JP2023031193A - Uv-curable inkjet ink composition - Google Patents

Abstract

To provide a technology relating to an inkjet ink composition capable of using not only after PSR phenomenon but also after final cure.SOLUTION: A UV curable inkjet ink composition exhibits excellent viscosity and storage stability, adhesion and surface curability through the combination of four components. Excellent markings can be formed on printed circuit boards even after PSR cure, different from an existing inkjet ink composition. Therefore, the UV curable inkjet ink composition of the present invention overcomes the limitations of conventional inkjet ink compositions because it can be used when the process sequence of printed circuit boards is changed and marking formation is required after final curing.SELECTED DRAWING: Figure 1

Description

The present invention relates to a UV curable inkjet ink composition.

Marking inks are used in the final step of manufacturing printed circuit boards (hereinafter "PCBs") prior to the assembly of electronic components on the boards. Marking inks are used to indicate component designators, test points, and other features that aid in the assembly, evaluation, use, or repair of circuit boards. Marking inks are used on all printed circuit boards, but the field of use is not limited to this.

In the manufacture of printed circuit boards (PCBs), a photo solder resist (PSR) coating process is required to protect circuits. Generally, after the PSR process, markings are formed on the required portions of the PCB surface. Conventional inkjet ink compositions are typically used primarily to form markings after PSR development, and then curing the PSR and markings together through a final cure. This is because when marking is formed after the final curing of PSR, the adhesion to the substrate is remarkably insufficient and the marking is not sufficiently formed.

Therefore, in the case of conventional inkjet ink compositions, their use is limited when the process sequence is changed to form markings after the final curing.

Korean Patent Publication No. 10-2015-0050581

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems, and provides a technique related to an inkjet ink composition that can be used not only after PSR development but also after final curing.

1. One embodiment of the present invention relates to a UV curable inkjet ink composition comprising (A) one or more radically curable functional groups and one or more cationically curable functional groups; (B) a monomer containing a functional group capable of forming a crosslinkable bond with the cationically curable functional group of the heteropolymerizable monomer; (C) a thermosetting compound; and (D) crosslink with the thermosetting compound. It contains monomers containing polar functional groups capable of forming bonds.

2. In one embodiment, the radical-curable functional group of the heteropolymerizable monomer (A) is one or more selected from the group consisting of ethylenically unsaturated groups, acryloyl groups, acrylate groups, methacrylate groups, and vinyl groups. may

3. In one embodiment, the cationically curable functional groups of the heteropolymerizable monomer (A) are from the group consisting of epoxy groups, thioether groups, trioxane groups, oxazoline groups, caprolactone groups, tetrahydrofuran groups, oxetane groups, acrylate groups and vinyl ether groups. It may be one or more selected.

4. In one embodiment, the heteropolymerizable monomer (A) is 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-hydroxy-3-acryloyloxypropyl (Meth)acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2-methyl-1,3-butylene glycol di(meth)acrylate, 1,4-butane Diol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 3-methyl-1,5 -pentanediol di(meth)acrylate, ethoxylated 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate Acrylates, polyethylene glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, polyethylene glycol 1000 di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol 400 from the group consisting of di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, glycerine di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate It may be one or more selected.

5. In one embodiment, the functional group of monomer (B) is one or more selected from the group consisting of epoxy group, thioether group, trioxane group, oxazoline group, caprolactone group, tetrahydrofuran group, oxetane group, and vinyl ether group. may

6. In one embodiment, monomer (B) may be one or more selected from the group consisting of epoxy compounds, oxetane compounds, and vinyl ether compounds.

7. In one embodiment, the epoxy compound may be one or more selected from the group consisting of alicyclic epoxy resins, novolak-type epoxy resins, phenol-type epoxy resins, phenol novolak-type epoxy resins, and naphthalene-type epoxy resins. .

8. In one embodiment, the novolac-type epoxy resin may be a cresol novolac-type epoxy resin.

(ここで、nは1以上の整数である) 9. In one embodiment, the cresol novolak-type epoxy resin may have the structure of Formula 1 below.

(where n is an integer greater than or equal to 1)

10. In one embodiment, the thermosetting compound (C) is one selected from the group consisting of amine resins, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. or more.

11. In one embodiment, thermosetting compound (C) may be a blocked isocyanate compound.

12. In one embodiment, the isocyanate compound can be an aromatic isocyanate, an aliphatic isocyanate or a cycloaliphatic isocyanate.

13. In one embodiment, the isocyanate compound is 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, diisocyanate, tetramethyl-1,3-xylylene diisocyanate, 2,4-tolylene dimer, dimethyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,1,6,6-tetrahydroperfluoro-hexamethylene diisocyanate ( 1,1,6,6,-Tetrahydroperfluoro-hexamethylene diisocyanate (THFDI), methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trans-1 ,4-cyclohexane diisocyanate, dimethyl diisocyanate, bicycloheptane triisocyanate; adducts, birets or isocyanurates thereof; and combinations thereof.

14. In one embodiment, the isocyanate buret compound may be 1,3,5-tris(6-isocyanatohexyl) buret.

15. In one embodiment, the polar functional groups of monomer (D) are from hydroxyl, carboxy, amino, amine, carbonyl, acryl, acryloyl, nitrile, vinyl, halogen, urethane and ester groups. It may be one or more selected from the group consisting of.

16. In one embodiment, monomer (D) is 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, 2-hydroxy-3phenoxyethyl (meth)acrylate, 1-4-cyclohexanedimethanol mono(meth)acrylate, 2 -hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate , and 2-hydroxypropyl (meth)acrylate.

17. In one embodiment, the UV curable inkjet ink composition comprises, based on the weight of the total composition, 5-40% by weight of heteropolymerizable monomer (A); 0.05-10% by weight of monomer (B); weight percent thermosetting compound (C); and 1 to 15 weight percent monomer (D).

18. In one embodiment, the UV curable inkjet ink composition contains 10 to 30 wt% or 15 to 25 wt% heteropolymerizable monomer (A); 0.1 to 5 wt% or 0.5 to It may contain 1.5% by weight monomer (B) and 5 to 20% by weight or 10 to 20% by weight thermosetting compound (C).

19. In one embodiment, the UV curable inkjet ink composition may further comprise one or more of a multifunctional monomer, a radical photoinitiator, a colorant, a dispersant, a thermosetting polymerization inhibitor, and a leveling agent.

20. In one embodiment, the UV curable inkjet ink composition may be characterized as containing no cationic photoinitiator.

21. In one embodiment, the coloring agent may be rutile titanium oxide or anatase titanium oxide.

22. In one embodiment, the UV curable inkjet ink composition may be for marking formation after PSR final cure on a printed circuit board.

23. One embodiment of the present invention may relate to a printed circuit board comprising a cured product formed from the UV curable inkjet ink composition according to one embodiment.

The UV curable inkjet ink composition according to one embodiment of the present invention exhibits excellent adhesion and surface curability after curing, maintains low viscosity properties, and exhibits excellent storage stability. Due to these properties, the inkjet ink composition has excellent performance for forming markings not only after PSR development, but also after the final curing of PSR on a PCB substrate.

Schematic diagram (a) showing the curing process when using a conventional inkjet ink composition, and schematic diagram (b) showing the curing process when using a UV curable inkjet ink composition according to one embodiment of the present invention. are compared. Specifically, when the conventional inkjet ink composition is used after curing the developed PSR, the adhesiveness is remarkably deteriorated and the marking is hardly formed. On the other hand, the UV curable inkjet ink composition according to an embodiment of the present invention can be formed to exhibit excellent adhesion and excellent marking even after PSR development as well as after PSR curing. .

Various embodiments or examples described herein are exemplified for the purpose of clearly explaining the technical idea of the present invention. The technical spirit of the present invention includes various modifications, equivalents, alternatives, and all or all of each embodiment or example described herein. It includes embodiments or examples that are selectively combined from one part. Also, the technical idea of the present invention is not limited to the various embodiments or examples presented below and the specific descriptions thereof.

Terms used herein, including technical or scientific terms, may have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. Terms such as those defined in common dictionaries are to be construed to have a meaning consistent with the meaning they have in the context of the relevant art, and unless expressly defined in the present invention, are not ideal or overly formal terms. not be interpreted as meaning

As used herein, expressions such as "comprise," "may include," "comprise," "may comprise," "have," "may have," etc. refer to features (e.g., functions, actions) of interest. or components), does not exclude the presence of other additional features. That is, such expressions are to be understood as open-ended terms that encompass the possibility of including other embodiments.

Singular expressions used herein may include plural meanings, unless the context dictates otherwise, and this applies equally to singular expressions recited in the claims.

As used herein, "A, B and C", "A, B or C", "A, B and/or C" or "at least one of A, B and C", "A, B or at least one of C", "at least one of A, B and/or C", "at least one selected from A, B and C", "select from A, B or C Expressions such as "at least one selected from", "at least one selected from A, B and/or C" refer to each listed item or all possible combinations of listed items. can.

The term "about" as used in the present invention can indicate a normal error range for each value, as is widely known to those skilled in the art. This is in the context of the numerical values or ranges set forth herein, in one embodiment the stated or claimed numerical value or range is ±20%, ±15%, ±10%, ±9% , ±8%, ±7%, ±6%, ±5%, ±4%, ±3%, ±2%, or ±1%.

References to dimensions, numerical values and ranges thereof as used herein are not limited only to such dimensions, numerical values and ranges thereof, and may mean equivalent ranges inclusive thereof, unless otherwise specified by the context. .

Various embodiments of the invention are described below.

[UV curable inkjet ink composition]
One embodiment of the present invention relates to a UV curable inkjet ink composition.

In one embodiment, the UV curable inkjet ink composition comprises (A) a heteropolymerizable monomer comprising one or more radically curable functional groups and one or more cationically curable functional groups; (B) said heteropolymerizable (C) a thermosetting compound; and (D) a monomer containing a polar functional group capable of forming a crosslink with the thermosetting compound. obtain. The UV curable inkjet ink composition exhibits excellent viscosity and storage stability, adhesion and surface curability through the combination of these four components. These four components can exhibit even better effects when each is contained in a specific compounding ratio. In particular, even if it is used after the final curing of PSR, it shows excellent adhesion on the printed circuit board, and it can be used as an ink composition for marking even after curing of PSR, so it is superior to existing ink compositions. effect can be achieved.

[Heterogeneous Polymerizable Monomer (A)]
In one embodiment, the heteropolymerizable monomer (A) is not particularly limited as long as it is a compound having one or more different functional groups. Here, the different functional groups may be a radical curable functional group and a cationic curable functional group. The different polymerizable monomers (A) can exhibit mutually different curing reactivity by having mutually different functional groups, for example, they can have radical curing reactivity and cationic curing reactivity. This can contribute to excellent adhesion and pencil hardness, and can exhibit excellent properties in reaction speed.

The radical curable functional group may be one or more selected from the group consisting of ethylenically unsaturated groups, acryloyl groups, acrylate groups, methacrylate groups, and vinyl groups, but is not limited thereto. .

The cationically curable functional group may be one or more selected from the group consisting of an epoxy group, a thioether group, a trioxane group, an oxazoline group, a caprolactone group, a tetrahydrofuran group, an oxetane group, an acrylate group and a vinyl ether group, It is not limited to this.

Specifically, the heteropolymerizable monomer (A) is 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-hydroxy-3-acryloyloxypropyl (Meth)acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2-methyl-1,3-butylene glycol di(meth)acrylate, 1,4-butane Diol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 3-methyl-1,5 -pentanediol di(meth)acrylate, ethoxylated 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate Acrylates, polyethylene glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, polyethylene glycol 1000 di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol 400 from the group consisting of di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, glycerine di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate It may be one or more selected, but is not limited to this.

[Monomer (B)]
In one embodiment, the monomer (B) can be used without any particular limitation as long as it contains a functional group capable of forming a cross-linked bond by reacting with the cationically curable functional group of the heteropolymerizable monomer (A). Such a monomer (B) can form a cross-linking bond with a different polymerizable monomer by irradiation with energy rays even in the absence of a cationic photoinitiator. Such cross-linking allows the UV-curable inkjet ink composition of the present invention to exhibit excellent viscosity, storage stability, adhesion and surface curability.

The functional groups of the monomer (B) capable of forming a crosslinked bond by reacting with the cationically curable functional group of the heteropolymerizable monomer (A) include epoxy group, thioether group, trioxane group, oxazoline group, caprolactone group, tetrahydrofuran group, It may be one or more selected from the group consisting of an oxetane group and a vinyl ether group, but is not limited thereto.

Monomer (B) may be one or more selected from the group consisting of epoxy compounds, oxetane compounds, and vinyl ether compounds.

The epoxy compound may be a polyfunctional epoxy compound, and is one or more selected from the group consisting of alicyclic epoxy resins, novolak-type epoxy resins, phenol-type epoxy resins, phenol novolac-type epoxy resins, and naphthalene-type epoxy resins. may be Specifically, the novolak-type epoxy resin may be a cresol novolac-type epoxy resin, and the cresol novolac-type epoxy resin may have a structure represented by Formula 1 below.

Here, n indicates a repeating unit, and n can be an integer of 1 or more. For example, n can be an integer between 1 and 20 inclusive. The mass or mass-to-charge ratio (m/z) of a single isotope of such repeating units can be 176.0837.

The content of the cresol novolac epoxy resin contained in the UV curable inkjet ink composition is measured by Liquid Chromatography Time-of-Flight Mass Spectrometry (LC-TOF-MS). be able to. For example, 3D-map analysis of LC-TOF-MS analysis and comparison of m/z values with reference samples can be used to detect cresol novolac-type epoxy components contained in inkjet ink compositions. Specifically, by confirming the ion species and m/z corresponding to the repeating unit (n = 1 to 6) of the cresol novolak type epoxy from the 3D-map analysis of an arbitrary sample, the retention time (e.g. 11 to 13 minutes) A peak with a repeating unit difference (Δm/z = 176) of cresol novolac-type epoxy can be found in (ion species: ammonium adduct [M + NH4] +, which is, for example, the following may be derived from a 10 mM ammonium acetate aqueous solution, as shown in Table 1). Thus, the 3D-map analysis results and m/z values for any sample can be compared with a reference sample to confirm the presence of a cresol novolak-type epoxy component within any sample. For example, a reference sample is obtained by ultrasonically mixing a product containing a commercially available cresol novolac type epoxy resin (e.g., IJR-400 LW300, Korea Taiyo Ink Co., Ltd.) with a tetrahydrofuran (THF) solvent to obtain an appropriate epoxy resin content (e.g., 0.5% by weight), it can be used for experiments after pretreatment filtration (eg, Pall membrane filter, material: polytetrafluoroethylene (PTFE), pore size: 0.2 μm).

[LC-TOF-MS analysis conditions]
LC-TOF-MS analysis can be performed using a Waters Xevo G2-S instrument under the conditions shown in Table 1 below.

Specifically, alicyclic epoxy resin compounds include 3,4,3′,4′-diepoxybicyclohexyl, 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis (3,4-epoxycyclohexyl)-1,3-hexafluoropropane, bis(3,4-epoxycyclohexyl)methane, 1-[1,1-bis(3,4-epoxycyclohexyl) ] Ethylbenzene, bis(3,4-epoxycyclohexyl)adipate, 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl)methyl-3 ',4'-epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-bis(3,4-epoxycyclohexanecarboxylic acid) ester, cyclohexene oxide, 3,4-epoxycyclohexylmethyl alcohol, 3,4 Examples include, but are not limited to, alicyclic epoxy resin compounds having an epoxy group such as -epoxycyclohexylethyltrimethoxysilane. Commercially available products include, for example, Celoxide 2000, Celoxide 2021, Celoxide 3000, and EHPE3150 manufactured by Daicel Chemical Industries, Ltd.; Epomic VG-3101 manufactured by Mitsui Chemicals, Inc.; and E-1031S manufactured by Yuka Shell Epoxy Co., Ltd. TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd.; EPB-13 and EPB-27 manufactured by Nippon Soda Co., Ltd., but not limited thereto. Oxetane compounds include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3- Oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate , (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate and their oligomers or copolymers, as well as oxetane alcohols and novolac resins, poly(p -Hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, etherified products with resins having a hydroxyl group such as silsesquioxane, unsaturated monomers having an oxetane ring and alkyl (meth)acrylates Examples include, but are not limited to, oxetane compounds such as copolymers of The oxetane compound can also be a polyfunctional oxetane compound. Commercially available products include, for example, ethanecol OXBP, OXMA, OXBP, EHO manufactured by Ube Industries, Ltd., xylylene bisoxetane, and Aron oxetane OXT-101, OXT-201, OXT-211, OXT manufactured by Toagosei Co., Ltd. -221, OXT-212, OXT-610, PNOX-1009, etc., but not limited thereto.

Examples of vinyl ether compounds include cyclic ether-type vinyl ethers such as isosorbite divinyl ether and oxanorbornene divinyl ether (vinyl ethers having a cyclic ether group such as an oxirane ring, oxetane ring, and oxolane ring); allyl vinyl ethers such as phenyl vinyl ether; n-butyl vinyl ether , octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexanedivinyl ether, cyclohexanedimethanol divinyl ether, at the α and/or β positions; includes, but is not limited to, vinyl ether compounds having substituents such as alkyl groups and allyl groups. Examples of commercially available products include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE) and triethylene glycol divinyl ether manufactured by Maruzen Petrochemical Co., Ltd. , but not limited to.

[Thermosetting compound (C)]
In one embodiment, the thermosetting compound (C) is not particularly limited as long as it is a compound that can be cured by heating. Such a thermosetting compound (C) can be crosslinked with the monomer (D) to improve adhesion.

The thermosetting compound (C) may be one or more selected from the group consisting of amine resins, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. good.

Amine resins may be those known in the art such as methylol benzoguanamine, benzoguanamine, methylol glycoluril, methylol urea, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea. It is not restricted. Here, the alkoxymethyl group may be a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, or a butoxymethyl group, but is not limited thereto.

An isocyanate compound can mean a compound having one or more isocyanate groups in one molecule, and a blocked isocyanate compound means a compound having one or more blocked isocyanate groups in one molecule. can.

As the isocyanate compound, for example, aromatic isocyanate, aliphatic isocyanate or alicyclic isocyanate is used. Specific examples of aromatic isocyanates include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, Diisocyanate, tetramethyl-1,3-xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of aliphatic isocyanates include dimethyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,1,6,6-tetrahydroperfluoro-hexamethylene diisocyanate (1,1,6,6,-Tetrahydroperfluoro-hexamethylene diisocyanate, THFDI), methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylenebis(cyclohexyl isocyanate). Specific examples of cycloaliphatic isocyanates include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexane diisocyanate, dimethyl diisocyanate, and bicycloheptane triisocyanate. Also included are adducts, burettes and isocyanurates of the isocyanate compounds listed above. For example, the isocyanate compound may be 1,3,5-Tris(6-isocyanatohexyl)biuret.

The blocked isocyanate group contained in the blocked isocyanate compound means that the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated at a given temperature, the blocking agent is dissociated to generate isocyanate groups.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. The isocyanate compound that can react with the blocking agent includes isocyanurate type, burette type, adduct type, and the like. As this isocyanate compound, for example, the same aromatic isocyanate, aliphatic isocyanate or alicyclic isocyanate as mentioned above is used.

Examples of isocyanate blocking agents include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; ε-caprolactam (ε-CAP), δ-valerolactam, γ-butyrolactam and β-propiolactam, etc. active methylene blocking agents such as diethyl malonate (DEM), ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether alcohol-based blocking agents such as , ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldoxime, acetoxime , methylethyl ketoxime (MEKO), diacetyl monoxime, cyclohexanone oxime and other oxime blocking agents; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, ethylthiophenol and other mercaptan blocking agents; acid amide blocking agents such as acetic amide and benzamide; imide blocking agents such as succinimide and maleic acid imide; amine blocking agents such as xylidine, aniline, butylamine and dibutylamine; imidazoles such as imidazole and 2-ethylimidazole system blocking agents; imine blocking agents such as methyleneimine and propyleneimine; pyrazole blocking agents such as methylpyrazole (e.g., 3,5-dimethylpyrazole) and ethylpyrazole; do not have.

The blocked isocyanate compound may be commercially available, for example, BI7683, BI7642, BI201, BI220, BI7950, BI7951, BI7960, BI7961, BI7963, BI7981, BI7982, BI7990, BI7991, BI7992 (manufactured by Baxenden, Product name), Sumidule BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (all trade names manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B-874 , B-882 (manufactured by Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (manufactured by Asahi Kasei Chemicals, trade name), etc. can be used, but is not limited to this.

The above isocyanate compounds or blocked isocyanate compounds may be used singly or in combination of two or more.

The type of the cyclocarbonate compound is not particularly limited as long as it is a known carbonate compound used as a thermosetting component. For example, ethylene carbonate, propylene carbonate, butylene carbonate, or 2,3-carbonatopropyl methacrylate etc., but not limited to these.

Examples of polyfunctional epoxy compounds include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation; Epiclon 840, Epiclon 850, Epiclon 1050, and Epiclon 2055 manufactured by DIC Corporation; 011, YD-013, YD-127, YD-128, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by Dow Chemical Company, Sumie-Epoxy ESA-011, ESA-014, ELA manufactured by Sumitomo Chemical Co., Ltd. -115, ELA-128, A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664, etc. (all trade names) manufactured by Asahi Kasei Corporation; jERYL903 manufactured by Mitsubishi Chemical Corporation; jERYL903 manufactured by Mitsubishi Chemical Corporation; Epiclon 152, Epiclon 165, Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDB-400, YDB-500, Dow Chemical Co., Ltd. D.E.R.542, Sumitomo Chemical Co., Ltd. Sumie-Epoxy ESB-400, ESB-700, Asahi Kasei Co., Ltd. Brominated epoxy resins such as A.E.R.711 and A.E.R.714 (both trade names) manufactured by the company; jER152 and jER154 manufactured by Mitsubishi Chemical Corporation; D.E.N.431 and D.E.N.438 manufactured by Dow Chemical Co.; -730, Epiclon N-770, Epiclon N-865, Epotote YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN manufactured by Nippon Kayaku Co., Ltd. -104S, RE-306, Sumie epoxy ECN-195X, ECN-220 manufactured by Sumitomo Chemical Co., Ltd., A.E.R. ECN-235, ECN-299 manufactured by Asahi Kasei Corporation, etc. (all trade names) novolac type epoxy resins; Bisphenol F type epoxy resins such as Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Epotote YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (all trade names); Hydrogenated bisphenol A type epoxy resins such as Epotote ST-2004, ST-2007, ST-3000 (trade name) manufactured by Sumikin Chemical Co., Ltd.; jER604 manufactured by Mitsubishi Chemical Co., Ltd.; Glycidylamine type epoxy resins such as Epototo YH-434 and Sumie Epoxy ELM-120 (both trade names) manufactured by Sumitomo Chemical Co., Ltd.; hydantoin type epoxy resins; Cyclic epoxy resins; YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Co., etc. (all trade names) trihydroxyphenylmethane type epoxy resins; Mitsubishi Chemical Corporation Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, and YL-6121 (all trade names) manufactured by Nippon Kayaku Co., Ltd.; EBPS-200 manufactured by Nippon Kayaku Co., Ltd.; EPX-30 manufactured by DIC Corporation, bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by DIC Corporation; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation Tetraphenylolethane type epoxy resin such as jERYL-931 (both trade names) manufactured by Nissan Chemical Industries, Ltd.; heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Industries, Ltd.; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd.; Naphthalene group-containing epoxy resins such as -4750 and EXA-4700; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; CP-50S and CP-50M manufactured by NOF Corporation Glycidyl methacrylate copolymer epoxy resins such as; further copolymer epoxy resins of cyclohexyl maleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, etc.), CTBN-modified epoxy resins (for example, , YR-102 YR-450 manufactured by Tohto Kasei Co., Ltd.) and the like, but are not limited thereto. These epoxy resins can be used alone or in combination of two or more.

Polyfunctional oxetane compounds include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl- 3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, oligomers or copolymers thereof, oxetane alcohols and novolac resins , poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, or etherified products with resins having hydroxyl groups such as silsesquioxane, etc., but are not limited to these. isn't it. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates. Commercially available products include, for example, ethanecol OXBP, OXMA, OXBP, EHO manufactured by Ube Industries, Ltd., xylylene bisoxetane, and Aron oxetane OXT-101, OXT-201, OXT-211, OXT manufactured by Toagosei Co., Ltd. -221, OXT-212, OXT-610, PNOX-1009 and the like.

Examples of the episulfide resin include, but are not limited to, bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Also, an episulfide resin obtained by replacing the oxygen atom of the epoxy group of the novolac type epoxy resin with a sulfur atom by using the same synthesis method can be used.

The above thermosetting compounds can be used singly or in combination of two or more.

[Monomer (D)]
In one embodiment, monomer (D) may contain polar functional groups capable of reacting with thermosetting compound (C) to form cross-links. Such a monomer (D) can improve the adhesion after curing of the UV-curable inkjet ink composition of the present invention, which is achieved by forming a cross-linked bond with the thermosetting compound (C). be done.

The polar functional group of the monomer (D) is not particularly limited as long as it can react with the thermosetting compound (C) to form a crosslinked bond. For example, the polar functional group is selected from the group consisting of hydroxyl group, carboxyl group, amino group, amine group, carbonyl group, acryl group, acryloyl group, nitrile group, vinyl group, halogen group, urethane group, and ester group. There may be more than one, but it is not limited to this.

The monomer (D) is used without particular limitation as long as it can react with the thermosetting compound (C) to form a crosslinked bond. For example, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate , 2-hydroxy-3-phenoxyethyl (meth)acrylate, 1-4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, one or more selected from the group consisting of 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, and 2-hydroxypropyl (meth)acrylate; can be, but is not limited to.

[Content of each component]
In one embodiment, the content of the heteropolymerizable monomer (A) is about 5 to about 40% by weight, about 7 to about 35% by weight, about 10 to about 30% by weight, based on the total weight of the composition of the present invention. , about 15 to about 25 weight percent, about 18 to about 22 weight percent, or about 19 to about 21 weight percent. When the content of the heteropolymerizable monomer (A) is at least the above minimum value, the adhesion and surface curability to be achieved in the UV curable inkjet ink composition of the present invention are further improved, and the above maximum value is achieved. In the case of the following, the effects (adhesion, surface curability, viscosity and storage stability) to be achieved by the present invention are achieved.

In one embodiment, the content of monomer (B) is about 0.05 to about 10 wt%, about 0.1 to about 9 wt%, about 0.1 to about 7 wt%, about 0.5 wt%, based on the total weight of the composition of the present invention. from about 5%, from about 0.5% to about 3%, from about 0.5% to about 2%, from about 0.5% to about 1.5%, or from about 0.5% to about 1%. When the content of the monomer (B) is at least the above minimum value, the viscosity, storage stability, and adhesion to be achieved in the UV curable inkjet ink composition of the present invention can be achieved, and when it is at most the above maximum value, Viscosity and storage stability and surface curability are achieved.

In one embodiment, the content of thermosetting compound (C) is about 2 to about 30% by weight, about 5 to about 25% by weight, about 5 to about 20% by weight, based on the total weight of the composition of the present invention. , about 7 to about 20 weight percent, about 10 to about 20 weight percent, about 12 to about 18 weight percent, or about 14 to about 16 weight percent. When the content of the thermosetting compound (C) is at least the above minimum value, the adhesion to be achieved in the UV curable inkjet ink composition of the present invention is achieved, and when it is at most the above maximum value, the present invention The desired effects (adhesion, surface curability, viscosity and storage stability) are achieved.

In one embodiment, the content of monomer (D) is about 1 to about 15 wt%, about 5 to about 15 wt%, about 7 to about 13 wt%, about 9 wt%, based on the total weight of the composition of the present invention. may be up to about 11% by weight. When the content of the monomer (D) is at least the above minimum value, the adhesion to be achieved in the UV curable inkjet ink composition of the present invention is achieved. When the content of the monomer (D) is less than the above maximum value, the surface curability to be achieved in the UV curable inkjet ink composition of the present invention is achieved, and when the content of the monomer (D) exceeds the above maximum value. However, due to the low viscosity, printability such as bleeding of the ink during printing may be poor, and there is a possibility that the chemical resistance and tilting will be weak.

[Other Additives]
In one embodiment, a UV curable inkjet ink composition can include one or more of a multifunctional monomer, a radical photoinitiator, a colorant, a dispersant, a thermosetting polymerization inhibitor, and a leveling agent.

Any known polyfunctional monomer can be used without particular limitation as long as it is a monomer having two or more or three or more functional groups. Examples include trimethylolpropane triacrylate, trimethylolpropane tri(meth) Acrylate, propoxylated trimethylolpropane tri(meth)acrylate, or pentaerythritol tri(meth)acrylate can be used, but not limited thereto. Such polyfunctional monomers can improve the pencil hardness and chemical resistance after curing of the UV-curable inkjet ink composition of the present invention.

As the radical photoinitiator, known ones can be used without particular limitation. It may contain at least one or more selected from oxides or oxime esters. More specifically, for example, biacetyl, benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1-methylethyl-phenolketone, p-isopropyl-α-hydroxyisobutylphenone, N,N-dimethylaminoacetophenone, 2-methyl-1- [4-(methylthio)phenyl]-2-morpholinopropan-1-one, ethyl-p-dimethylaminobenzoate, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2- amyl anthraquinone, 2-aminoanthraquinone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzyl dimethyl ketal, benzophenone, methylbenzophenone, trimethylbenzophenone (TZT), 4-benzoyl- 4'-methyldiphenyl sulfide, 4,4'-dichlorobenzophenone, diethylthioxanthone (DETX), 2-isopropylthioxanthone (ITX), 4,4'-bisdiethylaminobenzophenone, 2-methyl-1-[4-(methylthio) phenyl]-2-morpholinopropanone-1 (IRGACURE907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (IRGACURE 369), 2-dimethylamino-2-(4- methylbenzyl)-1-(4-morpholinylphenyl)-butanone-1 (IRGACURE 379), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (OMNIRAD 819 or IRGACURE 819), diphenyl (2, 4,6-trimethylbenzoyl)phosphine oxide (Mosaphoto 348), bis(eth-5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl ] titanium, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl- Indan-5-yl}-2-methyl-propan-1-one (ESACURE ONE), 1-propanone-1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[( 4-methylphenyl)sulfonyl] (ESACURE 1001M), bis-N,N-[4-dimethylaminobenzoyl)oxyethylene-l-yl]-methylamine (ESACURE A198) or mixtures of two or more thereof can be used, but is not limited to this.

As the coloring agent, known coloring agents such as red, blue, green, yellow, white, and black can be used. Two or more kinds can be used in combination.

The white colorant may be titanium oxide. The titanium oxide may be rutile titanium oxide or anatase titanium oxide. Rutile-type titanium oxide can be used in consideration of the colorability, hiding power, and stability of the UV-curable inkjet ink composition. The rutile-type titanium oxide may be rutile-type titanium oxide surface-treated (coated) with one or more of Si, Al, and Zr, specifically, surface-treated with Al and Si. It may be (coated) rutile titanium oxide or rutile titanium oxide surface-treated (coated) with Si, Al and Zr, but is not limited thereto. TiONA ^(R) 595 can be used as titanium oxide.

Black colorants include carbon black, perylene black, iron oxide, manganese dioxide, aniline black, activated carbon, etc., but are not limited to these.

Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone colorants. is mentioned. Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, Monoazo red coloring agents such as 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268 and 269; disazo red coloring agents such as Pigment Red 37, 38 and 41; and Pigment Red 48: 1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, monoazo lake red colorants such as 63:1, 63:2, 64:1 and 68; benzimidazolone red colorants such as Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185 and Pigment Red 208; Perylene red colorants such as Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, Pigment Red 254 , Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272, Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 , Pigment Red 242 and other condensed azo red colorants, Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207 and other anthraquinone red colorants, Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, and other quinacridone red colorants, but are not limited thereto.

Blue colorants include phthalocyanines, anthraquinones, and the like, and pigments are compounds classified as pigments, specifically: Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60, etc., but not limited thereto. Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, etc. can be used, but is not limited to this. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of green colorants include phthalocyanine, anthraquinone, and perylene. Specific examples include Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, and Solvent Green 28. can be used, but is not limited to this. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone colorants. Specific examples include the following. Anthraquinone yellow colorants such as Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202, Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179 , isoindolinone-based yellow colorants such as Pigment Yellow 185; condensed azo-based yellow colorants such as Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, and Pigment Yellow 180; Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 and other benzimidazolone yellow colorants, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10 , 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, monoazo yellow coloring agents, pigment yellow Disazo yellow colorants such as 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 can be used. However, it is not limited to this.

Colorants such as purple, orange, brown and black may be added for the purpose of adjusting the color tone. Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 17, C. I. Pigment Orange 24, C. I. Pigment Orange 34, C. I. Pigment Orange 36, C. I. Pigment Orange 38, C. I. Pigment Orange 40, C. I. Pigment Orange 43, C. I. Pigment Orange 46, C. I. Pigment Orange 49, C. I. Pigment Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment Orange 73, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Black 1, C.I. can be used, but is not limited to this.

The colorant content is about 1 to about 20%, about 5 to about 20%, about 10 to about 20%, about 12 to about 18%, or , from about 14 to about 16% by weight.

As the dispersant, any known one can be used without any particular limitation, and from the aspect of being suitable for the dispersibility of the colorant contained in the composition of the present invention, BYK's DISPERBYK-111 and DISPERBYK are commercially available. -110, DISPERBYK-118, DISPERBYK-140, DISPERBYK-142, DISPERBYK-163, DISPERBYK-2150, DISPERBYK-2200, DISPERBYK-2205, DISPERBYK-2163, DISPERBYK-2013, DISPERBYK-180, DISPERBYK-2155, DISPERBYK-2009 , DISPERBYK-168, DISPERBYK-2164, DISPERBYK-2118, DISPERBYK-2008, DISPERBYK-9076, DISPERBYK-9077 and DISPERBYK-2055, but are not limited thereto.

The content of the dispersant is about 0.1 to about 5 wt%, about 0.5 to about 2 wt%, about 0.7 to about 1.5 wt%, about 0.9 to about 1.3 wt%, or , from about 0.9 to about 1.1% by weight.

The thermosetting polymerization inhibitor may be used without any particular limitation as long as it is used to maintain the storage stability of the ink. The UV curable inkjet ink composition of the present invention contains a thermosetting compound, for example a blocked isocyanate. Such thermosetting compounds are blocked and maintain a stable state before heating. may reduce storage stability. A thermosetting polymerization inhibitor is used to prevent such decrease in storage stability and maintain the storage stability of the inkjet ink composition. For example, using one or more of hydroquinone, phenols such as tert-butylcatechol and butylhydroxyanisole, quinones such as para-benzoquinone, amines such as nitrohydroxyamine and phenylenediamine, mercaptans, and dithiocarbamates. can be used, but is not limited to this. The thermosetting polymerization inhibitor is an amine such as Tris(N-hydroxy-N-nitrosophenylamineto-O,O')aluminum or Nitrohydroxyamine aluminum salt (Q-1301; Wako) can be used.

The content of the thermosetting polymerization inhibitor is about 0.01 to about 0.5 wt%, about 0.01 to about 0.3 wt%, about 0.05 to about 0.2 wt%, about 0.05 to about 0.15, based on the total weight of the composition of the present invention. % by weight, or from about 0.05 to about 0.1% by weight. When the content of the thermosetting polymerization inhibitor is at least the above minimum value, the storage stability of the UV curable inkjet ink composition is sufficiently achieved, and when the content is at most the above maximum value, curing by heating is the purpose. It is achieved as much as

Any leveling agent can be used without particular limitation as long as it increases adhesion on the finally cured PSR substrate and solves the repelling problem (pinhole phenomenon). For example, the leveling agent may be any commercially available silicone-based or non-silicone leveling agent from BYK, in terms of suitability for the leveling properties of the composition of the present invention, and may be used in combination of two or more. Alignment can be used. Silicone leveling agents include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-325N, BYK-326, BYK-327, BYK-329, BYK-331, BYK-333, BYK-342, BYK-346, BYK-345, BYK-348, BYK-349, BYK-370, BYK-377, BYK- 378, BYK-3455, BYK-3456, BYK-3450, BYK-3451, BYK-3480, BYK-3481, BYK-3760, BYK-UV-3500, BYK-UV-3505, BYK-UV-3530, BYK- It may be one or more of UV-3535, BYK-UV-3570, BYK-UV-3575, and BYK-UV-3576, but is not limited thereto. Non-silicone leveling agents are BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-381, BYK-392, BYK-394, BYK-399, BYK-3440 , BYK-3441, BYK-3560, and BYK-3566.

The content of the leveling agent is about 0.1 to about 1.0 wt%, about 0.2 to about 0.8 wt%, about 0.3 to about 0.7 wt%, or about 0.4 to about 0.6 wt% based on the total weight of the composition of the present invention. may be When the content of the leveling agent is equal to or greater than the above minimum value, it is possible to achieve desired adhesion or produce a UV curable inkjet ink composition free from repelling problems (pinhole phenomenon). When it is equal to or less than the above maximum value, it is possible to produce a UV curable inkjet ink composition that satisfies reactivity and achieves adhesion.

In one embodiment, the UV curable inkjet ink composition further comprises one of dispersants, defoamers, rheology modifiers, foaming agents, surfactants, antioxidants, antistatic agents, and brighteners. above, in which case they may be added in small amounts relative to the weight of the total ink composition.

In one embodiment, the UV curable inkjet ink composition can be characterized as containing no cationic photoinitiator. The inkjet ink composition of the present invention is characterized in that a monomer having a functional group capable of forming a cross-linking bond with a heterogeneous polymerizable monomer and a cationic curable functional group is cured by an active energy ray without using a cationic photoinitiator. have Due to such characteristics, the inkjet ink composition of the present invention can exhibit excellent viscosity or storage stability and exhibit excellent surface curability.

The present invention should be further clarified through the embodiments described above and the examples described below. Hereinafter, the present invention will be described in detail so that those skilled in the art can easily understand and implement the present invention through examples described with reference to the following tables. However, these examples are for illustrative description of the present invention, and the scope of the present invention is not limited to these examples.

I. Manufacture of inkjet ink composition and marking ink substrate

1. Preparation of UV curable inkjet ink composition The reactants having the ingredients and contents shown in Tables 2 and 3 below were mixed at 45°C at a speed of 2,000 rpm for 1.5 hours using a stirrer, and then pigments and dispersions were prepared. The agent was added and dispersed for 3 hours using zirconia beads with a particle size of 0.2 μm. After that, it was filtered through a 1 μm filter to prepare a UV curable inkjet ink composition.

The specific components listed in Tables 2 and 3 are as follows.

1) Heterogeneous polymerizable monomer (A): 2-(2-vinyloxyethoxy)ethyl (meth)acrylate (manufactured by Nippon Shokubai Co., Ltd.)
2) Monomer (B) (cresol novolac type epoxy): BH-50 (manufactured by JB Caltech Co., Ltd.; this product is a product with a ratio of 12:0.7 of trifunctional blocked isocyanate: cresol novolak type epoxy, and cresol The novolac type epoxy compound is added as a mixture blended with trifunctional blocked isocyanate.After blending (based) in a large amount according to the content ratio in Tables 2 and 3, it is divided and used.)
3) Thermosetting compound (C) (trifunctional blocked isocyanate): BH-50 (manufactured by JB Caltech Co., Ltd.; contains 1,3,5-tris(6-isocyanatohexyl) buret, cresol (added as a blended mixture with novolac epoxy)
4) Monomer (D) (monofunctional monomer containing hydroxyl group): 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.)
5) Polyfunctional monomer: trimethylolpropane triacrylate (manufactured by Allnex)
6) Other monomers: 1,6-hexanediol diacrylate (Hexanediol diacrylate; HDDA; manufactured by Allnex)
7) Radical photoinitiator: a mixture of OMNIRAD 819 (manufactured by IGM Resin BV) and MOSAPHOTO 348 (manufactured by UFC Corporation) (OMNIRAD 819 and MOSAPHOTO 348 mixed at a ratio of 1.2:1.8)
8) Titanium oxide: TiONA 595 (manufactured by Tronox)
9) Thermosetting polymerization inhibitor: Q-1301 (manufactured by Wako)
10) Leveling agent: BYK-307 (manufactured by BYK)
11) Cationic photoinitiator: Omnicat 250 (manufactured by IGM Resin BV)

2. Manufacture of photo solder resist (PSR) substrate Taiyo photo solder resist PSR-4000 MB (screen type PSR) and PSR-4000 SP71 (spray type PSR) were printed on a 1.6T printed circuit board using screen printing and spray printing methods. After printing on FR-4 (thickness 40um±2), it was dried at 90°C for 30 minutes. In order to pattern and expose the dried PSR, a development film (PET film) was applied with an exposure machine (OTS Technology, YH-7090 8K), and after exposure at 400 mJ/cm ² , a development machine (Pectu Enterprises, TRUMAN DI442) was applied. , Na2CO3 1wt%, 60sec) to fabricate a patterned and developed substrate. To final cure the developed PSR, a final cure was performed at 150°C for 60 minutes in a hot air circulating drying oven to produce a PSR substrate for evaluation of the marking ink.

3. Manufacture of marking ink substrate The UV curable inkjet ink composition manufactured in item 1 above is applied to an inkjet printer (Microcraft MJP2013K1-DU), a piezoelectric type print head, and the composition described in item 2 above is used. 1.6T FR-4 (150 mm x 95 mm) circuitized printed wiring board manufactured by the Company and having the PSR final cured. After that, the UV LED lamp (385nm, 395nm) attached to the inkjet printer is used to irradiate the marking ink solution applied on the printed circuit board with UV rays at a total cumulative light intensity of 400mJ/cm ² to proceed with photocuring. rice field. After the above photocuring, heat curing was proceeded at a temperature of 150° C. for 60 minutes in a hot air circulating drying oven to produce a marking ink coating film.

II. Characteristic test The marking ink coating films produced as described above were subjected to the following evaluations, and the UV curable inkjet ink compositions of Examples and Comparative Examples were evaluated. The evaluation results are shown in Tables 2 and 3, respectively.

1. Adhesion 100 square (□) scales (10 x 10) were made on the surface of the cured composition at an angle of 30° using a cutter to a width of 1 mm, and then adhered with an adhesive tape, and then instantaneously peel off to After peeling off, the peeled form was evaluated for adhesion according to Table 2 below.

2. Surface hardening (Tacky)
After rubbing the surface of the cured composition with a white cloth moistened with alcohol, check the extent to which the ink oozes out on the white cloth, and touch the surface of the cured composition with your hand. The surface curability was evaluated based on the presence or absence of transfer of .
⊚: There is no transfer of the fingerprint of the hand, and the ink does not ooze out at all.
Good: No fingerprints were transferred, but a little bleeding of the ink was observed.
Δ: A fingerprint of the hand was transferred, and a little bleeding of the ink was observed.
x: A fingerprint of the hand was transferred, and the ink disappeared.

3. Viscosity and Storage Stability Viscosity was measured (initial viscosity) for the UV curable inkjet ink composition produced by the above method. After that, the composition was stored in a sealed container at 50° C. for 2 weeks, and the viscosity was measured again to confirm the change in viscosity according to the following formula.

(A=初期粘度、B=2週間保存後の粘度)

(A=initial viscosity, B=viscosity after 2 weeks storage)

The change in viscosity calculated in this way was evaluated according to the following criteria.
Viscosity change 0% to 2% or less: ◎
Viscosity change over 2% and 8% or less: ○
Viscosity change from 8% to 15%: △
Over 15% change in viscosity: ×

According to Examples 1 to 17 in Tables 2 and 3, the UV curable inkjet ink composition according to one embodiment of the present invention comprises a heteropolymerizable monomer (A), a monomer (B), and a thermosetting compound (C). and monomer (D), exhibiting overall excellent viscosity and storage stability, adhesion and surface curability. On the other hand, according to Table 2, Comparative Examples 1 to 4 lacking any one of the components (A), (B), (C), and (D) of the UV curable inkjet ink composition of the present invention In this case, the characteristics of the UV-curable inkjet ink composition to be achieved by the present invention could not be achieved. In the case of Comparative Examples 1 to 4, it can be confirmed that the adhesion is very poor, and with such properties, marking is not sufficiently formed after the final curing of PSR. In particular, in the case of Comparative Example 2, it was confirmed that the surface curability was very poor because the heteropolymerizable monomer (A) was not included. Also, in the case of Comparative Example 5 containing a cationic photoinitiator, it was confirmed that the surface curability, viscosity and storage stability were very poor. The inkjet composition of the present invention can achieve excellent surface curability, viscosity and storage stability by not using such a cationic photoinitiator.

Claims (23)

(A) heteropolymerizable monomers containing one or more radically curable functional groups and one or more cationically curable functional groups;
(B) a monomer containing a functional group capable of forming a cross-linking bond with the cationically curable functional group of the heteropolymerizable monomer;
(C) a thermosetting compound; and
(D) containing a monomer containing a polar functional group capable of forming a cross-linking bond with the thermosetting compound,
A UV curable inkjet ink composition. The radical-curable functional group of the heteropolymerizable monomer (A) is one or more selected from the group consisting of an ethylenically unsaturated group, an acryloyl group, an acrylate group, a methacrylate group, and a vinyl group.
The UV curable inkjet ink composition according to claim 1. 1, wherein the cationically curable functional group of the heteropolymerizable monomer (A) is selected from the group consisting of an epoxy group, a thioether group, a trioxane group, an oxazoline group, a caprolactone group, a tetrahydrofuran group, an oxetane group, an acrylate group and a vinyl ether group; is one or more
The UV-curable inkjet ink composition according to claim 1 or 2. The heteropolymerizable monomer (A) is 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate. , hydroxypivalyl hydroxypivalate di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2-methyl-1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate ) acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate (Meth)acrylates, ethoxylated 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, polyethylene glycol 1000 di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate 1 selected from the group consisting of acrylates, polypropylene glycol 700 di(meth)acrylate, glycerin di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate is one or more
The UV-curable inkjet ink composition according to any one of claims 1 to 3. The functional group of the monomer (B) is one or more selected from the group consisting of an epoxy group, a thioether group, a trioxane group, an oxazoline group, a caprolactone group, a tetrahydrofuran group, an oxetane group, and a vinyl ether group.
The UV-curable inkjet ink composition according to any one of claims 1 to 4. The monomer (B) is one or more selected from the group consisting of epoxy compounds, oxetane compounds, and vinyl ether compounds.
The UV curable inkjet ink composition according to any one of claims 1 to 5. The epoxy compound is one or more selected from the group consisting of alicyclic epoxy resins, novolak-type epoxy resins, phenol-type epoxy resins, phenol novolac-type epoxy resins, and naphthalene-type epoxy resins.
The UV curable inkjet ink composition according to claim 6. The novolak-type epoxy resin is a cresol novolac-type epoxy resin,
The UV curable inkjet ink composition according to claim 7. The cresol novolak type epoxy resin has a structure of the following formula 1,
The UV curable inkjet ink composition according to claim 8.

(Here, n is an integer greater than or equal to 1.) The thermosetting compound (C) is one or more selected from the group consisting of amine resins, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins.
The UV curable inkjet ink composition according to any one of claims 1 to 9. The thermosetting compound (C) is a blocked isocyanate compound,
The UV curable inkjet ink composition according to claim 10. The isocyanate compound is an aromatic isocyanate, an aliphatic isocyanate or an alicyclic isocyanate,
The UV curable inkjet ink composition according to claim 11. The isocyanate compounds include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, tetra methyl-1,3-xylylene diisocyanate, 2,4-tolylene dimer, dimethyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,1,6,6-tetrahydroperfluoro-hexamethylene diisocyanate (1,1, 6,6,-Tetrahydroperfluoro-hexamethylene diisocyanate (THFDI), methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexane diisocyanate, dimethyl diisocyanate, bicycloheptane triisocyanate; adducts, burettes or isocyanurates thereof; and one or more selected from the group consisting of combinations thereof,
The UV curable inkjet ink composition according to claim 12. The isocyanate buret compound is 1,3,5-tris(6-isocyanatohexyl) buret,
The UV curable inkjet ink composition according to claim 13. the polar functional group of the monomer (D) is selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an amine group, a carbonyl group, an acrylic group, an acryloyl group, a nitrile group, a vinyl group, a halogen group, a urethane group, and an ester group; is one or more selected
The UV curable inkjet ink composition according to any one of claims 1 to 14. The monomer (D) is 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, 2-hydroxy-3phenoxyethyl (meth)acrylate, 1-4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, and 2 - is one or more selected from the group consisting of hydroxypropyl (meth)acrylate,
The UV curable inkjet ink composition according to any one of claims 1 to 15. Based on total composition weight
5-40% by weight of heteropolymerizable monomer (A);
0.05-10% by weight of monomer (B);
2 to 30% by weight of a thermosetting compound (C); and
1-15% by weight of monomer (D)
including,
The UV curable inkjet ink composition according to any one of claims 1 to 16. Based on total composition weight
10-30% by weight or 15-25% by weight of heteropolymerizable monomer (A);
0.1 to 5% by weight or 0.5 to 1.5% by weight of monomer (B) and
5-20% by weight or 10-20% by weight of thermosetting compound (C)
including,
The UV curable inkjet ink composition according to claim 17. further comprising one or more of a multifunctional monomer, a radical photoinitiator, a colorant, a dispersant, a thermosetting polymerization inhibitor, and a leveling agent;
The UV curable inkjet ink composition according to any one of claims 1 to 18. characterized in that it does not contain a cationic photoinitiator,
The UV curable inkjet ink composition according to any one of claims 1 to 19. The coloring agent is rutile-type titanium oxide or anatase-type titanium oxide,
The UV curable inkjet ink composition according to claim 20. The UV curable inkjet ink composition is for forming markings after final curing of PSR on a printed circuit board.
The UV curable inkjet ink composition according to any one of claims 1-21. A printed circuit board comprising a cured product formed from the UV curable inkjet ink composition according to any one of claims 1 to 22.

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