TW200418938A - Compositions - Google Patents

Abstract

A non-aqueous, substantially solvent-free, radiation curable ink having a viscosity less than 30m Pa.s at 60 DEG C, comprising: (iv) a colorant (v) a photo-initiator, and (vi) a mixture of (meth)acrylate compounds; wherein: (a) the colorant is present in the ink in an amount of 0.1 to 14.9% by weight relative to the total weight of ink; and (b) the mixture of (meth)acrylate compounds comprises c% of one or more mono (meth)acrylate compounds, d% of one or more di (meth)acrylate compounds and e% of one or more compounds having three or more (meth)acrylate groups, wherein the values of c%, d% and e% are by weight relative to the total weight of the mono (meth)acrylate compounds, di (meth)acrylate compounds and compounds having three or more (meth)acrylate groups and are such that the value of Formula (1) is less than or equal to 60.

Description

200418938 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to radiation-curable inks and their use in jet printing. [Prior Art] Inkjet printing is a non-contact method by which ink droplets are sprayed onto a substrate through a thin nozzle. There are many stringent performance requirements for inks used in inkjet. For example, a clear and featherless image should be provided, which has good water resistance, solvent resistance, light and ozone fastness, attractive color and high optical density. For inkjet printing inks, other desirable properties include fast drying time (to facilitate high-speed printing), low viscosity to enable the ink to be used on a wide range of inkjet feeders, and mechanical resistance (to avoid imprinting (Wipe off) 'Low curl and good adhesion to series of substrates. Organic ink contains organic solvents to reduce the viscosity. However, such solvents can produce undesirable odors, especially at home and in small, poorly ventilated offices. Avoid including organic solvents with low foetal point to minimize the release of volatile organic solvents into the air. Including high-boiling solvents can significantly increase the drying time of the ink. Wu Guo Patent No. 5,270,368 discloses a radiation-hardenable 'resistance composition' for inkjet printing. The composition contains most of monofunctional and bifunctional precursors and a large amount of organic solvents such as methanol. A sufficiently low viscosity is obtained for spraying. The US patent 4,303,924 + τ π μ a does not expose the radiation-hardenable inkjet printing ink, which contains an organic solvent and a large number of trifunctional monomers. 87997 200418938 〇 02/3 8688 discloses a low-viscosity, radiation-hardenable composition which is solvent-free and has a small amount of difunctional and tri- or more functional monomers. [Summary of the Invention] The first aspect of this month provides a non-aqueous, substantially solvent-free, radiation-hardenable ink having a viscosity of less than 30 mPa.s at 60 t, including: (i) a colorant; (ii) a photoinitiator; and (in) a mixture of a lauryl (meth) acrylic acid vinegar compound; wherein: (a) a colorant is present in the ink in an amount of 0.01% to 14.9% relative to the total weight of the ink ; And (b) a mixture of lauryl (meth) acrylate compounds includes one or more c% monolauryl (meth) acrylate compounds, and d% one or more dilauryl (meth) acrylate compounds And e% one or more compounds having three or more lauryl (meth) acrylate groups, where the values of c%, d%, and e% are relative to monolauryl (fluorenyl) propanoic acid The total weight of the ester compound, the dilauryl (fluorenyl) acrylic acid ester compound, and the compound having three or more lauryl (fluorenyl) acrylic acid ester groups, and is the value of formula (1) Value less than or equal to 60: C% + 0.628 / d% + e% \ 'sin 60 tan 60 / Formula ⑴ 87997 200418938

Preferably, the value of the formula ⑴ is from 40 to 6G and from 49 to 55_8. More preferably, it is 42.6 to 57 '. In the ink, the amount of the colorant is from 0.1% to 14%, more preferably 10 /? 100 /, based on the total weight of the ink. It is h 1% to 8%. Preferably, the coloring agent and the η coloring agent are yellow, magenta, blue-green, black, black, and so on. * Violet, green, orange, and red titanium oxide. Shoot the color of this composition. Preferably, the ink does not contain two. The colorant is preferably a dye, a pigment, or a mixture thereof. Preferred dyes and pigments do not contain ionic groups, such as disperse dyes. Pigments that are not water-soluble are particularly preferred, or inorganic. The pigment is preferably organic and the mouth is human hair straight II: non :: of; mouth. Typically, these * are 0.003⑼ The average particle diameter of the pigment is preferably _, more preferably 4 to 5 and the best grade = \ Through the particles of this particle size, the storage stability of the ink and the Mouth: The second one ... the advantages in terms of degrees. When the nozzle has a particularly large nozzle, pigments exceeding this particle size range can be used. For example, in European patent 0M952, fluorene patent 5,538,548, phase patent 5,443 fluorene, 200418938 gambenazole, monoazo and bisazobenzimidazolone, isoindolinone, monoazonacresol, diaryl Oxazolinone, rhodamine, indigo, quinacridone diazopine ketone, diphenylaniline ... different than salinyl, bifenanilide, green onion net, four different flowers _, two Df , Monoazopropene halide compound. Brain plus acrylide), anthracene and mixtures thereof. Examples of carbon black pigments include: 400r, MogL, mftexTM 32Q from CabOt, or carbon black 8 from the company, Speciai Black 25, special black 35, special Black 55, Printex ^ 25, PrintexTM35. Printex ^ 55 ^ p ^ ntex ^! 50T ^ and Pigment Black 7. Examples of other pigments include C 丄 Pigment Yellow 17, C 丄 Pigment Blue 27, CI 枓 Pigment Red 49: 2, C 丄 Pigment Red 81: Bu CI.Pigment Red 81: 3, P 匸 丄 Pigment Red, C 丄 Pigment Yellow 83, CL Red 57: 1, ci · Pigment Red 49: i, C 丄 Pigment Violet 23, CL Pigment Green 7, 0.Pigment Blue 61, cj · Pigment Red Immortal, ci.Pigment Red 52:; 1, CI Pigment Purple Bu Pigment White 6, CI • Pigment Blue i5, c i. Pigment Yellow 12, CL Pigment Blue 56, CI. Pigment 镫 5, c 丄 Pigment Black 7, ci. Pigment Yellow u, c 丄 Pigment Red 48: 2, CJ Pigment Blue i5: 3, ㈡.Pigment Yellow [, CL Pigment Yellow 3, (M • Pigment Yellow 13, ci • Pigment Orange i6, C 丄 Pigment Tone 55, ^ _Red 41, ^ Pigment Dial 34, 〇. Pigment Blue 62 , ^ .Pigment Red 22, C 丄 Pigment Red 170, αι · Pigment Red ci, ci · Pigment Yellow i5i,. 丄 Pigment Red 184, CI Yan oblique 誃, ο τ each y, C.1.Pigment Red 3 , CI · Pigment Blue 15: 1 m Material Blue 15m Pigment Blue 151C.L Pigment Red 23, υ.Pigment Red 112, 〇 · Pigment Yellow 126, 〇 · Pigment m69, ci · Pigment Lamp η, CI Pigment Red H0, 12 , Mouth · Pigment Blue ... Mouth Pigment Yellow 42, Mouth 87997 -10- 200418938 Pigment Red 101, C_I · Pigment Brown 6 CI Pigment Brown 7, CI Pigment Brown 7: X, CI Pigment Black U, C, Pigment Metallic Color 1, c.I_Pigment Metallic Color 2, CI Pigment Yellow 128, CI Pigment Yellow 93, CI Pigment Yellow 74 , CI · Pigment Yellow 138, CI · Pigment Yellow 139, c.I_Pigment Yellow 154, C_I.Pigment Yellow 185, CI Pigment Yellow 180, CI · Pigment Red 122, CI · Pigment Red 184, and Bridged Aluminum Phthalocyanine Pigment Other pigments are listed in the "Color Index" and its updated editions, especially the third edition, 1982, pages 6-146. The better pigment series pigment yellow 128, 93, 17, 74, 138, 139, 154, 185, 180; Pigment Red 122, 57: 1, 184; Pigment Blue 15: 3, 15: 4 and Carbon Black. Chevrolet dyes include azo, diazo, xanthene, anthraquinone , Triarylmethyl &, alpha yam, thiazine, phthalocyanine dyes and aniline black. The dyes can be used alone or in combination with 14 other dyes and / or pigments. The dyes are preferably dispersible or soluble in solvents , Examples of which can be selected from the "color index", especially 3rd edition, 1982, pages 147-263. Dyes can be metalized or non-metalized. Ink can also contain dispersion if necessary When the colorant is a dispersible dye, a dispersant is usually not needed because the dye can be dissolved in the formulation. Similarly * when the pigment is self-dispersible (that is, the pigment has dispersible groups or is surface-modified to become dispersible Self-dispersing), no additional dispersant needed. However, when the tint colorant is not bathable in a mixture of lauryl (meth) acrylate compounds (component (丨 丨 丨)), it is preferable to include a dispersant in the ink to help storage stability. Powders include, for example, polyesters, polyurethanes and polyacrylates, especially those in the form of high molecular weight block copolymers. Examples of dispersants include DisperbykTM (ex B γκ and 87997 -11-200418938

SolsperseTM (ex Avecia) dispersant. For a detailed list of dispersants for non-polymers and some polymers, see, for example, McCutcheon, Functional Materials, North American Edition, Manufacturing Confectioner Publishing Co., Glen

Rock, N.J., pp. 110-129 (1990), the entire disclosure of which is incorporated herein by reference. German patent 19636382, US patent 5,720,802, US patent 5,713,993, PCT / GB95 / 02501, US patent 5,085,689 and UK patent 2303376 also disclose dispersants suitable for use with pigments. When the ink contains a dispersant, it is preferably 50 ° / based on the weight of the colorant. Up to 150 ° /. The amount exists. Examples of the self-dispersing pigment include surface-treated carbon black with a carboxyl group, a continuous acid salt and / or an ethyleneoxy group. The pigment and dispersant are preferably added to the ink as a mixture. For example, a mixture of pigment and dispersant can be prepared by grinding the pigment in a small lauryl (meth) acrylic acid ester component c), magic and e) with a grinding medium such as glass beads. The pigment dispersion is then typically sieved and slowly added to dilute the remaining ink components. Based on the total weight of the ink, the preferred photoinitiator includes acyloins and their corresponding ethers. The amount of the photoinitiator in the ink is from 0.1% to 15%, more preferably from 3% to 12%, relative to the oil. Diketone, alpha diyan I or monoketal of keto acid, even

Chromophore-substituted dental triazines and chromophore-substituted dental methyls; diazoles xadiozoles). Specific examples of the photoinitiator include acetophenone, phenylpropanidine, 2-phenyl-acetophenone, 2_chloro_2_phenyl_acetophenone, 2_2_dichloro! Phenyl-benzylacetone, 2-butoxy-2_phenylacetophenone, 2 sense dimethoxy_2_phenyl-phenylethyl 87997 -12-200418938 different, 2,2-diethoxy Methyl-acetophenone, 2-hydroxymethylmethoxyphenyl-acetophenone, benzophenone, 4-trichloromethylbenzophenone, dihydroindenone, 13-indanedione, glutamate I, Xanthones, thioxanthone, 2-chlorothioxanthone, anthraquinone, 2-ethylanthraquinone, dioxin, glyoxal, 1,2-indanedione, p-chlorophenyl-ethylenedioxane Aldehyde, bibenzyl t, camphorquinone, and benzoin esters and ethyl esters. Commercially available photoinitiators particularly suitable for use in the present invention include SpeedcureTM ITX and IrgacureTM369. The ink may optionally include one or more synergistic initiators or amine synergists to improve the hardening speed. Examples include isopropylthioxanthone, ethyl 4- (dimethylamino) benzoate, 2-ethylhexyl dimethylaminobenzoate, and dimethylaminoethyl methacrylate. Preferably, the photoinitiator is not a cationic photoinitiator. Preferably, the photoinitiator is a free radical photoinitiator. Preferably, the photoinitiator is soluble in the ink. A single photoinitiator can be used, although two or more photoinitiators are preferred because this can result in a broader spectral response, improved hardening depth, and improved hardening speed of opacifying pigments such as carbon black. Preferably, the ink further includes a stabilizer to improve the storage stability of the ink and prevent premature hardening. The stabilizer is preferably an antioxidant, a ndicai trap, a group quencher, or the like, such as phenol, thiol, benzene, hydroquinone, amine, xanthate, or N- Alkyl amine or ice aryl aniline. Too much stabilizer will completely prevent hardening, so the preferred stabilizing amount is 0% to 10%, more preferably 0.01% to 5%, and particularly 0.1% to 3% with respect to the total weight of the ink. For the best ink storage life, stabilizer mixtures are preferred. Preferably, the ink is transparent through photochemical rays or particle beams, especially 87997-13-13200418938 is hardened by UV or electron beam rays. Flat lauryl (meth) acrylate compound wheel or methacrylate group. As is known in the art, a dimer is polymerizable when it is irradiated in the presence of a photoinitiator. Month 2) The acrylate group can be expressed by the following formula:

〇 where R is fluorene or methyl. The monolauryl (meth) acrylate compound is preferably a monomer. Examples of monolauryl (meth) acrylate monomers include cyclotrimethylolpropane, n-lauryl (meth) acrylate, ethoxylated tetrahydrofurfuryl lauryl (meth) acrylate, and phenoxyethyl lauryl (Meth) acrylate, trihydroxypropane n-lauryl (meth) acrylate, lauryl (meth) acrylate, octadecyl lauryl (meth) acrylate, monomethoxypivalyl Alcohol propoxylated monolauryl (meth) acrylate, monomethoxytripropylene glycol monolauryl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl lauryl (methyl ) Acrylate, isodecyl lauryl (meth) acrylate, isooctyl lauryl (meth) acrylate, isononyl lauryl (fluorenyl) acrylate, tridecyl lauryl (meth) Acrylate, iso-bornyl lauryl (meth) acrylate, ethoxynonylphenol lauryl (meth) acrylate, ethoxylated phenol lauryl (fluorenyl) acrylate, 2-hydroxyethyl lauryl (Fluorenyl) acrylate, 4-hydroxybutyl lauryl (methyl) Enoate, 2-hydroxypropyl lauryl (meth) acrylate, isobutyl lauryl (meth) acrylate, third butyl lauryl (meth) acrylate, cetyl lauryl ( Methacrylic acid ester, cyclohexyl lauryl (meth) acrylate 87997 -14- 200418938, ethylhexyl lauryl (meth) acrylate, 2-diamidoethyl lauryl (meth) acrylate Acid purine, trifluoroethyl lauryl (meth) propanoic acid S purine, 3-methoxybutyl lauryl (meth) acrylate, dicyclopentenyl lauryl (fluorenyl) acrylate, Polyethylene glycol monolauryl (meth) acrylate and polypropylene glycol monolauryl (fluorenyl) acrylate. Preferred monolauryl (meth) acrylate monomers include lauryl (fluorenyl) propionate, tetrahydrofurfuryl lauryl (meth) acrylate, 2- (2-ethoxyethoxy) Ethyl lauryl (meth) acrylate, isooctyl lauryl (meth) acrylic acid, isodecyl lauryl (meth) acrylic acid, tridecyl lauryl (meth) acrylic acid Ester, dodecyl lauryl (meth) acrylate, isobornyl lauryl (meth) acrylate, cyclotrimethylolpropane n-lauryl (fluorenyl) propanoic acid g purpose. Particularly preferably, the one or more monomer lauryl (meth) acrylate compounds are or include isobornyl acrylate. Dilauryl (meth) acrylate compounds have two (and only two) groups selected from acrylates and fluorenyl acrylates. A preferred dilauryl (meth) propionate compound is a dilauryl (meth) acrylate monomer such as 1,4-butanediol, ι, 6-hexanediol, neopentyl glycol, mono , Di, tri and polyethylene glycol, mono, di, tri and polypropylene glycol, monomethoxyethoxylated trimethylol, propane, propoxylated neopentyl glycol, ethoxylated neopentyl Alcohol, 1,2-butanediol and ethoxylated hexanediol as the dilauryl (methyl) propionate. Particularly preferably, the one or more dilauryl (meth) acrylate compounds are or include 1,6-hexano-acrylic acid. The compound having three or more lauryl (meth) acrylate groups has 87997 -15 to 200418938 and has three or more groups selected from acrylates and methacrylates. The compound having two or more lauryl (meth) acrylate groups is preferably a monomer, oligomer, or polymer, and preferred examples thereof include tris (methyl) propane = trilauryl (methyl) Acrylate, ethoxylated trimethylolpropane trilauryl (fluorenyl) acrylate, propoxylated trihydroxymethylpropane trilauryl (meth) acrylate, glycerol trilauryl (曱Group) acrylate, propoxylated propylene glycol trilauryl (meth) acrylate, pentaerythritol trilauryl (meth) acrylate, pentaerythritol tetralauryl (fluorenyl) acrylate, ginseng (2-hydroxyethyl) Group) isocyanate triacrylate, di-trimethylolpropane tetralauryl (meth) acrylate, ethoxylated pentaerythritol tetralauryl (meth) acrylate, ethoxylated di-pentaerythritol Tetralauryl (meth) acrylate, Tetramethylolmethane Tetralauryl (meth) acrylate, Multifunctional lauryl (meth) acrylate amino phosphonate, Lauryl (fluorenyl) acrylate- Polyester and lauryl (meth) acrylate acrylic Acid resin. Particularly preferably, the one or more compounds comprising three or more lauryl (fluorenyl) acrylate groups are or include trimethylolpropane triacrylate and / or ethoxylated Acrylic acid g purpose. When exposed to light or particle beam radiation, inks containing acrylates polymerize faster than those containing lauryl (fluorenyl) propionate. Therefore, the amount of lauryl (meth) acrylate is preferably not more than 20% of component (iii), more preferably not more than 10% and especially not more than 5%. Particularly preferably, the component (ni) is free of lauryl (meth) propionate. The ink may optionally include a polymer or oligomer that does not contain a lauryl (meth) acrylate group. Preferably, the polymers and oligomers which do not contain a lauryl (meth) acrylate group 87997 -16- 200418938 are in the ink in an amount of 0% to, more preferably 0% to, based on the total weight of the ink. It is present in an amount of 10% and optimally 0% to 5%. 0 The ink of the present invention is substantially free of solvents. That is, there is no solvent or water in the ink, except for trace solvents which may be present as impurities in any ink component. Preferably, the amount of any such residue relative to the total weight of the ink is less than 2%, more preferably less than 0.5% and especially less than 0.01%. As mentioned above, the ink of the present invention is particularly suitable for inkjet printing. The preferred inkjet type of the ink of the present invention is piezoelectric inkjet printing. The viscosity of the ink of the present invention is 60t; preferably 1 to 30011 ^ 3, and more preferably 2 to 25 mPa.s. The ink composition may have a higher viscosity at room temperature as needed. The limitation is that the finished ink meets the above viscosity requirements at the above temperature. The surface tension of the ink of the present invention is preferably lower than 40 dyne / cm. The ink of the present invention is preferably free of particulate impurities which tend to clog the ink nozzles. For this purpose the ink is preferably filtered through a sieve with a pore size of less than 10 Am, more preferably less than 3 and especially less than 1 pore size. The particularly preferred ink of the present invention is an ink that is anhydrous, substantially free of solvents, can be hardened by radiation, and has a viscosity of 1 to 30 mPa.s at 60 ° C. The ink is dry: (i) yellow, fuchsia, blue-green , Black, blue, indigo, purple, green, orange or red pigments or a mixture comprising two or more of these pigments; (ii) a photoinitiator; and (iii) a lauryl (fluorenyl) acrylate compound; wherein : 87997 -17- 200418938 (a) Pigments are present in the ink in an amount relative to the total weight of the ink; (b) Lauryl (meth) propionate compounds include one of c0 / 〇 One or more monolauryl (fluorenyl) acrylate compounds, one or more d% dilauryl (meth) acrylate compounds, and one or more e% having three or more lauryl (meth) acrylate groups Compounds in which the values of c%, ^, and% and e% have three or more lauryl (methyl) groups relative to the monolauryl (meth) acrylate compound and the dilauryl (meth) acrylate compound. ) The total weight of the acrylate group of compounds, and should In order to make the value of formula (丨) from 40 to 60: C% + 0.628 / + e% \

Vsin 60 tan 60 / formula (C) photoinitiator is 3% to 12 in the ink relative to the total weight of the ink. / 〇 the amount is present; (d) — or more monolauryl (fluorenyl) acrylate compounds are selected from the group consisting of: bad bis fluorenyl propane n-lauryl (meth) acrylate, ethyl Tetrahydrofurfuryl lauryl (meth) acrylate, oxyethyl lauryl (meth) acrylate, trimethylolpropane n-lauryl (fluorenyl) acrylate, lauryl lauryl ( Methyl) propionate, octadecyl lauryl (meth) acrylate, monomethoxy neopentyl glycol propoxylated monolauryl (meth) acrylate, monomethoxytripropylene glycol mono Lauryl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl lauryl (meth) acrylate, isodecyl lauryl (meth) acrylate, isooctyl lauryl ( (Meth) acrylate, isononyl lauryl (meth) acrylate 87997 -18-200418938, tridecyl lauryl (meth) acrylate, isobornyl lauryl (fluorenyl) acrylate, Ethoxynonylphenylpanyllauryl (meth) propanoate, ethoxylated phenylpanyllauryl Methyl) propanoic acid g, 2-Ethylethyllauryl (meth) acrylate, 4-hydroxybutyllauryl (meth) acrylic acid, 2-Ethylpropyllauryl (fluorenyl) ) Acrylic acid ester, isobutyl lauryl (meth) acrylate, third butyl lauryl (meth) acrylate, cetyl lauryl (meth) acrylate, cyclohexyl lauryl (methyl Group) acrylate, ethylhexyl lauryl (meth) acrylic acid, 2-dimethylaminoethyl lauryl (meth) acrylate, trifluoroethyl lauryl (meth) acrylate, 3-methoxybutyl lauryl (meth) acrylate, dicyclopentenyl lauryl (meth) acrylate, polyethylene glycol monolauryl (meth) propanoate, and polypropylene glycol mono Lauryl (meth) acrylates and mixtures thereof; (e) —One or more dilauryl (meth) acrylate compounds are selected from the group consisting of: 1,4-butanediol, 1 Hexanediol, neopentyl glycol, mono, di, tri and polyethylene glycol, mono, di, tri and polypropylene glycol, monomethoxyethoxylated tri Dimethylolpropane, propoxylated neopentyl glycol, ethoxylated neopentyl glycol, 1,2-butanediol, and ethoxylated hexanediol as dilauryl (meth) acrylates and mixtures thereof ; And (f) or a chemical species having two or more lauryl (meth) acrylate groups is sent to a group composed of the following: · trimethylol sulfonated monolauryl ( (Meth) acrylates, ethoxylated trimethylolpropane trilauryl (meth) acrylate, propoxylated trimethylolpropane trilauryl (meth) acrylate, glycerol trilauryl (^ Yl) acrylate, propoxylated glycerol trilauryl (meth) acrylate, pentaerythritol March 97997 -19- 200418938 lauryl (meth) acrylate, pentaerythritol tetralauryl (meth) acrylate Ester, tris (2-hydroxyethyl) isouranyl triacrylate, di-trimethylolpropane tetralauryl (meth) acrylate, ethoxylated pentaerythritol tetralauryl (meth) acrylate , Ethoxylated di-pentaerythritol, tetralauryl (meth) acrylic acid, tetramethylolmethane (Meth) acrylates, polyfunctional lauryl (meth) acrylates-ethyl amino phosphonates, lauryl (meth) acrylic acid esters-polyS, and lauryl (meth) acrylates Sour Acrylic Acrylic Resin and Its Mixture. In the ink of this car, the mixture of lauryl (meth) acrylate compounds is preferably 70% to 95.9%, more preferably M% to 95.9% and particularly, relative to the total weight of the ink. An amount of 78% to 95.9% is present in the oil. Any weight difference between components ⑴, ⑼, and ㈣ is complemented by other commonly used ink additives, such as flow control agents, dispersants, fungicides, rheology modifiers, etc., except water or organic solvents. In addition to the above components (i) to (iii), the ink of the present invention may contain other, and knives such as preservatives, bactericides, rheology modifiers, surfactants, leveling agents, defoamers, Anticoagulants and compositions thereof. A second aspect of the present invention provides a method for printing an image on a substrate, the method comprising applying the ink of the first aspect of the present invention to an inkjet printer and hardening the ink, preferably using an electron beam. Or better yet use ultraviolet light. The printed substrate obtained by this method forms another aspect of the present invention. The parent substrate is metal, plastic, ceramic, glass, wood, printed paper, and coated paper. Preferred applications include home or office e 87997 -20-200418938, bags, labels and bar codes, especially complex images, printed images, printed circuit board production, signs, signs, wall decorations and decorative sheets. According to the third aspect of the present invention, there is provided an ink cartridge for a printer, which includes a cartridge and an ink ', wherein the ink exists in the cartridge and is defined as the first aspect of the present invention. The following examples further illustrate the invention, in which all parts and percentages are by weight unless otherwise specified. [Embodiment] Example 1 A thread-curable ink containing the following components: Component Type

Solsperse ™ 32000 1.09 Dispersant

Solsperse ™ 5000

Irgacure ™ 369

Speedcure ™ EHA Speedcure ™ ITX 0.06 2.80 2.80 1.40 Dispersant Photoinitiator Amine synergist Photoinitiator The process for preparing the above inks is as follows: By combining Regal 250R pigment with a small amount of SartomerTM 256 spear SartomerTM 238 and SolsperseTM 32000 and 5000 dispersants The grinding matrix was prepared by ball milling until a fine particle dispersion was formed. Then add the remaining components in the dark and mix the mixture evenly, then use 丨 "87997 -21-200418938

WhatmanTM syringe screen filter. Based on the total weight of the compound (100%), monolauryl (meth) acrylate (16.7%), dilauryl (meth) acrylate (16.7%), and trilauryl (meth) acrylate The percentage of ester (66.6%) makes the value of formula (1) (16.7 + 0.628X (16.7 / sin 60 + 66.6 / tan 60)) = 52.93. Comparative Example 1 Preparation of a radiation-curable ink containing the following components (In a manner similar to Example 1): Component Weight (S) Type Sartomer ™ 256 39.55 Monoacrylate Sartomer ™ 238 9.89 Diacrylate Sartomer ™ 3 51 9.89 Tripropion Regal ™ 250R 1.73 Pigment Solsperse ™ 32000 1.08 Dispersant Solsperse ™ 5000 0.06 Dispersant Irgacure ™ 3 69 2.76 Photoinitiator Speedcure ™ EHA 2.76 Amine synergist Speedcure ™ ITX 1.38 _ ---_ Photoinitiator ---______ Relative to the total weight of this compound, single laurel The percentage of base (fluorenyl) acrylate, dilauryl (meth) acrylate, and trilauryl (fluorenyl) acrylate makes the value of formula (1) 84.79. Results The inks described in Example 1 and Comparative Example 1 were applied to a light-emitting card using an 8 // m K-rod applicator. Use a Fusion Systems device to harden and coat 87997-22-200418938 layers. This device is equipped with 300 "0" bulbs per inch at a belt / hardening speed of 25M / minute or 15M / minute using UVA〇3m uVB 〇 ″ 72 to 〇 99, UVC 0.07-0.11 hardening energy. The XRite 938 densitometer was used in the density state, and the light sources D50 and 2 were used. The emission optical density (r0d) of the hardened coated luminescent card was measured at an observation angle. Chemical resistance (% loss) was determined by rubbing twice on a hardened coated luminous card with 5x MEK (methyl ethyl ketone) and then measuring 1101 in the rubbed area. Then the chemical resistance (% loss) value can be expressed as ... Chemical resistance (% loss) ",-(initial ^

Initial ROD Therefore, a small chemical resistance (% loss) value represents higher solvent resistance. By using a Brookfield viscometer '50. [, 100 rpm operating conditions and measurement of viscosity using UL spindle. The surface tension of the ink was measured at 25 ° C using a Kruss surface tension scale. Use the method of reed to estimate the hardness of printing by using the wrong pens of different hardnesses, which is the lowest hardness hardness measurement value that can form scratches on the print. Example 1 Into / Again ... and Comparative Example 1 ROD 1.821 1.668 Chemical resistance (% Loss) 1.7 29.2 Viscosity (@ 50 ° C) mPa.s 11.5 4.32 Surface tension (@ 25 ° C) dyne / cm 37 37 Pencil hardness 4H 6B Band hardening speed 25 15 The above table shows the comparison of the ink of Example 1 Example 1 has better chemical resistance and a faster hardening speed of 87997 -23-200418938, while still maintaining a low viscosity suitable for inkjet printing. Moreover, Example 1 has better pencil hardness and higher ROD than Comparative Example 1. The ink described in Example 1 can be easily sprayed with a Spectra Galaxy printhead. Preparation of other inks of the present invention (in a manner similar to Example 1) containing the following components: Ingredients yellow% magenta% blue green% black% Sartomer ™ 506 isobornyl acrylate 8.73 8.18 8.58 8.57 Sartomer ™ SR238 1, 6 Hexylene glycol diacrylate 22.48 30.84 25.42 22.74 Sartomer ™ 306 tripropylene glycol diacrylate 3.7 5.95 2.97 4.18 Sartomer ™ SR351 trimethylolpropane triacrylate 34.9 24.53 32.54 33.48 Sartomer ™ SR454 ethoxylated trimethylolpropane Triacrylate 17.45 12.26 16.28 16.74 Tegorad ™ 2100 ST modifier (acrylic silicone resin) 0.15 0.15 0.15 0.15 Irgacure ™ 369 photoinitiator 4 4 4 4 Speedcure ™ EHA amine synergist 4 4 4 4 Speedcure ™ ITX photoinitiator Agent 2 2 2 2 Paliotol ™ Yellow D1819 Pigment 2 0 0 0 Hostaperm ™ Red E5B02 Pigment 0 5 0 0 Irgalite ™ Pigment 0 0 2.5 0 87997 -24- 200418938 Blue GLVO Regal ™ 250 Pigment 0 0 0 2.5 Solsperse ™ 32000 Dispersant 0.6 3 1.5 1.56 Solsperse ™ 5000 Dispersant 0 0.1 0.05 0.09 These inks pass through Specta Galaxy The print head to print showed excellent performance, and has the very good chemical resistance. 87997 25-

Claims (1)

200418938 The scope of patent application: 1 · A non-aqueous, essentially solvent-free, radiation-hardenable ink with a viscosity of less than 30 mPa.s at 60 ° C, the ink includes ... (i) colorants , (11) a photoinitiator; and (iii) a mixture of a lauryl (meth) propanoate compound; wherein: (a) the colorant in the ink relative to the total weight of the ink is 0.1% to Present in an amount of 14.9%; and (b) a mixture of lauryl (meth) propanoate compounds includes one or more mono-lauryl (fluorenyl) acrylate compounds, and one or more d% Lauryl (meth) acrylate compounds and one or more compounds having three or more lauryl (meth) acrylate groups, wherein the values of c%, d%, and e% are relative to The monolauryl (meth) acrylate compound, the dilauryl (meth) acrylate compound, and the compound having two or more lauryl (meth) acrylate groups are based on the weight of the formula (1) The value is less than or equal to 60. c% + 0.628 (d% + ^ \ 'sin 60 tan 60 / formula 2. 2. If the ink of the scope of the patent application, the colorant is a pigment. 3. If the ink of the scope of the patent application, the monolauryl (fluorenyl) acrylate compound and dilauric (Fluorenyl) acrylate compound is a monomer. The ene 4. For example, the ink of the scope of the patent application for item 丄, where the formula (^ is to "^. 87997 200418938 Shi Shen. Monthly ink of the scope of the first item, where The photoinitiator is a free radical photoinitiator. The ink of item i in the Shishen-Yue patent, wherein one or more of the lauryl (methato) propene I compounds are or include isobornyl acrylate. 7. For example, the oldest ink in the scope of patent application, where one or more of the dilauryl (meth) acrylate compounds are or include hexamethylene glycol diacrylate. 8. In the ink of the first scope of the patent, where One or more compounds having three or more lauryl (meth) acrylate groups are or include trimethylolpropane triacrylate and / or ethoxylated trimethylolpropane triacrylate. 9 . Such as The ink of the scope of the patent, please include the dispersant and / or amine synergist. 10. If the ink of the scope of the patent, the colorant is 1.1% to 8% relative to the total weight of the ink. The amount exists. 11 · If the ink in the scope of patent application No. 1 in which the colorant is not white. 12 · If the ink in the scope of patent application 丨 is free of titanium dioxide. 13. If the scope of patent application is 丨Ink, in which the photoinitiator is present in an amount of 3% to 12% relative to the total weight of the ink. 14. If the ink of the scope of patent application item 1 includes: (i) yellow, fuchsia, blue green, black , Blue, indigo, purple, green, orange or red pigments or a mixture comprising two or more of these pigments; (ii) a photoinitiator; and (iii) a lauryl (meth) acrylate compound; 87997 200418938 Among them: 0) Pigment in the ink is 1.1% to 8 based on the total weight of the ink. (B) lauryl (meth) acrylate compounds include one or more monolauryl (meth) acrylic acid compounds of c0 / 〇, d% one or more dilauryl (methyl ) Acrylate compounds and one or more compounds having three or more lauryl (meth) acrylate groups e / 0, where the values of c%, (1 and% and e%) are relative to Based on the total weight of a compound having two or more lauryl (meth) acrylate groups, the lauryl (meth) acrylate compound and the dilauryl (meth) acrylate compound should be such that The value is from 40 to 60: 0% + 0.628 / + e% \ \ sin 60 tan 60 / Formula (c) Photoinitiator in the ink in an amount of 3% to 12% relative to the total weight of the ink Exists; (d) one or more monolauryl (fluorenyl) acrylate compounds are selected from the group consisting of: cyclotrimethylolpropane n-lauryl (fluorenyl) acrylate, ethoxy Tetrahydrofurfuryl lauryl (meth) acrylate, phenoxyethyl lauryl (meth) acrylate, trimethyl Propyl n-lauryl (meth) propionate, lauryl (fluorenyl) acrylate, octadecyl lauryl (meth) acrylate, monomethoxyneopentyl glycol propoxylated mono Lauryl (meth) acrylate, monomethoxytripropylene glycol monolauryl (meth) acrylate, 2- (2-87997 200418938 ethoxyethoxy) ethyl lauryl (meth) acrylate, isopropyl Decyl lauryl (meth) acrylate, isooctyl lauryl) acrylate, isononyl lauryl (meth) acrylate, tridecyl lauryl (meth) acrylate, isobornyl laurel (Meth) acrylate, ethoxynonylphenol lauryl (meth) acrylate, ethoxylated benzenelauryl (meth) acrylate, 2-methyl ethyl lauryl (meth) Acrylate, 4-hydroxybutyl lauryl (meth) acrylate, 2-hydroxypropyl lauryl (meth) acrylate, isobutyl lauryl (meth) acrylate, third butyl lauryl ( (Meth) acrylate, cetyllauryl (meth) acrylate, Hexyl lauryl (fluorenyl) acrylate, ethylhexyl lauryl (meth) acrylic acid, 2-diamidoethyl lauryl (fluorenyl) acrylate, diethyl ethyl lauryl (methyl) Acrylate, methoxybutyl lauryl (meth) acrylate, dicyclopentenyl (meth) acrylate, polyethylene glycol monolauryl (meth) acrylate, and polypropylene glycol Monolauryl (meth) acrylates and mixtures thereof; (e)-one or more dilauryl (meth) acrylate compounds are selected from the group consisting of: 丨, butanediol, 丨, 6_Hexanediol, neopentyl glycol, mono-, di-, tri- and polyethylene glycol, mono-, di-, tri- and polypropylene glycol, monomethoxyethoxylated trihydroxyfluorenylpropane, propoxylated neo Pentyl glycol, ethoxylated neopentyl glycol, 2-, 2-butanediol, and ethoxylated hexanediol dilauryl (meth) acrylates and mixtures thereof; and ⑴ one or more having three or more The compound of multiple lauryl (meth) acrylates 87997 200418938 is selected from the group consisting of Groups ·· Three sulfonyl acryl trilauryl (fluorenyl) acrylic acid ester, ethoxylated three sulfonyl acryl difluorinated dilauryl (fluorenyl) propionic acid s purpose, propoxylated three Dream ① Pyroyl propane trilauryl (fluorenyl) acrylic acid ester, glycerol trilauryl (meth) propanoic acid s purpose, propoxylated glycerol trilauryl (methyl) acrylate , Pentaerythritol trilauryl (meth) acrylate, pentaerythritol tetralauryl (fluorenyl) acrylate, trilauryl (2-merylethyl) isouric fL acid S, dipropionic acid g, di-tris Tetralauryl (meth) acrylate, ethoxylated pentaerythritol tetralauryl (meth) acrylate, ethoxylated di · pentaerythritol tetralauryl (meth) acrylate, tetrahydroxy Methylmethane tetralauryl (meth) acrylate, polyfunctional lauryl (meth) acrylate_urethane 'lauryl (meth) acrylate_polyester and lauryl (meth) acrylate Acrylic resins and mixtures thereof. a As the oldest ink in the scope of patent application, it transitions through a sieve with a low spleen pore size. 16. As the oldest ink in the scope of patent application, it is used for inkjet printing. 17. A method for printing an image on a substrate. Desire Heart Network-Nai Qing ° Hai method includes using an oil as described in the application of any one of the targets 1 to 16 and hardening the ink. Print an image on Kibe 18. If the method of the scope of patent application "item" is used, the coin is hardened with external light. Using a pen light beam or purple 19. A printed matrix soil shell筮! 7 = Winner. The method of my brother's item is 87997 200418938 2 0. An inkjet printing ink cartridge, which includes a box and ink, where the ink exists in the box and is defined as the first item in the scope of patent application. 2 1 — A substrate with printed images printed using the inks listed in item 1 of the scope of patent application. 22. — A substrate with printed images printed using the area listed in item 17 of the patent application. The method to print the image. 87997 200418938 柒 Designated representative map: (1) The designated representative map in this case is: (二) The component representative symbols of this representative map are simply explained: 捌 If there is a chemical formula in this case, please reveal the best display Inventive chemical formula: (none) 87997