CN102241919A - Ink composition for roller printing - Google Patents

Abstract

Disclosed is an ink composition for roller printing. A fluorine-based solvent is added to the ink composition to reduce the surface tension of the ink, thereby providing excellent coating performance, effectively preventing lateral and vertical stripes, and improving defoaming performance.

Description

The roll printing ink composite

Technical field

Disclosed hereinly the present invention relates to a kind of ink composite that is used for roll printing (roll printing); More specifically, relate to a kind of like this ink composite that is used for roll printing, it has the outstanding coating performance and the antifoam performance of improvement by the surface tension that reduces printing ink.

Background technology

Used fine pattern in the display unit (for example semiconductor circuit arrangement, LCD and PDP) adopts photo-resist to form by photoetch method usually.Although photoetch method has the advantage that can accurately obtain required pattern, defective is: need to implement a lot of steps, use the material of a lot of types to make the photoresist maximum effect, and use a large amount of photo-resists during handling (as coating).

Therefore, at present, as the method for future generation that overcomes the photoetch method defective, suggestion is adopted roll printing method or ink jet printing method and is obtained the technology of fine pattern.

By adopting roll printing to form in the process of fine pattern, can use polytype method, as offset printing, counter-rotating offset printing (reverse offset printing), cylinder turnover printing (roll-to-roll printing) etc.Therefore, they can be widely used in R (redness), G (green) and these colors of B (blueness), and they are components of the pattern of colour filter, black matrix" (BM) pattern, the electrode that forms thin film transistor (TFT) and plasma display panel (PDP) and the pattern transfer of partition (partition) material etc.

Adopting reverse offset printing (it is one of representative roll printing method) to form in the process of pattern, pattern forms by following three steps: from blanket (blanket) the coating printing ink of coating machine to cylinder, with stereotype undesired pattern of transfer printing from the blanket, then with pattern transfer remaining on the blanket on glass substrate.

The most basic integral part of drive unit conduct that Zylinderdruckwerk generally can comprise coating machine, cylinder, drum drive, stereotype or substrate platen and be used to proofread and correct this platform; In addition, also can comprise stereotype and/or tube cleaning arrangement, be absorbed in drying installation and the polytype sensor device that solvent on the blanket comes dry blanket by absorbing those.

Adopt the levels of precision and the pattern transfer effect of the formed pattern of roll printing method to depend on processing condition to a great extent, for example printing ink is from the coating machine impression pressure that the interval between platform and the blanket forms when situation that the blanket of cylinder is coated with, volatilization degree that the coating back is being transferred to solvent before stereotype or the substrate and waiting time and the transfer printing.

Especially, the formation of the homogeneity of whole pattern and various stains is determined by the coating condition that is applied in the blanket process as the roll printing the first step.Therefore, when expanding when the solvent that is comprised in the blanket absorption coating printing ink, the variation in thickness of this blanket self can greatly influence the pattern transfer process of implementing by roll printing.

In addition,, then can increase after coating printing ink up to the waiting time of solvent evaporates if the rate of volatilization of contained solvent is lower in the printing ink, thus the time that the printing ink of increase treatment time and coating contacts with blanket.Therefore, blanket is understood further lyosorption and is expanded.

In addition, in order to be coated with evenly, require the surface energy of printing ink should be lower than the surface energy of blanket.Through being often used as the material of blanket, and use tensio-active agent to reduce the surface energy of printing ink usually based on the material of polydimethylsiloxane (PDMS).Silica-based or the fluorine based surfactant of the general employing of tensio-active agent for this purpose; And, use excessive tensio-active agent usually in order to reduce the surface energy of printing ink.But, although but in this case the surface energy of printing ink some reduce, thereby the antifoam performance of printing ink descends and produces coating defects, as horizontal and vertical striped etc.In addition, if even excessive tensio-active agent has been used in coating during printing ink, then the surface tension of printing ink can be hanged down so that institute's pattern that forms can be able to reduce in the sintering rear surface very much, and can be to last handling process (for example coating (overcoating) process) again generation remarkably influenced.

Therefore; when coming the transfer printing fine pattern, make that used solvent preferably should have following character in the printing ink with roll printing: can farthest reduce the expansion of blanket, volatilization fast, antifoam performance and coating performance outstanding, after curing, have very high surface energy so that can not produce remarkably influenced last handling process (for example applying the process of supercoat).In addition, roll printing should not influence the dispersing of pigments ability with solvent used in the printing ink.

Summary of the invention

The invention provides a kind of ink composite that is used for roll printing, it has outstanding blanket coating performance and antifoam performance, can not produce defective (as longitudinal stripe), and have high surface energy.

Specific embodiments of the present invention provides the ink composite that is used for roll printing, and it comprises a kind of fluorine-based solvent as solvent.

The content of described solvent is based on whole 100 weight part composition meters, can be for about 50 to about 90 weight parts.

The content of the fluorine-based solvent in the described solvent can be for about 0.2 to about 5.0 weight parts.

Fluorine-based solvent can be and is selected from a kind of based in the solvent of hydrogen fluorine ether.

Fluorine-based solvent can be 2-trifluoromethyl-3-oxyethyl group ten difluoro hexanes (2-trifluoromethyl-3-ethoxydodecafluorohexane).

In addition, this ink composite that is used for roll printing also can further comprise tinting material, adhesive resin, polyfunctional monomer and initiator.

So, can comprise about 2 tinting materials to about 15 weight parts; About 1 adhesive resin to about 20 weight parts; About 1 polyfunctional monomer to about 30 weight parts; And about 0.1 initiator to about 5.0 weight parts.

The ink composite that is used for roll printing also can comprise about 5 or the tensio-active agent of weight part still less in addition, based on the gross weight meter of said composition.

Embodiment

Hereinafter, will elaborate the present invention.

The present invention is used for the ink composite of roll printing, except that the moiety of routine, also comprises a kind of fluorine-based solvent especially as a kind of solvent composition.

Fluorine-based solvent of the present invention is to be selected from based on one or more of the solvent of hydrogen fluorine ether, its boiling point about 70 ℃ to about 170 ℃ of scopes, and can be 2-trifluoromethyl-3-oxyethyl group ten difluoro hexanes.

If the boiling point of fluorine-based solvent is low excessively, then solvent is easy to volatilize and reduces the effect deterioration of surface energy as tensio-active agent.On the contrary, if boiling point is too high, then printing back solvent is difficult to dryly, and therefore is difficult to obtain the pattern wanted.

The example of fluorine-based solvent of the present invention comprises from the HFE-7000 of 3M company, HFE-7100, HFE-7200, HFE-7300, HFE-7500, HFE-7600, FC-3283, FC4430 and EGC-1720.

Although traditional fluorine based surfactant can reduce the surface energy of printing ink, this tensio-active agent deterioration the antifoam performance of printing ink, thereby produce coating defects, as horizontal and vertical striped.In addition, even after, with excessive tensio-active agent coating printing ink the surface tension of printing ink can hang down very much so that the pattern that forms its surface energy reduction and last handling process (coating procedure again) had remarkably influenced behind sintering.

But fluorine-based solvent of the present invention does not have problems by using fluorine based surfactant, and effectively reduces the surface energy of printing ink.

Among the present invention, based on the composition meter of whole 100 weight parts, the content of solvent can for about 50 to about 95 weight parts, preferred about 70 to about 90 weight parts.When the amount of solvent was less than about 50 weight parts, the viscosity of printing ink became Tai Gao so that printing ink is unsuitable for coating process.When the amount of solvent during greater than about 95 weight parts, the solids content of printing ink is too low so that for making the required coating thickness of film thickness that obtains to want behind the sintering become blocked up, thereby the ink setting speed after the coating became slowly to have influence on printing process.

In addition, based on the composition of whole 100 weight parts, in the solvent content of fluorine-based solvent can for about 0.2 to about 5.0 weight parts, preferred about 0.3 to about 2.0 weight parts.

When the content of fluorine-based solvent was less than about 0.2 weight part, the surface tension of printing ink can not fully reduce, and levelling property or wettability during coating are bad, thereby are not easy to realize coating.When the content of solvent during greater than about 5.0 weight parts, but the compatibility deterioration of solvent and resin causing coacervation, but and use excessive solvent deterioration antifoam performance.

With regard to solubility, pigment dispersibility and application properties, as roll printing with the solvent that is comprised in the ink composite, except fluorine-based solvent, following solvent also can be separately or used with the form of two or more mixtures wherein: one or more are selected from benzene, toluene, ethylbenzene, dimethylbenzene, Resorcinol and hexane based on the solvent of aromatic hydrocarbon; One or more are selected from methyl alcohol, ethanol, Virahol, Tetraglycol 99, methoxypropanol, oxyethyl group propyl alcohol, butoxy propyl alcohol and phenylcarbinol based on the solvent of alcohol; One or more are selected from Monomethylamine, monoethylamine, monoethanolamine, 1-amino-2-propyl alcohol, 2-methylethylolamine, dimethylethanolamine, methyl-2-pyrrolidone, diethanolamine, DEAE diethylaminoethanol and trolamine based on the solvent of amine; One or more are selected from butyrolactone, propyl acetate, ethyl acetate, ethyl propionate, Pyruvic Acid Ethyl ester, butylacetate, ethyl lactate, 2-hydroxy-methyl isobutyl acid, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 2-ethoxy ethyl ester, propionic acid ethyl ethoxylated ester, n-Butyl lactate, diethylene glycol monomethyl ether acetic ester, diethylene glycol monobutyl ether acetic ester, ethylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetic ester based on the solvent of acetic ester (acetate); One or more are based on the solvent of ether, be selected from tetrahydrofuran (THF), 1,4-dioxane, 1-methoxyl group-2-propyl alcohol, anisole, dibutyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene Glycol B ether, diethylene glycol diethyl ether, dipropylene glycol list ether, dipropylene glycol monomethyl ether, dipropylene glycol butyl ether, phenyl ether and acetate 3-methoxyl group butyl ester; And one or more are based on the solvent of ketone, are selected from acetic ester, pimelinketone, methyl butyl ketone, 2-heptanone and butyrolactone.

In addition, outside desolventizing, the ink composite that the present invention is used for roll printing also can further comprise tinting material, adhesive resin, polyfunctional monomer, initiator and other additives.

The kind of tinting material is as follows.

The present invention is used for the ink composite of roll printing, the example that is used for showing the red pigment of color character can comprise: naphthol red pigment, as Pig.Red#1 (C.I.12070), Pig.Red#2 (C.I.12310), Pig.Red#3 (C.I.12120), Pig.Red#4 (C.I.12085), Pig.Red#5 (C.I.12490), Pig.Red#6 (C.I.12090), Pig.Red#7 (C.I.12420), Pig.Red#8 (C.I.12355), Pig.Red#9 (C.I.12460), Pig.Red#10 (C.I.12440), Pig.Red#11 (C.I.12430), Pig.Red#12 (C.I.12385), Pig.Red#13 (C.I.12395), Pig.Red#14 (C.I.12380), Pig.Red#15 (C.I.12465), Pig.Red#16 (C.I.12500), Pig.Red #17 (C.I.12390), Pig.Red #18 (C.I.12350), Pig.Red #21 (C.I.12300), Pig.Red#22 (C.I.12315), Pig.Red#23 (C.I.12355), Pig.Red#31 (C.I.12360), Pig.Red#32 (C.I.12320), Pig.Red#95 (C.I.15897), Pig.Red#112 (C.I.12370), Pig.Red#114 (C.I.12351), Pig.Red#119 (C.I.12469), Pig.Red#146 (C.I.12485), Pig.Red#147 (C.I.12433), Pig.Red#148 (C.I.12369), Pig.Red#150 (C.I.12290), Pig.Red#151 (C.I.15890), Pig.Red#184 (C.I.12487), Pig.Red#187 (C.I.12486), Pig.Red#188 (C.I.12467), Pig.Red#210 (C.I.12474), Pig.Red#245 (C.I.12317), Pig.Red#253 (C.I.12375), Pig.Red#258 (C.I.12318) and Pig.Red#261 (C.I.12468); The complex compound of naphthols and metal is as Pig.Red#49 (C.I.15630), Pig.Red#49:1 (C.I.15630:1), Pig.Red#49:2 (C.I.15630:2), Pig.Red#49:3 (C.I.15630:3), Pig.Red#50:1 (C.I.15500:1), Pig.Red#51:1 (C.I.15580:1), Pig.Red#53 (C.I.15585), Pig.Red#53:1 (C.I.15585:1), Pig.Red#68 (C.I.15525), Pig.Red#243 (C.I.15910) and Pig.Red#247 (C.I.15915); Tetrazo pyrazoline ketone is as Pig.Red#37 (C.I.21205), Pig.Red#38 (C.I.21210) and Pig.Red#41 (C.I.21200); The disazo condensation thing is as Pig.Red#144 (C.I.20735), Pig.Red#166 (C.I.20035), Pig.Red#220 (C.I.20055), Pig.Red#221 (C.I.20065) and Pig.Red#242 (C.I.20067); 2-hydroxyl-3-naphthoic acid metal complex is as Pig.Red#48:1 (C.I.15865:1), Pig.Red#48:2 (C.I.15865:2), Pig.Red #48:3 (C.I.15865:3), Pig.Red #48:4 (C.I.15865:4), Pig.Red#48:5 (C.I.15865:5), Pig.Red#52:1 (C.I.15860:1), Pig.Red#52:2 (C.I.15860:2), Pig.Red#57:1 (C.I.15850:1), Pig.Red#58:2 (C.I.15825:2), Pig.Red#58:4 (C.I.15825:4), Pig.Red#63:1 (C.I.15880:1), Pig.Red#63:2 (C.I.15880:2), Pig.Red#64 (C.I.15800), Pig.Red#64:1 (C.I.15800:1) and Pig.Red#200 (C.I.15867); The naphthene sulfonic acid metal complex is as Pig.Red#60:1 (C.I.16105:1), Pig.Red #66 (C.I.18000:1) and Pig.Red #67 (C.I.18025:1); Triaryl carbon is as Pig.Red#81:1 (C.I.45160:1), Pig.Red#81:3 (C.I.45160:3) and Pig.Red#169 (C.I.45160:2); The anthraquinone class is as Pig.Red#89 (C.I.60745) and Pig.Red#177 (C.I.65300); The thioindigo class is as Pig.Red#88 (C.I.73312) and Pig.Red#181 (C.I.73360); The quinacridine ketone is as Pig.Red#122 (C.I.73915), Pig.Red#207 (C.I.73900) and Pig.Red#209 (C.I.73905); The perylene class is as Pig.Red#123 (C.I.71145), Pig.Red#149 (C.I.71137), Pig.Red#178 (C.I.71155), Pig.Red #179 (C.I.71130), Pig.Red #190 (C.I.71140), Pig.Red #194 (C.I.71100) and Pig.Red#224 (C.I.71127); The benzoglyoxaline ketone is as Pig.Red#171 (C.I.12512), Pig.Red#175 (C.I.12513), Pig.Red#176 (C.I.12515), Pig.Red#185 (C.I.12516) and Pig.Red#208 (C.I.12514); The pyranthrone class is as Pig.Red#216 (C.I.59710); Diketopyrrolopyrrolecocrystals is as Pig.Red#254 (C.I.56110); And the isoindoline class, as Pig.Red#260 (C.I.56295).

The example of violet pigment can comprise: triaryl carbon, as Pig.Violet#1 (C.I.45170:2), Pig.Violet#2 (C.I.45175:1), Pig.Violet#3 (C.I.42535:2), Pig.Violet#27 (C.I.42535:3) and Pig.Violet#39 (C.I.42555:2); The anthraquinone class is as Pig.Violet#5:1 (C.I.58055:1); Aphthols is as Pig.Violet#25 (C.I.12321) and Pig.Violet#50 (C.I.12322); The quinacridine ketone is as Pig.Violet#19 (C.I.73900); Dioxazine is as Pig.Violet#23 (C.I.51319) and Pig.Violet#37 (C.I.51345); The perylene class is as Pig.Violet#29 (C.I.71129); And the benzoglyoxaline ketone, as Pig.Violet#32 (C.I.12517).

The example of blue pigments can comprise: triaryl carbon, as Pig.Blue#1 (C.I.42595:2), Pig.Blue#2 (C.I.44045:2), Pig.Blue#9 (C.I.42025:1), Pig.Blue#10 (C.I.44040:2), Pig.Blue#14 (C.I.42600:1), Pig.Blue#18 (C.I.42770:1), Pig.Blue#19 (C.I.42750:1), Pig.Blue#56 (C.I.42800) and Pig.Blue#62 (C.I.44084); The Cu phthalocyanines is as Pig.Blue#15 (C.I.74160) and Pig.Blue#15:1 (C.I.74160); The metal-free phthalocyanine class is as Pig.Blue#16 (C.I.74100); The indanthrone class is as Pig.Blue#60 (C.I.69800) and Pig.Blue#64 (C.I.69825); Indigo class is as Pig.Blue#66 (C.I.73000) and Pig.Blue#63 (C.I.73015:x).

The example of veridian can comprise: triaryl carbon, as Pig.Green#1 (C.I.42040:1), Pig.Green#2 (C.I.42040:1) and Pig.Green#4 (C.I.42000:2); The Cu phthalocyanines is as Pig.Green#7 (C.I.74260) and Pig.Green#36 (C.I.74265); And metal complex, as Pig.Green#8 (C.I.10006) and Pig.Green#10 (C.I.12775).

The example of yellow ultramarine can comprise: the monoazo class, as Pig.Yeuow#1 (C.I.11680), Pig.Yellow#2 (C.I.11730), Pig.Yellow#3 (C.I.11710), Pig.Yellow#5 (C.I.11660), Pig.Yellow#6 (C.I.11670), Pig.Yellow#10 (C.I.12710), Pig.Yellow#49 (C.I.11765), Pig.Yellow#65 (C.I.11740), Pig.Yellow#73 (C.I.11738), Pig.Yellow#74 (C.I.11741), Pig.Yellow#75 (C.I.11770), Pig.Yellow#97 (C.I.11767), Pig.Yellow#98 (C.I.11727), Pig.Yellow#111 (C.I.11745), Pig.Yellow#116 (C.I.11790) and Pig.Yellow#167 (C.I.11737); Monoazo metal complex is as Pig.Yeuow#61 (C.I.13880), Pig.Yellow#62:1 (C.I.13940:1), Pig.Yellow #100 (C.I.19140:1), Pig.Yellow #168 (C.I.13960), Pig.Yellow#169 (C.I.13955) and Pig.Yellow#183 (C.I.18792); Di-acetyl acetyl aryl class (bisacetoacetarylride) is as Pig.Yeuow#16 (C.I.20040); P-diaminodiphenyl (diarylride) class is as Pig.Yellow#12 (C.I.21090), Pig.Yellow#13 (C.I.21100), Pig.Yellow#14 (C.I.21095), Pig.Yellow#17 (C.I.21105), Pig.Yellow#55 (C.I.21096), Pig.Yellow#63 (C.I.21091), Pig.Yellow#81 (C.I.21127), Pig.Yellow#83 (C.I.21108), Pig.Yellow#87 (C.I.21107:1), Pig.Yellow#113 (C.I.21126), Pig.Yellow#114 (C.I.21092), Pig.Yellow#124 (C.I.21107), Pig.Yellow#126 (C.I.21101), Pig.Yellow#127 (C.I.21102), Pig.Yellow#152 (C.I.21111), Pig.Yellow#170 (C.I.21104), Pig.Yellow#171 (C.I.21106), Pig.Yellow#172 (C.I.21109), Pig.Yellow#174 (C.I.21098); Flavanthrones is as Pig.Yellow#24 (C.I.70600); The diazonium condenses is as Pig.Yellow#93 (C.I.20710), Pig.Yellow#94 (C.I.20038), Pig.Yellow#95 (C.I.20034), Pig.Yellow#128 (C.I.20037) and Pig.Yellow#166 (C.I.20035); The anthraquinone class is as Pig.Yellow#123 (C.I.65049) and Pig.Yellow#147 (C.I.60645); The aldazine class is as Pig.Yeuow#101 (C.I.48052); Naphthene sulfonic acid-metal complex is as Pig.Yeuow#104 (C.I.15985:1); The anthracene miazines is as Pig.Yellow#108 (C.I.68420); The isoindoline ketone is as Pig.Yellow#109 (C.I.56284), Pig.Yellow#110 (C.I.56280), Pig.Yellow#139 (C.I.56298) and Pig.Yellow#185 (C.I.56290); The benzoglyoxaline ketone is as Pig.Yellow#123 (C.I.11783), Pig.Yellow#154 (C.I.13980), Pig.Yellow#175 (C.I.11784), Pig.Yellow#180 (C.I.21290) and Pig.Yellow#181 (C.I.11777); Quinophthalone (quinophthalone) class is as Pig.Yellow#138 (C.I.56300); Metal complex is as Pig.Yellow#117 (C.I.48043), Pig.Yellow#129 (C.I.48042), Pig.Yellow#150 (C.I.12764), Pig.Yellow#153 (C.I.48545), Pig.Yellow#177 (C.I.48120) and Pig.Yellow#179 (C.I.48125).

In addition, the example of orange pigments can comprise: the monoazo class, as Pig.Orange#1 (C.I.11725) and Pig.Orange#6 (C.I.12730); Aphthols is as Pig.Orange#2 (C.I.12060), Pig.Orange#5 (C.I.12075), Pig.Orange#22 (C.I.12470), Pig.Orange#24 (C.I.12305) and Pig.Orange#38 (C.I.12367); Naphthols-metal complex is as Pig.Orange #17 (C.I.15510:1), Pig.Orange #17:1 (C.I.15510:2) and Pig.Orange#46 (C.I.15602); Tetrazo pyrazoline ketone is as Pig.Orange#13 (C.I.21110) and Pig.Orange#34 (C.I.21115); Diphenyl amine is as Pig.Orange#15 (C.I.21130), Pig.Orange#16 (C.I.21160); Naphthene sulfonic acid-metal complex is as Pig.Orange#19 (C.I.15990); The disazo condensation thing is as Pig.Orange#31 (C.I.20050); The benzoglyoxaline ketone is as Pig.Orange#36 (C.I.11780) and Pig.Orange#60 (C.I.11782); Pyranthrone is as Pig.Orange#40 (C.I.59700); Purple cyclic ketones (perinone) class is as Pig.Orange#43 (C.I.71105); The quinacridine ketone is as Pig.Orange#48 (C.I.73900); And the isoindoline class, as Pig.Orange#61 (C.I.11265), Pig.Orange#66 (C.I.48210) or Pig.Orange#69 (C.I.56292).

The tinting material that comprises black pigment can be the mixture of carbon black and two or more tinting pigments.The sooty example can comprise: SEAST 5HIISAF-HS, SEAST KH, SEAST 3HHAF-HS, SEAST NH, SEAST 3M, SEAST 300HAF-LS, SEAST 116HMMAF-HS, SEAST 116MAF, SEAST FMFEF-HS, SEAST SOFEF, SEAST VGPF, SEAST SVHSRF-HS and SEAST SSRF that Tokai Carbon company produces; The DIAGRAM BLACK II that MitsubishiChemical company produces, DIAGRAM BLACK N339, DIAGRAM BLACK SH, DIAGRAM BLACK H, DIAGRAMLH, DIAGRAM HA, DIAGRAM SF, DIAGRAM N550M, DIAGRAM M, DIAGRAM E, DIAGRAM G, DIAGRAM R, DIAGRAM N760M, DIAGRAM LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B; The PRINITEX-U that Degussa company produces, PRINITEX-V, PRINITEX-140U, PRINITEX-140V, PRINITEX-95, PRINITEX-85, PRINITEX-75, PRINITEX-55, PRINITEX-45, PRINITEX-300, PRINITEX-35, PRINITEX-25, PRINITEX-200, PRINITEX-40, PRINITEX-30, PRINITEX-3, PRINITEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100 and LAMP BLACK-101; And the RAVEN-1100ULTRA of Colombia Carbon company production, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA and RAVEN-1170.

The example of the tinting material that can use with carbon black can comprise: CARMINE 6B (C.I.12490), PHTHALOCYANINE GREEN (C.I.74260), PHTHALOCYANINE BLUE (C.I.74160), MITSUBISHI CARBON BLACK MA100, PERYLENE BLACK (BASF K0084.K0086), CYANINE BLACK, LIONOL YELLOW (C.I.21090), LIONOL YELLOW GRO (C.I.21090), BENZIDINE YELLOW 4T-564D, MITSUBISHI CARBON BLCAKMA-40, VITTORIA PURE BLUE (C.I.42595), C.I.PIGMENT RED97,122,149,168,177,180,192,215, C.I.PIGMENT GREEN 7,36, C.I.PIGMENT BLUE 15:1,15:4,15:6,22,60,64, C.I.PIGMENT 83,139, C.I.PIGMENT VIOLET 23, white pigment and high-visibility pigment.In addition, above-mentioned tinting material can be separately or is used obtaining black with the form of its two or more mixtures, but is not limited only to these.

Among the present invention,, can comprise about 2 to about 15 weight parts, preferred about 2.5 tinting materials to about 13 weight deals based on the gross weight of composition.When the amount of tinting material is less than about 2 weight parts, may not produce required dead color.On the contrary, when the amount of tinting material during greater than about 15 weight parts, but the pigment content in the formed coated thin film is so high so that its physical properties of deterioration.

The used adhesive resin of ink composite that the present invention is used for roll printing can comprise the acryl multipolymer of band ethylenic unsaturated group, but is not limited only to this.

The acryl multipolymer of employed band ethylenic unsaturated group can prepare in the following manner among the present invention: reactive group is introduced in the copolymer resin, and monomer and the multiple monomer of described copolymer resin by will containing acid groups carries out copolymerization through addition reaction by polymer reaction and obtains.

The monomeric example that contains acid groups can comprise and is selected from the following material one or more: (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, toxilic acid, fumaric acid, monomethyl toxilic acid, isoprene sulfonic acid and styrene sulfonic acid, but be not limited only to these.

Can comprise in the following material one or more with the monomeric example that the monomer that contains acid groups carries out copolymerization: vinylbenzene; chloro-styrene; alpha-methyl styrene; Vinyl toluene; (methyl) methyl acrylate; (methyl) ethyl propenoate; (methyl) butyl acrylate; (methyl) benzyl acrylate; (methyl) dimethylaminoethyl acrylate; (methyl) isobutyl acrylate; (methyl) tert-butyl acrylate; (methyl) cyclohexyl acrylate; (methyl) isobornyl acrylate; (methyl) vinylformic acid 2-phenoxy ethyl; (methyl) tetrahydrofurfuryl acrylate; (methyl) Hydroxyethyl acrylate; (methyl) vinylformic acid 2-hydroxypropyl acrylate; (methyl) vinylformic acid 2-hydroxyl-3-chloropropyl ester; (methyl) vinylformic acid 4-hydroxyl butyl ester; (methyl) vinylformic acid acyl group octyl group oxygen-2-hydroxypropyl acrylate; EHA; (methyl) vinylformic acid 2-methoxyl group ethyl ester; (methyl) vinylformic acid 3-methoxyl group butyl ester; ethoxydiglycol (methyl) acrylate; methoxyl group triglycol (methyl) acrylate; methoxyl group tripropylene glycol (methyl) acrylate; methoxy poly (ethylene glycol) (methyl) acrylate; phenoxy group glycol ether (methyl) acrylate; to Nonylphenoxy polyoxyethylene glycol (methyl) acrylate; to Nonylphenoxy polypropylene glycol (methyl) acrylate; (methyl) vinylformic acid tetrafluoro propyl ester; (methyl) vinylformic acid 1; 1; 1; 3; 3; 3-hexafluoro isopropyl ester; (methyl) vinylformic acid octafluoro pentyl ester; (methyl) vinylformic acid 17 fluorine esters in the last of the ten Heavenly stems; (methyl) vinylformic acid tribromophenyl; succsinic acid hydrogen β-(methyl) acryloxy ethyl ester (β-(meth) acyloloxyethylhydrogen succinate); the alpha-hydroxymethyl methyl acrylate; the alpha-hydroxymethyl ethyl propenoate; alpha-hydroxymethyl propyl acrylate and alpha-hydroxymethyl butyl acrylate, but be not limited only to these.

In addition, be used for the example that the ethylenic unsaturated group is incorporated into the reactive group of copolymer resin tackiness agent can be comprised one or more of following material: (methyl) glycidyl acrylate, vinyl benzyl glycidyl ether, vinyl glycidyl ether, glycidyl allyl ether, 4-methyl-4,5-epoxy amylene, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxy propyl-triethoxysilicane and norcamphyl derivative, but be not limited only to these.

Contain the ethylenic unsaturated group the acryl multipolymer acid number preferably about 0 to about 200KOH mg/g scope.Different with photo-resist used in the photoetch method, the used thermosetting ink composition of roll printing does not need the alkali development treatment, so multipolymer does not need to have any acid number.When the acid number of resin greater than about 200 the time, disadvantage is that the content of ethylenic unsaturated group reduces, thus state of cure reduces because of crosslinking reaction.

In addition, contain the ethylenic unsaturated group AP-52 weight-average molecular weight preferably about 1,000 to about 200,000, more preferably from about 3,000 to about 30,000 scope.

The amount of acryl multipolymer that contains the ethylenic unsaturated group is based on the ink composite meter that is used for roll printing, can for about 1 to about 20 weight parts, preferred about 2 to about 16 weight parts.When the amount of the propylene-based copolymer that contains the ethylenic unsaturated group during, be used for the resinous principle deficiency of bonding each moiety, thereby can not satisfy the color filter pattern physical properties desired, as basic thermotolerance and chemical resistant properties less than about 1 weight part.When the amount of this multipolymer during greater than about 20 weight parts, the viscosity of prepared composition is too high so that be difficult to keep the homogeneity of film when coating, and the content of other components (as pigment and so on) reduces, thereby can not satisfy needed chromatic characteristic.

In addition, the polyfunctional monomer that ink composite comprised that the present invention is used for roll printing can comprise a kind of like this functional monomer, but this monomer has been introduced a kind of unsaturated group and boiling point about 100 ℃ or higher compound or caprolactone that contains at least one addition polymerization in dividing.

But contain unsaturated group and boiling point about 100 ℃ or the higher compound of at least one addition polymerization, can comprise being selected from one or more following monofunctional monomers: polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate and (methyl) vinylformic acid phenoxy ethyl; And be selected from one or more following polyfunctional monomers: polyoxyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, trimethylolethane trimethacrylate acrylate, Viscoat 295, neopentyl glycol (methyl) acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate and dipentaerythritol acrylate, but be not limited only to these.

In addition, the polyfunctional monomer of having introduced caprolactone can comprise: introduced KAYARAD DPCA-20,30,60 and 120 Dipentaerythritol, introduce the vinylformic acid tetrahydrofuran ester of KAYARAD TC-110S, or introduced neopentyl glycol hydroxy new pentane acid ester of KAYARAD HX-220 and 620 etc.

Other example that is applicable to polyfunctional monomer of the present invention can comprise: the epoxy acrylate of bisphenol-a derivative, phenolic aldehyde-epoxy acrylate and based on the polyfunctional acrylic ester (as U-324A, U15HA or U-4HA) of carbamate.Polyfunctional monomer can be separately or is used with the form of two or more mixtures wherein.

The amount of this polyfunctional monomer is based on the composition total weight meter, can have (based on the solids content base of the ink composite that is used for roll printing, amount is about 5 to about 50 weight %) to about 25 weight parts to about 30 weight parts, preferred about 2 for about 1.When the amount of polyfunctional monomer was less than about 1 weight part, the intensity of coated thin film reduced.When the amount of polyfunctional monomer during greater than about 30 weight parts, the adhesive power of ink resin layer is too high, the undercapacity of film, and easily adhere to impurity.

The example that is used for the used initiator of ink composite of roll printing can comprise: thermal polymerization, as azonitrile compound, as V-60, V-65, V-59, V-70 and V-40; The azo ester compound is as V-601; The azo amide compound is as VA-086, VA-085, VA-080, Vam-110, Vam-111 and VF-096; The azo amidine compound is as V-50, VA-044, VA-046B, Aam-027, VA-060, VA-057 and VA-061; And the macromole azo initiator, as VPS-0501, VPS-1001, VPE-0201, VPE-0401, VPE-0601 and VPTG-0301, more than all can buy from Wako Pure Chemical Industries company, but be not limited only to these.

The content of thermal polymerization is preferably about 0.1 to about 5.0 weight parts based on the gross weight meter of composition.When the amount of thermal polymerization during less than about 0.1 weight part, the insufficient generation of heat polymerization, thereby the physical properties of ink film is easy to deterioration.When the amount of thermal polymerization during greater than about 5.0 weight parts, use excessive thermal polymerization can be reduced in solubility in the printing ink, thus the precipitation of generation; The thermal decomposition product of thermal polymerization produced pollution when perhaps it can be owing to thermofixation.

Being used for the ink composite of roll printing, optionally use silica-based or fluorine based surfactant.Especially, the example of silica-based surfactant can comprise: the product that can buy from BYK-Chemie, its trade mark is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380 or BYK-390.

In addition, can to comprise that one or more are selected from following from DaiNippon Ink﹠amp for the example of fluorine based surfactant; The product that Chemicals (DIC) buys: trade mark is F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441 or TF-1442, but be not limited only to these.

It is about tensio-active agent of 18 to about 23mN/m that the ink composite that is used for roll printing also can comprise surface energy in addition.By further comprising the tensio-active agent of surface energy in this scope, further improved the coating performance and the antifoam performance of blanket.

The content of tensio-active agent is based on the gross weight meter of composition, can be about 1.0 or weight part still less.That is to say that the present invention comprises fluorine-based solvent, thereby can not comprise tensio-active agent, preferably with about 1.0 or still less weight part comprise tensio-active agent on a small quantity.When tensio-active agent when using routinely greater than the excessive amount of about 1.0 weight parts, disadvantage is and can has problems, as the antifoam performance deterioration.

If necessary, the ink composite that is used for roll printing also can contain one or more additives in addition, as is selected from curing catalyst, thermal polymerization inhibitor, softening agent, adhesion promotor and filler.Content of additive is preferably about 0.01 to about 2 weight parts based on the gross weight meter of composition.

Hereinafter, will explain in more detail to the present invention with the following Examples.But these embodiment only provide for the example illustration purpose, are not intended to the scope of the invention is limited.

Embodiment 1

Based on the roll printing of whole 100 weight parts blue ink meter, following material is mixed: the PIGMENT BLUE#15:6 of 2.29 weight parts and the PIGMENT VIOLET#23 of 0.94 weight part are as tinting material; 4.206 a kind of like this polymkeric substance of weight part (Mw=9,000, A.V.90) as resin glue, in this polymkeric substance, mol ratio is 70: 30 ((methyl) benzyl acrylates: introduced glycidyl allyl ether in the multipolymer (methyl) vinylformic acid); 6.567 the dipentaerythritol acrylate of weight part is as the functional monomer; 0.5 the thermal polymerization of the azo-based acid amides of weight part (V-40, Wako Pure Chemical Industries company), 1.616 weight parts based on the 3-methacryloxypropyl trimethoxy silane of the dispersion agent of polyester and 0.1 weight part as additive; And the acetone of pure and mild 7.255 weight parts of methoxy propyl of the propylene glycol monoethyl ether acetate of 49.197 weight parts, 26.879 weight parts is as solvent; And the HFE-7500 of 0.45 weight part from 3M company mixed with gained solution as fluorine-based solvent.Subsequently, this mixture is stirred 5 hours with preparation printing ink composition.

Embodiment 2

A kind of blue ink that is used for roll printing makes in the mode identical with embodiment 1, only is to use HFE-7000 to replace among the embodiment 1 the HFE-7500 that comes from 3M company as fluorine-based solvent.

Embodiment 3

A kind of blue ink that is used for roll printing makes in the mode identical with embodiment 1, only is to use HFE-7100 to replace among the embodiment 1 the HFE-7500 that comes from 3M company as fluorine-based solvent.

Embodiment 4

A kind of blue ink that is used for roll printing makes in the mode identical with embodiment 1, only is to use FC-3283 to replace among the embodiment 1 the HFE-7500 that comes from 3M company as fluorine-based solvent.

Embodiment 5

A kind of blue ink that is used for roll printing makes in the mode identical with embodiment 1, just further contains F-480SF (the DaiNippon Ink﹠amp of 0.05 weight part of having an appointment; Chemicals) as fluorine based surfactant.

The comparative example 1

A kind of blue ink that is used for roll printing makes in the mode identical with embodiment 1, just contains F-480SF (the DaiNippon Ink﹠amp of 0.3 weight part of having an appointment; Chemicals), and use methoxypropanol to replace HFE-7500 as fluorine-based solvent as fluorine based surfactant.

The comparative example 2

A kind of blue ink that is used for roll printing makes in the mode identical with embodiment 1, just contains F-480SF (the DaiNippon Ink﹠amp of 5 weight parts of having an appointment; Chemicals), and use methoxypropanol to replace HFE-7500 as fluorine-based solvent as fluorine based surfactant.

EXPERIMENTAL EXAMPLE 1: the blanket coating performance of printing ink and the evaluation of longitudinal stripe

The printing ink of predetermined amount is joined in the ink fountain, use surge pump that printing ink is discharged with the rate of discharge of about 0.4ml/s through the slit spout, the cylinder that blanket twined that printing ink will be coated with turns clockwise with the speed of about 30mm/s.Printing ink is applied on the blanket, observes the dewetting that takes place in the edge part office of coated paint film and pin hole then to confirm coating performance.Like this, do not generate, think that then coating performance is very good if observe dewetting phenomenon and pin hole fully.

Be coated with blanket with printing ink, will be coated on the whole transfer printings of paint film that precipitate on the glass substrate that chromium is arranged then, and observe whether generated longitudinal stripe from the light of reflection.

EXPERIMENTAL EXAMPLE 2: antifoam performance

The printing ink of about 10g is placed the vial of 5930ml, acutely rock this bottle 10 times, stablize printing ink then to measure time up to lather collapse.

EXPERIMENTAL EXAMPLE 1 and 2 the results are shown in the following table 1.

[table 1]

As shown in table 1, confirmed, wherein only adopted the composition (embodiment 1 to 4) of fluorine-based solvent substitution list surface-active agent and wherein use the composition (embodiment 5) of low quantity of surfactant to have outstanding blanket coating performance, antifoam performance and the performance of avoiding producing longitudinal stripe.

But, comprising under the situation of fluorine based surfactant with the ink composite (comparative example 1) of replacement fluorine-based solvent, debatablely be: the antifoam performance deterioration, even and thereby the blanket coating performance still caused coating defects (as longitudinal stripe) remarkably.In addition, when with about 5 or the excessive amount of more weight parts when using fluorine based surfactant (comparative example 2), may owing to other materials (for example tackiness agent and linking agent) but the compatibility deterioration form the impurity of projection.

The present invention is used for the ink composite of roll printing, is not using under the tensio-active agent situation or by using a spot of tensio-active agent, is having outstanding antifoam performance and coating performance; And confirm, by using fluorine-based solvent (its rate of volatilization fast and not have to influence to dispersing of pigments) to improve blanket coating performance, antifoam performance and preventing to produce the performance of longitudinal stripe.

In addition, the ink composite (wherein add fluorine-based solvent is arranged) that is used for roll printing can reduce the surface tension of coating back printing ink, and need not to reduce the surface energy of the pattern that forms, and can not produce the problem that influences last handling process unfriendly.

More than disclosed theme be considered to Illustrative and nonrestrictive, appended claims is intended to contain all such modifications, improvement and other embodiment, and these all fall within the spirit and scope of the invention.Therefore, law allowed at utmost in, scope of the present invention will be determined by subsequently the claims and the most wide in range explanation that is allowed of equivalents thereof, and should do not retrained or limit by aforesaid specific descriptions.

Claims (9)

1. an ink composite that is used for roll printing comprises a kind of fluorine-based solvent as solvent.

2. the composition of claim 1, wherein said solvent comprise boiling point about 70 ℃ to about 170 ℃ hydrogen fluorine ether solvents as fluorine-based solvent.

3. the composition of claim 1, the content of wherein said solvent be based on the composition meter of whole 100 weight parts, for about 50 to about 90 weight parts.

4. the composition of claim 3, the content of wherein said fluorine-based solvent be based on the composition meter of whole 100 weight parts, for about 0.2 to about 5.0 weight parts.

5. the composition of claim 1, wherein said fluorine-based solvent is 2-trifluoromethyl-3-oxyethyl group ten difluoro hexanes.

6. the composition of claim 1 also further comprises tinting material, adhesive resin, polyfunctional monomer and initiator.

7. the composition of claim 6 wherein comprises about 2 tinting materials to about 15 weight parts; About 1 adhesive resin to about 20 weight parts; About 1 polyfunctional monomer to about 30 weight parts; And about 0.1 initiator to about 5.0 weight parts.

8. the composition of claim 6, also comprising a kind of surface energy in addition is about tensio-active agent of 18 to about 23mN/m, its amount is based on the gross weight meter of described composition, is about 1 or weight part still less.

9. the composition of claim 8, the content of wherein said tensio-active agent be based on the gross weight meter of described composition, is about 5 or weight part still less.