
Among the present invention, as cause the used Photoepolymerizationinitiater initiater of photopolymerization reaction can give an example as: the aryl ketones 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 a kind or will be more than 2 kinds and use.
Among the present invention, Photoepolymerizationinitiater initiater can contain with the combination of light sensitizer such as amine.Light sensitizer specifically can be given an example as trolamine (trietanolamine), 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, methyl (replacing) diethanolamine light sensitizers such as (ethyl diethanol amine).
More specifically 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); oxoethanoic acid aminomethyl phenyl ester; 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-phenyl-propane-1-ketone (2-Hydroxy-2-methyl-1-phenyl-propane-1-on); 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-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-propane-1-ketone (1-[4-(2-Hydroxyethoxy) phenyl]-2-hydroxy-2-methyl-1-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 isopropyl ether); bitter almond oil camphor isobutyl ether (Benzine isobutyl ether); benzyldimethylketal (Benzil dimethyl 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); 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.
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, methacrylic ester.
Other photoreactivity thinners more specifically, 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 (Isotetradecylacrylate), vinylformic acid isooctadecane base ester (Isosteary acrylate), isobornyl acrylate (Isobonylacylate), oxyethyl group-glycol ether acrylate (Ethoxy diethyleneglycol acrylate), 2-ethylhexyl-Trivalin SF acrylate (2-Ethylhexyl carbytol acrylate), neopentyl glycol benzoic ether acrylate (Neopentylglycol benzoate acrylate), Nonylphenoxy polyethylene glycol acrylate (Nonyl phenoxy polyethyleneglycol acrylate), ECH modification phenoxy group acrylate (Phenoxy acrylate, modified ECH), phenoxyethyl acrylate (Phenoxy ethylacrylate), to cumylphenol oxyethane modification acrylate, tristane dimethanol acrylate (Tricyclodecane dimethanol acrylate), caprolactam (Vinylcaprolactam) 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 (Dimethyrol dicyclopentane 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 methacrylic ester (2-Hydroxyethyl methacrylate), 2-hydroxyl-3-acryloxy propyl methyl acid esters (2-Hydroxy 3-phenoxy propyl acrylate) etc.
Ultraviolet-curing resin composition of the present invention except that aforesaid combination, can further 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 (Oligoether acrylateoligomer) etc.
Carbamate is an oligopolymer, specifically can give an example as the Ebecryl 230 of DAICEL-CYTEC COMPANY LTD, Ebecryl 244, Ebecryl 245, Ebecryl 270, Ebecryl 284, Ebecryl285, Ebecryl 4830, Ebecryl 4835, Ebecryl 4858, Ebecryl 1290, Ebecryl 210, Ebecryl 215, Ebecryl 4827, Ebecryl 4849, Ebecryl 6700, Ebecryl 204, Ebecryl8804, 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, the Actilane200TP20 of Akcros Chemicals company, Actilane210TP30, Actilane230HD30, Actilane250HD25, Actilane250TP25, Actilane270, Actilane280, Actilane290, Actilane 165, Actilance 167, Actilane 170; Sartomer Company, 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.), AronixM1200, AronixM-1600; The KAYARAD UX-2201 of Nippon Kayaku K. K, KAYARAD UX-2301, KAYARAD UX-3204, KAYARADUX-3301, KAYARAD UX-4101, KAYARAD UX-7101 etc.
Polyethers is that the concrete example of oligopolymer can be given an example as the PO84F of BASF AG, LR-8894 etc.
Epoxy is that the concrete example of oligopolymer can be given an example as Actilane300, Actilane310, Actilane320, Actilane320DA25, Actilane340, the Actilane330 of Akcros Chemicals company; The Ebecryl 600 of DAICEL-CYTECCOMPANY LTD, Ebecryl 3500, Ebecrtl 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-CYTECCOMPANY 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 COMPANY LTD, Ebecryl 767.
Appropriateness cooperation UV light absorber, oxidation inhibitor, thermal resistance are gathered stablizers such as agent as required in the ultraviolet-curing resin composition of the present invention; Correction agent, defoamer, thickening material, anti-sludging agent, pigment dispersing agent, static inhibitor, antifogging agent etc. are surfactant-based; Various additives such as wax, slip(ping)agent, near infrared ray absorption.Also can make microparticulate such as tinting pigment or filler pigment.
In addition, in order to improve coating or printing, or adjust the viscosity of ultraviolet-curing resin composition or the thickness of cured film (printing film), also can add the non-polymerization organic solvent or add synthetic resins plastic material.
Here, organic solvent can be given an example as ester class, halogenated hydrocarbon, hydro carbons etc. such as lower alcohols, ketone, ethers, cellosolve class, n-butyl acetate, single acetic acid glycol ether esters.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 pigment of record in: coating raw material brief guide 1970 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, pearly pigments; 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 azo pigments), as: diarylide yellow (Benzidine Yellow G), organic yellow (Hansa Yellow), 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 (PhthalocyanineBlue), phthalocyanine green (Phthalocyanine Green) etc.; Various chloride dyeing are formed sediment, if Dan Mingsedian (Rhodamine Lake), methyl violet color lake (Methyl Violet Lake) etc.; Various mordanting dye series pigments are as quinoline color lake, fast sky blue (Fast Sky blue) etc.; Various vat pigment series pigments are face material (perinone pigments) as anthraquione pigmentss (anthraquinone pigments), thioindigo series pigments (thioindigo pigments), ペ リ ノ Application; Various quinacridone 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 ferrocyanide compounds, as: Prussian blue various metal oxides such as (Iron Blue), as: titanium dioxide (TitaniumDioxide), zinc white (Zinc Oxide), titan yellow (Nickel Antimony Titanium 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 (Cadmiumyellow), 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 Micapigments) of covering metal oxide form, mica shape iron oxide pigment (Micaceous iron oxide pigments) etc.; Graphite, carbon black etc.
That filler pigment can be given an example is white as: precipitation threshold barium sulfate (Precipitaed Barium sulfate), chalk, precipitated chalk, Calcium hydrogen carbonate, white Wingdale, aluminium, silicon-dioxide, moisture fine particle silica, super-fine powder anhydride silica (aerosil), silica sand, talcum, precipitation threshold magnesiumcarbonate, bentonite (bentonute), clay (China Clay), kaolin (Hydrated Aluminium Sillcate), loess (Ochre) etc.
Ultraviolet curable ink of the present invention can be used as silk screen printing and uses such as other general printing inks, coating, tackiness agent.
Ultraviolet curable ink of the present invention also can be implemented printing or spraying and bonding for difficult binding property plastic materials such as polyolefine such as polypropylene, polyethylene (Port リ オ レ Off イ Application) and ethylene-vinyl alcohol (エ チ レ Application one PVC ニ Le ア Le コ one Le) multipolymers.And, for plastic material such as polycarbonate, polyester, vinylchlorid, processing PET and paper, metal etc. easily the adherent material also can implement printing or spraying and bonding.
The method that ultraviolet curable ink 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 curable ink of the present invention carries out uviolizing after coating on the material, can form cured coating film.And, further on this cured coating film, be coated with repeatedly and solidify, can carry out the laminated coating of multilayer shape.
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.
As described above, ultraviolet curable ink of the present invention is by the polyester chloride acrylic ester that contains 43～83 weight parts, the acryloyl morpholine of 10～50 weight parts, comprise Photoepolymerizationinitiater initiater, with PP, it is good that the plastic material of the polyolefine of PE etc. and polycarbonate, propenyl, vinylchlorid, processing PET also can binding property, can implement printing, spraying, bonding etc.Therefore can be used as printing-ink, coating, tackiness agent etc. is widely used.
Below, according to more detailed embodiment, describe in detail with regard to ultraviolet curable ink of the present invention.
The printing ink of present embodiment is behind the printing ink of spraying specified amount on the printing material, makes it to solidify with uviolizing.Thereby, on this material, can form printing epithelium (cured film).
As the printing material that forms the printing epithelium, be not particularly limited, for example, PP, plastic materials such as difficult fusible plastic material, polycarbonate, polyester such as polyolefine such as PE (Port リ オ レ Off イ Application) and ethylene-vinyl alcohol (エ チ レ Application one PVC ニ Le ア Le コ one Le) multipolymer, and the material of highly adhesive such as paper, metal etc.
The method of this routine printing ink of spraying is not particularly limited on above-mentioned materials, for example, can adopt printing processes such as woodburytype, silk screen print method.
At PP, when implementing printing on the difficult fusible plastic materials such as Polyolefin and ethylene-vinyl alcohol copolymer such as PE, for the binding property that improves the printing epithelium etc., the face that is printed that is preferably in this plastic material is implemented pre-treatments such as flame treating or corona treatment.
When implementing these pre-treatments, measure according to JISK 6768 regulations " soaking into the tension test method ".For the infiltration tension force (ぬ れ Zhang power) that makes the face of being printed is being more than the 40mN/m on the PP material, is being for more than the 46mN/m, to its enforcement flame treating or corona treatment on the PE material more than the 46mN/m, on the ethylene-vinyl alcohol copolymer material.
Preferred infiltration tension force is: for more than the 48mN/m, being more than the 54mN/m on the PE material on the PP material, is more than the 54mN/m on the ethylene-vinyl alcohol copolymer material.
Below just embodiment and comparative example describe.
(embodiment 1～6) (comparative example 1～7)
As ultraviolet curing resin constituent of the present invention, embodiment 1～the 6, (unit: printing ink weight %) of the blending ratio shown in the comparative example 1～7 in the following table 1,3 have been made.
As printing material, prepare the PP plate of thickness 1.5mm and the polyester chips of thickness 0.2mm, the PP plate is carried out pre-treatment, make the infiltration tension force of the face of being printed reach 46mN/m.Then, the PP plate by silk screen print method, is printed on the face that is printed of each printing material with the printing ink of each embodiment, and obtains printed matter with the half tone of 320 meshcounts with the half tone of 460 meshcounts, polyester chips.
With these printed matters, under the metal halide lamp of 80W/cm 1 lamp, pass through once with the speed of travelling belt 5m/min, irradiation ultraviolet radiation makes cured coating film (printing epithelium).
Placement is after 24 hours down at 20 ℃ for each cured coating film, and " cross-hatching " stipulated according to JIS K 5400 8.5.2 carries out adhesion test.The result as shown in Table.
【0041】
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Polyester chloride acrylic ester (Ebecryl 436) | 83 | 70 | 43 | 88 | 33 | |||
| Epoxy is an oligopolymer | 70 | |||||||
| Carbamate is an oligopolymer | 70 | |||||||
| The acrylic ester oligopolymer | 70 | |||||||
| Acryloyl morpholine (ACMO) | 10 | 23 | 50 | 5 | 60 | 23 | 23 | 23 |
| Photoepolymerizationinitiater initiater | 6 | 6 | 6 | 6 | 6 | 6 | 6 | 6 |
| Defoamer | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Binding property to the PP plate | 10 | 10 | 10 | 4 | 6 | 0 | 0 | 0 |
| Binding property to the PET plate | 10 | 10 | 10 | 6 | 4 | 0 | 0 | 0 |
Table 3
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 6 | Comparative example 7 | |
| Polyester chloride acrylic ester (Ebecryl 436) | 70 | 43 | 70 | 66 | 76 | 34 | 34 |
| Carbamate is an oligopolymer | 4 | 40 | |||||
| Acryloyl morpholine (ACMO) | 19 | 15 | 19 | 18 | 20 | 19 | 19 |
| The vinylformic acid phenoxy ethyl | 4 | 35 | 40 | ||||
| Photoepolymerizationinitiater initiater | 6 | 6 | 6 | 15 | 3 | 6 | 6 |
| Defoamer | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Table 4
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 6 | Comparative example 7 | |
| Binding property to the PP plate | 10 | 10 | 10 | 10 | 10 | 6 | 6 |
| Binding property to the PET plate | 10 | 10 | 10 | 10 | 10 | 6 | 4 |
[0042] with embodiment 2 and 6 and comparative example 3 and 7 in resulting printed matter carry out insert moulding with acrylate resin, obtain insert-molded article.In addition, embodiment 2 and 6 and comparative example 3 and 7 in establish the middle layer with vinylchlorid vinylacetic acid multipolymer printing ink on the resulting printed matter, use the acrylate resin insert moulding again, obtain the moulding product.Specularity with the resulting moulding product of visual valuation.In addition, resulting printed matter is carried out the binding property evaluation according to JIS K 5400-1990 8.5.3X tearing paper tape method.Its result is as shown in table 5.
Table 5
◎: very good zero: good △: poor *: extreme difference
Claims (10)
1. ultraviolet curable ink, this printing ink is with the polyester chloride acrylic ester of 43～83 weight parts, the acryloyl morpholine of 10～50 weight parts, and the photoreactivity thinner of 0～35 weight part and any one or two kinds in the polyreactive oligomers are as main component.
2. the described ultraviolet curable ink of claim 1 is characterized in that: add any one or two kinds in 4～35 weight part photoreactivity thinners and the polyreactive oligomers.
3. claim 1 or 2 described ultraviolet curable inks, it is characterized in that: it has further added the Photoepolymerizationinitiater initiater of 3～15 weight parts.
4. the described ultra-violet solidified printing ink of claim 3 is characterized in that: further contain light sensitizer in the described Photoepolymerizationinitiater initiater.
5. the described ultraviolet curable ink of claim 1, it is characterized in that: it further contains a kind of of stablizer, correction agent, defoamer, thickening material, anti-sludging agent, pigment dispersing agent, static inhibitor, antifogging agent, wax, slip(ping)agent, near infrared ray absorption and tinting pigment or several added ingredientss.
6. the described ultraviolet curable ink of claim 1, it is characterized in that: it further contains non-polymerization organic solvent or synthetic resins.
7. decoration printed matter, this printed matter uses the described ultraviolet curable ink of claim 1, and the silk screen execution decorating printing of plastic material with 320～460 meshcounts formed.
8. decorated resin moulding product, these moulding product use the described ultraviolet curable ink of claim 1, behind the silk screen execution decorating printing of plastic material with 320～460 meshcounts, further one middle layer is set and forms at printing surface.
9. the described decorated resin moulding of claim 6 product is characterized in that: in the described decorated resin moulding product resin layer is set, and these decorated resin moulding product are carried out insert moulding.
10. the described ultraviolet curable ink of claim 1 application in press.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710003266 CN101235235A (en) | 2007-02-02 | 2007-02-02 | Ultraviolet solidifying type ink and decoration printed matter using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710003266 CN101235235A (en) | 2007-02-02 | 2007-02-02 | Ultraviolet solidifying type ink and decoration printed matter using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101235235A true CN101235235A (en) | 2008-08-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710003266 Pending CN101235235A (en) | 2007-02-02 | 2007-02-02 | Ultraviolet solidifying type ink and decoration printed matter using the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101235235A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174998A (en) * | 2011-02-25 | 2011-09-07 | 江苏永兴多媒体有限公司 | Manufacturing method of LED lamp panel for converting blue light into white light |
| CN102218905A (en) * | 2010-03-23 | 2011-10-19 | 精工爱普生株式会社 | Recording method, recording apparatus, and ink set |
| CN102241920A (en) * | 2011-08-15 | 2011-11-16 | 江苏海田技术有限公司 | Ultraviolet (UV) transfer ink |
| CN102729587A (en) * | 2011-04-02 | 2012-10-17 | 深圳劲嘉彩印集团股份有限公司 | Gravure printing equipment, gravure printing method, and packaging box |
| CN103666014A (en) * | 2013-11-23 | 2014-03-26 | 铜陵方正塑业科技有限公司 | Ultraviolet curing printing ink with anti-static effect and preparation method thereof |
| CN105616171A (en) * | 2014-11-26 | 2016-06-01 | 河泰锡 | Mask pack and method for manufacturing same |
| CN114773902A (en) * | 2022-04-25 | 2022-07-22 | 北京金印联国际供应链管理有限公司 | UV offset printing ink and preparation method and application thereof |
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2007
- 2007-02-02 CN CN 200710003266 patent/CN101235235A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218905A (en) * | 2010-03-23 | 2011-10-19 | 精工爱普生株式会社 | Recording method, recording apparatus, and ink set |
| CN102218905B (en) * | 2010-03-23 | 2015-09-30 | 精工爱普生株式会社 | Recording method, tape deck, ink group |
| CN102174998A (en) * | 2011-02-25 | 2011-09-07 | 江苏永兴多媒体有限公司 | Manufacturing method of LED lamp panel for converting blue light into white light |
| CN102729587A (en) * | 2011-04-02 | 2012-10-17 | 深圳劲嘉彩印集团股份有限公司 | Gravure printing equipment, gravure printing method, and packaging box |
| CN102729587B (en) * | 2011-04-02 | 2015-10-14 | 深圳劲嘉彩印集团股份有限公司 | Gravure printing apparatus, gravure process and packing box |
| CN102241920A (en) * | 2011-08-15 | 2011-11-16 | 江苏海田技术有限公司 | Ultraviolet (UV) transfer ink |
| CN103666014A (en) * | 2013-11-23 | 2014-03-26 | 铜陵方正塑业科技有限公司 | Ultraviolet curing printing ink with anti-static effect and preparation method thereof |
| CN103666014B (en) * | 2013-11-23 | 2016-03-23 | 铜陵方正塑业科技有限公司 | A kind of UV curable ink with antistatic property and preparation method thereof |
| CN105616171A (en) * | 2014-11-26 | 2016-06-01 | 河泰锡 | Mask pack and method for manufacturing same |
| CN114773902A (en) * | 2022-04-25 | 2022-07-22 | 北京金印联国际供应链管理有限公司 | UV offset printing ink and preparation method and application thereof |
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Application publication date: 20080806 |