KR20230029315A - Uv curable type ink-jet ink composition - Google Patents

Abstract

One embodiment of the present invention relates to a UV curable inkjet ink composition. The UV curable inkjet ink composition exhibits excellent viscosity and storage stability, adhesion and surface curability through a combination of four components, and thus, unlike conventional inkjet ink compositions, excellent marking can be formed on a printed circuit board even after PSR curing. Therefore, the UV curable inkjet ink composition of the present invention can be used even when marking is required after final curing due to a change in the process sequence of the printed circuit board, thereby overcoming the limitations of the conventional inkjet ink compositions.

Description

UV curable inkjet ink composition {UV CURABLE TYPE INK-JET INK COMPOSITION}

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

Marking ink is used in the final stage of manufacturing a printed circuit board before assembling electronic components on a printed circuit board (hereinafter referred to as 'PCB'). Marking inks are used to mark component designators, test points, and other features that aid in assembling, evaluating, using, or repairing circuit boards. Marking ink can be used on all printed circuit boards, but the field of use is not limited thereto.

In the manufacture of a printed circuit board (PCB), a photo solder resist (hereinafter 'PSR') coating process is required to protect the circuit. Generally, after the PSR process, markings are formed on the required part of the PCB surface. Conventional inkjet ink compositions are mainly used to form markings after PSR development, and thereafter, it is common to cure the PSR and markings together through final curing. This is because when the marking is formed after the final curing of the PSR, the adhesion to the substrate is significantly insufficient and the marking is not properly formed.

Therefore, in the case of the conventional inkjet ink composition, when the process sequence is changed to form a marking after final curing, the use is limited.

Korean Patent Publication No. 10-2015-0050581

The present invention is to solve the above problems, and provides a technology 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, wherein the ink composition includes (A) a heteropolymerization monomer including at least one radical curable functional group and at least one cation curable functional group; (B) a monomer containing a functional group capable of forming a cross-link with the cation-curable functional group of the heteropolymer monomer; (C) a heat curable compound; and (D) a monomer containing a polar functional group capable of forming a cross-link with the thermosetting compound.

2. In one embodiment, the radical curable functional group of the heteropolymerization monomer (A) may be at least one selected from the group consisting of an ethylenically unsaturated group, an acryloyl group, an acrylate group, a methacrylate group, and a vinyl group.

3. In one embodiment, the cation-curable functional group of the heteropolymerization monomer (A) is 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 It may be one or more selected from the group consisting of ether groups.

4. In one embodiment, the heteropolymerization monomer (A) is 2-(2-vinyloxyethoxy)ethyl(meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-hydroxy- 3-acryloyloxypropyl (meth)acrylate, hydroxypivalylhydroxypivalate di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2-methyl-1,3- Butylene glycol di(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1, 10-decanedioldi(meth)acrylate, 3-methyl-1,5-pentanedioldi(meth)acrylate, ethoxylated 1,6-hexanedioldi(meth)acrylate, neopentylglycoldi(meth)acrylate 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, polypropylene glycol 700 di(meth)acrylate, glycerin di It may be at least one selected from the group consisting of (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate.

5. In one embodiment, the functional group of the monomer (B) is one 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 may be ideal

6. In one embodiment, the monomer (B) may be at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound.

7. In one embodiment, the epoxy compound may be at least one selected from the group consisting of an alicyclic epoxy resin, a novolac-type epoxy resin, a phenol-type epoxy resin, a phenol novolac-type epoxy resin, and a naphthalene-type epoxy resin.

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

9. In one embodiment, the cresol novolac-type epoxy resin may have a structure represented by Formula 1 below.

[Formula 1]

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

10. In one embodiment, the thermosetting compound (C) is at least one selected from the group consisting of an amine resin, an isocyanate compound, a block isocyanate compound, a cyclocarbonate compound, a multifunctional epoxy compound, a multifunctional oxetane compound, and an episulfide resin can

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

12. In one embodiment, the isocyanate compound may be an aromatic isocyanate, an aliphatic isocyanate or an alicyclic 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-xylyl Rendiisocyanate, m-xylylenediisocyanate, tetramethyl-1,3-xylene 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(cyclohexylisocyanate ), isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexane diisocyanate, dimeryl diisocyanate, bicycloheptane triisocyanate; adducts, biurets or isocyanurates thereof; And it may be one or more selected from the group consisting of combinations thereof.

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

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

16. In one embodiment, monomer (D) is 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, 2-hydroxy-3phenoxyethyl (meth)acrylate, 1-4-cyclo Hexane dimethanol 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 5 to 40% by weight of the heteropolymer monomer (A) based on the total weight of the composition; 0.05 to 10% by weight of monomer (B); 2 to 30% by weight of a heat curable compound (C); and 1 to 15% by weight of the monomer (D).

18. In one embodiment, the UV curable inkjet ink composition comprises 10 to 30% by weight or 15 to 25% by weight of the heteropolymerization monomer (A) based on the total weight of the composition; 0.1 to 5% by weight or 0.5 to 1.5% by weight of the monomer (B) and 5 to 20% by weight or 10 to 20% by weight of the thermosetting compound (C).

19. In one embodiment, the UV curable inkjet ink composition may further include at least one of a multifunctional monomer, a radical photoinitiator, a colorant, a dispersant, a heat curable polymerization inhibitor, and a leveling agent.

20. In one embodiment, the UV curable inkjet ink composition may be characterized in that it does not contain a cationic photoinitiator.

21. In one embodiment, the colorant can be rutile-type titanium oxide or anatase-type titanium oxide.

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

23. One embodiment of the present invention may relate to a printed circuit board characterized in that a cured product formed of the UV curable inkjet ink composition according to one embodiment is provided on a substrate.

The UV curable inkjet ink composition according to one embodiment of the present invention has excellent adhesion and surface curability after curing, and exhibits excellent storage stability by maintaining low viscosity characteristics. Due to these characteristics, the inkjet ink composition has excellent performance that can be used for marking formation not only after PSR development but also after final curing of PSR on a PCB substrate.

1 is a comparison between a schematic diagram (a) showing a curing process in the case of using a conventional inkjet ink composition and a schematic diagram (b) showing a curing process in the case of using a UV curable inkjet ink composition according to an embodiment of the present invention. Specifically, when the conventional inkjet ink composition is used after curing the developed PSR, it is difficult to form a mark due to significantly poor adhesion. On the other hand, the UV curable inkjet ink composition according to one embodiment of the present invention exhibits excellent adhesion even when used after PSR development as well as after PSR curing, so that excellent marking can be formed.

Various embodiments or examples described in this specification are illustrated for the purpose of clearly explaining the technical idea of the present invention. The technical idea of the present invention is the various modifications, equivalents, and alternatives of each embodiment or examples described herein, and embodiments selectively combined from all or part of each embodiment or examples. or examples. In addition, the technical spirit of the present invention is not limited to the various embodiments or examples or specific description thereof presented below.

Terms used in this specification, including technical or scientific terms, may have meanings commonly understood by those of ordinary skill in the art to which the present invention belongs, unless otherwise defined. Terms such as those defined in general dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present invention, they are not interpreted in an ideal or excessively formal meaning.

Expressions such as "comprises", "may include", "has", "may have", "has", "may have", etc. used herein refer to the target characteristics (eg: function, operation or component), and does not preclude the presence of other additional features. That is, such expressions should be understood as open-ended terms that include the possibility of including other embodiments.

Expressions in the singular form used in this specification may include plural meanings unless the context indicates otherwise, and this applies equally to expressions in the singular form described 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,” “at least one of A, B or C” one,” “at least one of A, B, and/or C,” “at least one selected from A, B, and C,” “at least one selected from A, B, or C,” “selected from A, B, and/or C. Expressions such as "at least one" may mean each listed item or all possible combinations of listed items.

As used herein, the term "about" can represent a typical error range for each value, as is well known to those skilled in the art. In the context of a numerical value or range set forth herein, this means in one embodiment ±20%, ±15%, ±10%, ±9%, ±8%, ±7% of the stated or claimed numerical value or range. , ±6%, ±5%, ±4%, ±3%, ±2%, or ±1%.

Description of dimensions, numerical values and ranges thereof used herein, unless otherwise specified in context, are not limited only to the corresponding dimensions, numerical values and ranges, and may mean equivalent ranges including these.

Various embodiments of the present 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 includes (A) a heteropolymerization monomer comprising at least one radical curable functional group and at least one cation curable functional group; (B) a monomer containing a functional group capable of forming a cross-link with the cation-curable functional group of the heteropolymer monomer; (C) a heat curable compound; and (D) a monomer containing a polar functional group capable of forming a crosslink with the thermosetting compound. The UV curable inkjet ink composition exhibits excellent viscosity and storage stability, adhesion and surface curing properties through the combination of these four components. These four components can exhibit more excellent effects when each is included in a specific mixing ratio. In particular, even when used after the final curing of PSR, it shows excellent adhesion on a printed circuit board, so that it can be used as an ink composition for marking even after curing of PSR, thereby exhibiting different effects superior to those of conventional ink compositions.

[Heteropolymerization Monomer (A)]

In one embodiment, the heteropolymerization monomer (A) may be used without particular limitation as long as it is a compound having at least one functional group different from each other. Here, the different functional groups may be a radical curable functional group and a cation curable functional group. The heteropolymerization monomer (A) may exhibit different curing reactivity by having different functional groups, and may have, for example, radical curing reactivity and cationic curing reactivity. This may contribute to excellent adhesion and pencil hardness, and may exhibit excellent characteristics of reaction rate.

The radical curable functional group may be at least one selected from the group consisting of an ethylenically unsaturated group, an acryloyl group, an acrylate group, a methacrylate group, and a vinyl group, but is not limited thereto.

The cation-curable functional group may be at least one 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, but is limited thereto. it is not going to be

Specifically, the heteropolymerization monomer (A) is 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-hydroxy-3-acrylo Iloxypropyl (meth)acrylate, hydroxypivalylhydroxypivalate di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2-methyl-1,3-butylene glycol di (meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanediol Di(meth)acrylate, 3-methyl-1,5-pentanedioldi(meth)acrylate, ethoxylated 1,6-hexanedioldi(meth)acrylate, neopentylglycoldi(meth)acrylate, pro Poxylated 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 Rate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, glycerine di(meth)acrylate rate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and may be one or more selected from the group consisting of triethylene glycol di (meth) acrylate, but is not limited thereto.

[Monomer (B)]

In one embodiment, the monomer (B) may be used without particular limitation as long as it contains a functional group capable of forming a crosslink by reacting with the cation-curable functional group of the heteropolymerization monomer (A). This monomer (B) can form a cross-link with the heteropolymerization monomer by energy ray irradiation even without the presence of a cationic photoinitiator. Due to such crosslinking, the UV curable inkjet ink composition of the present invention can exhibit excellent viscosity, storage stability, adhesion and surface curing properties.

The functional group of the monomer (B) capable of forming a crosslink by reacting with the cation-curable functional group of the heteropolymerization monomer (A) is an epoxy group, a thioether group, a trioxane group, an oxazoline group, a caprolactone group, and a tetrahydrofuran group. , an oxetane group, and may be at least one selected from the group consisting of a vinyl ether group, but is not limited thereto.

The monomer (B) may be at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound.

The epoxy compound may be a multifunctional epoxy compound, and may be at least one selected from the group consisting of an alicyclic epoxy resin, a novolac-type epoxy resin, a phenol-type epoxy resin, a phenol novolac-type epoxy resin, and a naphthalene-type epoxy resin. Specifically, the novolak-type epoxy resin may be a cresol novolak-type epoxy resin, and the cresol novolak-type epoxy resin may have a structure represented by Chemical Formula 1 below.

[Formula 1]

Here, n represents a repeating unit, and n may be an integer of 1 or more. For example, n may be an integer greater than or equal to 1 and less than or equal to 20. The monoisotopic mass or mass-to-charge ratio (m/z) of this repeating unit may be 176.0837.

The content of the cresol novolac type epoxy resin included in the UV curable inkjet ink composition can be measured by liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS). For example, the cresol novolak-type epoxy component included in the inkjet ink composition may be detected by comparing the m/z value with the 3D-map analysis and reference sample of LC-TOF-MS analysis. Specifically, from the 3D-map analysis of a random sample, when confirming the ionic species m/z corresponding to the repeating unit (n = 1 to 6) of the cresol novolac-type epoxy, during the holding time (eg, between 11 and 13 minutes) A peak with a difference in repeating units (Δm/z = 176) of cresol novolac-type epoxy can be found (ionic species: ammonium adduct [M+NH ₄ ] ⁺ , which is, for example, different from those shown in Table 1 below. may be derived from an aqueous 10 mM ammonium acetate solution). In this way, by comparing the 3D-map analysis result and the m/z value of the arbitrary sample with the reference sample, it can be confirmed that the cresol novolak-type epoxy component exists in the arbitrary sample. For example, a reference sample is a product containing a commercially available cresol novolak-type epoxy resin (e.g., Taiyo Ink Korea, IJR-400 LW300) mixed with tetrahydrofuran (THF) solvent by ultrasonic waves, and the appropriate epoxy resin content (e.g. : 0.5% by weight), and can be used for experiments after pretreatment filtration (eg Pall's membrane filter, material: polytetrafluoroethylene (PTFE), pore size: 0.2 μm).

[LC-TOF-MS Analysis Conditions]

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

Liquid chromatography (LC) remittance conditions 0.2 mL/min×30 min gradient
Mobile phase A: 10 mM ammonium acetate aqueous solution
Mobile phase B: acetonitrile
Mobile phase C: tetrahydrofuran (THF)
Mobile phase A: 95 % (0 min) → 2.5 % (10 to 15 min) → 95 % (20 min)
Mobile phase C: 2.5% (0 to 30 minutes)
20.5 minutes to 30 minutes: sending with initial conditions column BEH C18 2.1×100 mm Mass spectrometry (MS) ionization ESI(+) detection m/z 50~3000

Specifically, as the alicyclic epoxy resin compound, 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-epoxycyclohexylethyltrimethoxysilane and the like, but cycloaliphatic epoxy resin compounds having an epoxy group, etc. are exemplified, but are not limited thereto. As a commercial item, it is Daicel Kagaku Kogyo Co., Ltd. product Celoxide 2000, Celoxide 2021, Celoxide 3000, EHPE3150, for example; Epomic VG-3101 manufactured by Mitsui Chemicals Co., Ltd.; E-1031S manufactured by Emulsion 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 are not limited thereto. As the oxetane compound, 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)methylacrylate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxeta In addition to polyfunctional oxetanes such as methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, oligomers or copolymers thereof, oxetane alcohol, novolac resin, poly(p- Hydroxy styrene), cardotype bisphenols, calix arenes, calix resorcin arenes, or ether products with resins having a hydroxyl group such as silsesquioxane, and alkyl (meth)acrylates with unsaturated monomers having an oxetane ring. and oxetane compounds such as copolymers with, but are not limited thereto. The oxetane compound may also be a multifunctional oxetane compound. Examples of commercially available products include Eternacol OXBP, OXMA, OXBP, EHO manufactured by Ube Kosan Co., Ltd., xylylenebisoxetane, Alon Oxetane OXT-101, OXT-201, and OXT- manufactured by Toagosei Co., Ltd. 211, OXT-221, OXT-212, OXT-610, PNOX-1009, and the like, but are not limited thereto.

Examples of the vinyl ether compound include: cyclic ether type vinyl ethers such as isosorbite divinyl ether and oxanorbornene divinyl ether (vinyl ethers having cyclic ether groups such as oxirane rings, oxetane rings, and oxolane rings); aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; Polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, and cyclohexane dimethanol divinyl ether, having substituents such as alkyl groups and allyl groups at α and/or β positions Vinyl ether compounds and the like may be mentioned, but is not limited thereto. As a commercial item, for example, Maruzen Sekiyu Chemical Co., Ltd. product 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), tri ethylene glycol divinyl ether and the like, but are not limited thereto.

[Heat curable compound (C)]

In one embodiment, the heat-curable compound (C) may be used without particular limitation as long as it is a compound that can be cured by heating. This thermosetting compound (C) can be crosslinked with the monomer (D) to improve adhesion.

The heat curable compound (C) may be at least one selected from the group consisting of amine resins, isocyanate compounds, block isocyanate compounds, cyclocarbonate compounds, multifunctional epoxy compounds, multifunctional oxetane compounds, and episulfide resins.

The amine resin may be a known one such as methylol benzoguanamine, benzoguanamine, methylol glycoluril, methylol urea, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea, but is not limited thereto. . Here, the alkoxymethyl group may be a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, or a butoxymethyl group, but is not limited thereto.

The isocyanate compound may mean a compound having one or two or more isocyanate groups in one molecule, and the block isocyanate compound may mean a compound having one or two or more blocked isocyanate groups in one molecule.

As the isocyanate compound, aromatic isocyanate, aliphatic isocyanate or alicyclic isocyanate can be used, for example. 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, tetramethyl-1,3-xylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic isocyanate 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(cyclohexylisocyanate). Specific examples of the alicyclic isocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexane diisocyanate, dimeryl diisocyanate, and bicycloheptane triisocyanate. and adducts, biurets and isocyanurates of the above-listed isocyanate compounds. 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 and temporarily inactivated by reaction with a blocking agent. When heated to a predetermined temperature, the blocking agent dissociates and isocyanate groups are generated.

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with a blocking agent, an isocyanurate type, a biuret type, an adduct type, etc. are mentioned. As this isocyanate compound, aromatic isocyanate, aliphatic isocyanate or alicyclic isocyanate similar to the above can be used, for example.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as ε-caprolactam (ε-CAP), δ-valerolactam, γ-butyrolactam and β-propiolactam; active methylene-based 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, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycol alcohol-based blocking agents such as butyl acid, diacetone alcohol, methyl lactate and ethyl lactate; oxime-based blocking agents such as formaldehyde, acetaldoxime, acetoxime, methylethyl ketoxime (MEKO), diacetyl monooxime, and cyclohexane oxime; mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide-based blocking agents such as succinic acid imide and maleic acid imide; amine blocking agents such as xylidine, aniline, butylamine, and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine; Pyrazole-based blocking agents such as methyl pyrazole (eg, 3,5-dimethylpyrazole) and ethyl pyrazole may be used, but are not limited thereto.

The block isocyanate compound may be a commercially available one, for example, BI7683, BI7642, BI201, BI220, BI7950, BI7951, BI7960, BI7961, BI7963, BI7981, BI7982, BI7990, BI7991, BI7992 (above, manufactured by Baxenden, trade name), Sumi Module BL-3175, BL-4165, BL-1100, BL-1265, Desmodule TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmosam 2170, Desmosam 2265 (above, Sumitomo Bayer Urethane Co., Ltd.) Kaisha product, trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nippon Polyurethane Kogyo Co., Ltd. trade name), B-830, B-815, B-846, B-870, B- 874, B-882 (manufactured by Mitsui Takeda Chemicals Co., Ltd., trade name), TPA-B80E, 17B-60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (manufactured by Asahi Kasei Chemicals Co., Ltd.) , trade name), etc. may be used, but is not limited thereto.

The said isocyanate compound or block isocyanate compound can be used individually by 1 type or in combination of 2 or more types.

The type of cyclocarbonate compound is not particularly limited as long as it is a known carbonate compound used as a heat curing component, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, or 2,3-carbonate propyl methacrylate. Examples include, but are not limited to.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epiclone 840, Epiclone 850, Epiclone 1050, Epiclone 2055, and Nippon Steel Sumikin. Epotote YD-011, YD-013, YD-127, YD-128 manufactured by Kagaku Co., Ltd., D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by Dow Chemical Co., Ltd., Sumitomo Chemical Co., Ltd. bisphenol A type epoxy resins such as Sumi Epoxy ESA-011, ESA-014, ELA-115, ELA-128, A.E.R.330, A.E.R.331, A.E.R.661, and A.E.R.664 manufactured by Asahi Kasei Co., Ltd. (all are trade names); jERYL903 manufactured by Mitsubishi Chemical Co., Ltd., Epiclone 152 and Epiclone 165 manufactured by DIC Co., Ltd., Ephotot YDB-400 and YDB-500 manufactured by Nippon Steel Sumikin Chemical Co., Ltd., manufactured by Dow Chemical Co., Ltd. brominated epoxy resins such as D.E.R.542, Sumitomo Chemical Co., Ltd.'s Sumi Epoxy ESB-400 and ESB-700, Asahi Kasei Co., Ltd.'s A.E.R.711 and A.E.R.714 (all are trade names); Mitsubishi Chemical Corporation jER152, jER154, Dow Chemical Corporation D.E.N.431, D.E.N.438, DIC Corporation Epiclone N-730, Epiclone N-770, Epiclone N-865, Nippon Steel Sumikin EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical novolak-type epoxy resins such as Sumi Epoxy ESCN-195X and ESCN-220 manufactured by Asahi Kasei Co., Ltd. and A.E.R.ECN-235 and ECN-299 manufactured by Asahi Kasei Co., Ltd. (all are trade names); Bisphenol, such as Epiclone 830 by DIC Co., Ltd., jER807 by Mitsubishi Chemical Co., Ltd., and Epothoth YDF-170, YDF-175, YDF-2004 by Nippon Steel Sumikin Chemical Co., Ltd. (all are trade names) F type epoxy resin; hydrogenated bisphenol A-type epoxy resins such as Nippon Steel Sumikin Chemical Co., Ltd.'s Epototte ST-2004, ST-2007, and ST-3000 (trade name); Glycidylamines such as jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epothoth YH-434 manufactured by Nippon-Stetsu Sumikin Co., Ltd., and Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all are trade names) type epoxy resin; hydantoin type epoxy resin; Alicyclic epoxy resins, such as Celloxide 2021P by Daicel Co., Ltd. (brand name); Trihydroxyphenylmethane type epoxy resins, such as YL-933 by Mitsubishi Chemical Corporation, T.E.N. by Dow Chemical Co., Ltd., EPPN-501, and EPPN-502 (all are brand names); bixylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000, and YL-6121 (all are trade names) manufactured by Mitsubishi Chemical Corporation; or mixtures thereof; Bisphenol S-type epoxy resins, such as EBPS-200 by Nippon Kayaku Co., Ltd., EPX-30 by Asahi Denka Kogyo Co., Ltd., and EXA-1514 (trade name) by DIC Corporation; Bisphenol A novolak-type epoxy resins, such as jER157S (brand name) by Mitsubishi Chemical Corporation; Tetraphenylol ethane type epoxy resins, such as jERYL-931 by Mitsubishi Chemical Corporation (all are brand names); heterocyclic epoxy resins such as TEPIC manufactured by Nissan Chemical Industries, Ltd. (trade name); diglycidyl phthalate resins such as Blemmer DGT manufactured by Nippon Oil & Gas Co., Ltd.; tetraglycidylxylenoylethane resins such as Nippon Steel Sumikin Chemical Co., Ltd. ZX-1063; naphthalene group-containing epoxy resins such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. and HP-4032 manufactured by DIC Corporation, EXA-4750 and EXA-4700; Epoxy resins having dicyclopentadiene skeletons such as HP-7200 and HP-7200H manufactured by DIC Corporation; glycidyl methacrylate copolymerization type epoxy resins such as CP-50S and CP-50M manufactured by Nihon Yushi Co., Ltd.; Further copolymerization epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (eg PB-3600 manufactured by Daicel Kagaku Kogyo), CTBN-modified epoxy resins (eg YR-102 YR-450 manufactured by Toto Kasei Co., Ltd.), etc. However, it is not limited thereto. These epoxy resins can be used individually or in combination of 2 or more types.

As the polyfunctional oxetane compound, 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)methylacrylic rate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methylmethacrylate, (3-ethyl-3-oxetanyl)methylmethacrylate, these In addition to polyfunctional oxetanes such as oligomers of or copolymers thereof, oxetane alcohol, novolak resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcin arenes or silses etherified with a resin having a hydroxyl group such as quioxane; and the like, but are not limited thereto. In addition, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate are also exemplified. Examples of commercially available products include Eternacol OXBP, OXMA, OXBP, EHO manufactured by Ube Industries Co., Ltd., xylylene bisoxetane, Alon Oxetane OXT-101, OXT-201, and OXT- manufactured by Toagosei Co., Ltd. 211, OXT-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. Moreover, an episulfide resin etc. in which the oxygen atom of the epoxy group of a novolak-type epoxy resin is substituted by the sulfur atom can also be used using the same synthesis method.

The thermosetting compounds described above may be used alone or in combination of two or more.

[Monomer (D)]

In one embodiment, the monomer (D) may contain a polar functional group capable of forming a crosslink by reacting with the heat curable compound (C). This monomer (D) can improve the adhesion of the UV curable inkjet ink composition of the present invention after curing, which can be achieved by forming a cross-link with the heat curable compound (C).

The polar functional group of the monomer (D) is not particularly limited as long as it can form a cross-link by reacting with the thermosetting compound (C). For example, the polar functional group may be one or more selected from the group consisting of a hydroxyl group, a carboxy group, an amino group, an amine group, a carbonyl group, an acryl group, an acryloyl group, a nitrile group, a vinyl group, a halogen group, a urethane group, and an ester group. It is not limited.

The monomer (D) may be used without particular limitation as long as it can react with the heat-curable compound (C) to form a crosslink, and for example, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate , 2-hydroxy-3phenoxyethyl (meth)acrylate, 1-4-cyclohexane dimethanol mono (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) Acrylates, 4-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, and 2- It may be one or more selected from the group consisting of hydroxypropyl (meth) acrylate, but is not limited thereto.

[Content of each ingredient]

In one embodiment, the content of the heteropolymerization monomer (A) is about 5 to about 40% by weight, about 7 to about 35% by weight, about 10 to about 30% by weight, about 15 to about 15% by weight based on the total weight of the composition of the present invention. about 25 weight percent, about 18 to about 22 weight percent, or about 19 to about 21 weight percent. When the content of the heteropolymerization monomer (A) is greater than or equal to the minimum value, the desired adhesion and surface curability of the UV curable inkjet ink composition of the present invention can be achieved more excellently, and when the content is less than or equal to the maximum value, the effect to be achieved in the present invention is achieved. (adhesion, surface hardenability, and viscosity and storage stability) can be achieved.

In one embodiment, the content of the monomer (B) is about 0.05 to about 10% by weight, about 0.1 to about 9% by weight, about 0.1 to about 7% by weight, about 0.5 to about 5% by weight based on the total weight of the composition of the present invention. weight percent, about 0.5 to about 3 weight percent, about 0.5 to about 2 weight percent, about 0.5 to about 1.5 weight percent, or about 0.5 to about 1 weight percent. When the content of the monomer (B) is greater than or equal to the minimum value, desired viscosity, storage stability, and adhesion may be achieved in the UV curable inkjet ink composition of the present invention, and if the content is less than or equal to the maximum value, viscosity, storage stability, and surface curability may be achieved. can

In one embodiment, the content of the heat curable compound (C) is about 2 to about 30% by weight, about 5 to about 25% by weight, about 5 to about 20% by weight, about 7 to about 7% by weight based on the total weight of the composition of the present invention. 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 heat-curable compound (C) is greater than or equal to the minimum value, the desired adhesion may be achieved in the UV curable inkjet ink composition of the present invention, and when it is less than or equal to the maximum value, the desired effect (adhesion, surface curability, and viscosity and storage stability) can be achieved.

In one embodiment, the content of the monomer (D) is about 1 to about 15% by weight, about 5 to about 15% by weight, about 7 to about 13% by weight, about 9 to about 11% by weight based on the total weight of the composition of the present invention. % by weight. When the content of the monomer (D) is greater than or equal to the above minimum value, the desired adhesion in the UV curable inkjet ink composition of the present invention can be achieved. When the content of the monomer (D) is less than the maximum value, surface curability to be achieved in the UV curable inkjet ink composition of the present invention can be achieved, and when the content of the monomer (D) exceeds the maximum value, due to low viscosity During printing, printability such as smearing of ink may be deteriorated, and there is a possibility of weakness in terms of chemical resistance and hardness.

[Other additives]

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

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

A known radical photoinitiator may be used without particular limitation, and examples thereof include benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, and α-aminoacetophenes. It may contain at least one or more selected from paddy fields, acylphosphine oxides, or oxime esters. More specifically, for example, nonacetyl, benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2 -diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1-methylethyl-phenol ketone, p-isopropyl-α-hydroxyiso Butylphenone, N,N-dimethylaminoacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, ethyl-p-dimethylaminobenzoate, 2-methyl Anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone , 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzyldimethyl ketal, benzophenone, methyl benzophenone, trimethyl benzophenone (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 (etha 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)oxy Ethylene-l-yl] -methylamine (ESACURE A198) or a mixture of two or more thereof may be used, but is not limited thereto.

As the colorant, known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments can be used, and these can be used alone or in combination of two or more. there is.

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

As the black colorant, carbon black, perylene black, iron oxide, manganese dioxide, aniline black, activated carbon, etc. may be used, but is not limited thereto.

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Specifically, the following can hear 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 , 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, monoazo red colorants such as 269, disazo red colorants such as Pigment Red 37, 38, 41, pigments 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, 63:1, 63:2, 64:1, monoazo lake-based red colorants such as 68, Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208, etc. benzimidazolone red colorant, 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, perylene red colorants such as Pigment Red 224, diketopyrrolopyrrole red colorants such as Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, and Pigment Red 272, Pigment Red Condensed azo red colorants such as 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 168, Pigment Red 177, Pigment Anthraquinone-based red colorants such as Solvent Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207, Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209 and the like, but are not limited thereto.

Examples of 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, and the like, but are not limited thereto. As dye system, 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, solvent blue 70 or the like can be used, but is not limited thereto. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

As the green colorant, there are phthalocyanine-based, anthraquinone-based, parylene-based, etc., and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. It may be, but is not limited thereto. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

As the green colorant, there are phthalocyanine-based, anthraquinone-based, parylene-based, etc., and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. It may be, but is not limited thereto. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone, and specifically 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, Pigment Yellow 185, etc., isoindolinone-based yellow colorants, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Condensed azo yellow colorants such as Pigment Yellow 166 and Pigment Yellow 180, benzimida such as Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, and Pigment Yellow 181 Zolon-based yellow colorant, 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, monoazo yellow colorants such as 183, pigment yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, Disazo-based yellow colorants such as 170, 172, 174, 176, 188, and 198 may be used, but are not limited thereto.

Moreover, you may add coloring agents, such as purple, orange, brown, and black, for the purpose of adjusting color tone. Specifically, 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 16, 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 Orange 51, C. I. 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 C. I. Pigment Brown 23, C. I. Pigment Brown 25, C. I. Pigment Black 1, C. I. Pigment Black 7, and the like, but are not limited thereto.

The content of the colorant is about 1 to about 20% by weight, about 5 to about 20% by weight, about 10 to about 20% by weight, about 12 to about 18% by weight, or about 14 to about 20% by weight based on the total weight of the composition of the present invention. 16% by weight.

Any known dispersant may be used without particular limitation, and commercially available BYK's DISPERBYK-111, DISPERBYK-110, DISPERBYK-118, DISPERBYK-140, 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, One or more of DISPERBYK-2008, DISPERBYK-9076, DISPERBYK-9077 and DISPERBYK-2055 may be used, but is not limited thereto.

The content of the dispersant is about 0.1 to about 5% by weight, about 0.5 to about 2% by weight, about 0.7 to about 1.5% by weight, about 0.9 to about 1.3% by weight, or about 0.9 to about 0.9% by weight based on the total weight of the composition of the present invention. 1.1% by weight.

The heat-curable polymerization inhibitor may be used without particular limitation as long as it can be used to maintain the storage stability of the ink. The UV curable inkjet ink composition of the present invention includes a heat curable compound, for example, a blocked isocyanate. Such a heat-curable compound is blocked and maintains a stable state until heating, but in an environment of room temperature or medium temperature (about 30° C. to about 60° C.), some reaction of the heat-curable compound may progress, reducing storage stability. A heat-curable polymerization inhibitor may be used to prevent such a decrease in storage stability and maintain the storage stability of the inkjet ink composition. For example, phenols such as hydroquinone, tertiary butyl catechol, and butylhydroxyanisole, quinones such as para-benzoquinone, amines such as nitrohydroxyamine and phenylenediamine, mercaptans, and dithio One or more of the carbamates may be used, but is not limited thereto. The thermosetting polymerization inhibitor is tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminium which is an amine or nitro hydroxyl An amine aluminum salt (Q-1301; available from Wako) can be used.

The content of the thermosetting polymerization inhibitor is about 0.01 to about 0.5% by weight, about 0.01 to about 0.3% by weight, about 0.05 to about 0.2% by weight, about 0.05 to about 0.15% by weight, or about 0.05 to about 0.15% by weight based on the total weight of the composition of the present invention. 0.05 to about 0.1 weight percent. When the content of the heat-curable polymerization inhibitor is equal to or greater than the minimum value, storage stability of the UV curable inkjet ink composition may be sufficiently achieved, and when the content is equal to or less than the maximum value, curing by heating may be performed as desired.

The leveling agent may be used without particular limitation as long as it is intended to increase adhesion on the final cured PSR substrate and solve the hajiki problem (pin hole phenomenon). For example, the leveling agent may be commercially available silicone-based or non-silicone-based leveling agents from BYK, which are commercially available in terms of suitability for leveling properties of the composition of the present invention, and a combination of two or more may be used. Silicone-based leveling agents are 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-UV- It may be one or more of 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 It may be one or more of -3441, BYK-3560, and BYK-3566, but is not limited thereto.

The content of the leveling agent may be about 0.1 to about 1.0% by weight, about 0.2 to about 0.8% by weight, about 0.3 to about 0.7% by weight, or about 0.4 to about 0.6% by weight based on the total weight of the composition of the present invention. When the content of the leveling agent is equal to or greater than the minimum value, desired adhesion is achieved or a UV curable inkjet ink composition having no hajiki problem (pin hole phenomenon) can be prepared. When the content is equal to or less than the maximum value, the reactivity is satisfied and adhesion The UV curable inkjet ink composition achieved can be prepared.

In one embodiment, the UV curable inkjet ink composition may further include at least one of a dispersant, an antifoaming agent, a flow control agent, a foaming agent, a surfactant, an antioxidant, an antistatic agent, and a brightener, in this case based on the total weight of the ink composition. It can be added in small amounts.

In one embodiment, the UV curable inkjet ink composition may be characterized in that it does not include a cationic photoinitiator. The inkjet ink composition of the present invention is characterized in that a monomer having a heteropolymerization monomer and a cation-curable functional group and a functional group capable of forming a cross-link is cured by active energy rays, even if a cationic photoinitiator is not included or not. Due to these characteristics, the inkjet ink composition of the present invention can exhibit excellent viscosity or storage stability and excellent surface curability.

The present invention will become more clear through the foregoing embodiments and the following examples. Hereinafter, the embodiments described with reference to the following table will be described in detail so that those skilled in the art can easily understand and implement the present invention. However, these examples are intended to illustrate the present invention by way of example, and the scope of the present invention is not limited to these examples.

[Example]

I. Preparation of Inkjet Ink Compositions and Marking Ink Substrates

1. Preparation of UV Curable Inkjet Ink Composition

After mixing the reactants having the respective components and contents listed in Tables 2 and 3 below at 45° C. for 1.5 hours at a speed of 2,000 rpm using a stirrer, a pigment and a dispersant were added and zirconia beads having a particle diameter of 0.2 μm were used. Dispersed for 3 hours. Thereafter, it was filtered through a 1 μm filter to prepare a UV curable inkjet ink composition.

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

1) Heterogeneous polymerization 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 trifunctional block isocyanate: cresol novolak-type epoxy in a ratio of 12: 0.7, and the cresol novolak-type epoxy The compound is added as a blended mixture with trifunctional block isocyanate. Blended in large quantities according to the content ratios in Tables 2 and 3 (Based) and then subdivided for use)

3) Heat-curable compound (C) (trifunctional block isocyanate): BH-50 (manufactured by JB Caltech Co., Ltd.; contains 1,3,5-tris (6-isocyanatohexyl) biuret and is combined with cresol novolak-type epoxy added as a blended mixture)

4) Monomer (D) (monofunctional monomer containing a hydroxyl group): 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.)

5) Multifunctional monomer: trimethylolpropane triacrylate (manufactured by Allnex)

6) Other monomers: 1,6-hexanediol diacrylate (HDDA; manufactured by Allnex)

7) Radical Photoinitiator: A mixture of OMNIRAD 819 (manufactured by IGM Resin B.V.) and MOSAPHOTO 348 (manufactured by UFC Corporation) (mix OMNIRAD 819 and MOSAPHOTO 348 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 B.V.)

2. Photo Solder Resist (PSR) Substrate Manufacturing

Taiyo Photo Solder Resist PSR-4000 MB (Screen Type PSR), PSR-4000 SP71 (Spray Type PSR) is used to form a circuit using the screen printing method and the spray printing method on the printed circuit board 1.6T FR-4 (thickness 40um±2) After printing, it was dried at 90° C. for 30 minutes. In order to pattern and expose the dried PSR, a developing film (PET film) is applied in an exposure machine (OTS Technology, YH-7090 8K), and after exposure at 400mJ/cm ² , a developing machine (Baekdoo Enterprises, TRUMAN DI442, Na ₂ CO ₃ 1 wt%, 60 sec) to produce patterns and developing substrates. In order to final cure the developed PSR, a PSR substrate for evaluation of the marking ink was prepared by final curing at 150 ^° C. for 60 minutes in a hot air circulation drying furnace.

3. Manufacturing of marking ink substrate

The UV curable inkjet ink composition prepared according to item 1. above is applied to an inkjet printer (Microcraft MJP2013K1-DU) and a piezoelectric type print head, prepared according to item 2. above, and the PSR is finally cured. It was coated on a 1.6T FR-4 (150 mm x 95 mm) printed circuit board. Thereafter, photocuring was performed while irradiating ultraviolet rays with a total cumulative light amount of 400 mJ/cm ² using a UV LED lamp (385 nm, 395 nm) attached to an inkjet printer with respect to the marking ink solution applied on the printed wiring board. After the photocuring, thermal curing was performed at 150° C. for 60 minutes in a hot air circulation drying furnace to prepare a marking ink coating film.

II. characteristic test

The following evaluation was performed on the marking ink coating film prepared according to the above, and the UV curable inkjet ink compositions of Examples and Comparative Examples were evaluated. The evaluation results are shown in Table 2 and Table 3, respectively.

1. Adhesion

Make 100 square (□)-shaped graduations (10X10) on the surface of the cured composition at an angle of 30 ° using a knife with a width of 1 mm, attach them with adhesive tape, and then remove them instantly. After peeling off, the adhesiveness was evaluated according to the figure below.

: ◎

: ○

: △

: X

: ◎

: ○

: △

:X

2. Surface Hardness (Tacky)

After rubbing the surface of the cured composition with a white cloth soaked in alcohol, the degree of ink sticking to the white cloth was confirmed, and also, when the surface of the cured composition was touched with a hand, the surface curing property was evaluated with the presence or absence of handprint transfer.

◎: There is no transfer of handprints, and no ink smudges at all.

○: There is no transfer of handprints, but a little ink smearing is observed.

△: There is transcription of the handprint, and a little ink smearing is observed.

X: Handprints are transferred, and ink is erased.

3. Viscosity and Storage Stability

The viscosity of the UV curable inkjet ink composition prepared according to the above method was measured (initial viscosity). Then, the composition was stored at 50 ° C. for 2 weeks in a sealed container, and the viscosity was measured again to confirm the change in viscosity according to the following formula.

(A = 초기 점도, B = 2주간 보존 후 점도) ceremony :

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

The calculated viscosity change was evaluated based on the following criteria.

Viscosity change 0% to 2% or less: ◎

Viscosity change more than 2% and less than 8%: ○

Viscosity change more than 8% and less than 15%: △

Viscosity change greater than 15%: X

ingredient Example One 2 3 4 5 6 7 8 9 10 11 One) Heteropolymerization Monomer (A) 20 20 20 10 30 20 20 10 30 20 20 2) Monomer (B) One 0.1 5 One One One One 0.1 5 0.1 5 3) Thermosetting compound (C) 15 15 15 15 15 5 20 5 20 5 20 4) Monomer (D) 10 10 10 10 10 10 10 10 10 10 10 5) polyfunctional monomer 15 15 15 19 10 20 15 25 10 20 10 6) other monomers 18.4 19.4 14.3 24.4 13.4 23.4 13.4 29.4 4.3 24.4 14.3 7) radical photoinitiator 5 5 5 5 5 5 5 5 5 5 5 8) titanium oxide 15 15 15 15 15 15 15 15 15 15 15 9) polymerization inhibitor 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 10) leveling agent 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Sum 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 evaluation items adhesion ◎ ◎ ◎ △ ○ △ ○ △ ○ △ ○ Surface Hardness (Tacky) ◎ ◎ ◎ ◎ ○ ◎ ○ ○ △ ○ ○ Viscosity and storage stability ◎ ○ △ ◎ ◎ ◎ ○ △ ○ ○ △

ingredient Example comparative example 12 13 14 15 16 17 One 2 3 4 5 One) Heteromeric monomer (A) 20 20 5 40 20 20 20 0 20 20 20 2) Monomer (B) 0.05 10 One One One One 0 One One One One 3) Thermosetting compound (C) 15 15 15 15 2 30 15 15 0 15 15 4) Monomer (D) 10 10 10 10 10 10 10 10 10 0 10 5) polyfunctional monomer 15 10 24 4 23 5 20 25 25 20 15 6) other monomers 19.4 14.3 24.4 9.4 23.4 13.4 14.4 28.4 23.4 23.4 14.4 7) radical photoinitiator 5 5 5 5 5 5 5 5 5 5 4 8) titanium oxide 15 15 15 15 15 15 15 15 15 15 15 9) polymerization inhibitor 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 10) leveling agent 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 11) cationic photoinitiator 0 0 0 0 0 0 0 0 0 0 5 Sum 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 evaluation
item adhesion △ ○ ○ ○ △ △ X X X X △ Surface Hardness (Tacky) ○ ○ △ ○ △ ○ △ X △ △ X Viscosity and storage stability ○ △ ○ △ ○ △ △ △ △ △ X

According to Examples 1 to 17 of Tables 2 and 3, the UV curable inkjet ink composition according to an embodiment of the present invention includes a heteropolymerizable monomer (A), a monomer (B), a thermosetting compound (C) and a monomer (D). Including a combination of, overall exhibits excellent viscosity and storage stability, adhesion and surface hardening properties. On the other hand, according to Table 2, in the case of 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, The properties of the UV curable inkjet ink composition could not be achieved. In the case of Comparative Examples 1 to 4, it can be seen that the adhesiveness is very poor, and with these characteristics, marking cannot be properly formed after the final curing of the PSR. In particular, in the case of Comparative Example 2, since the heteropolymerizable monomer (A) was not included, it was confirmed that the surface curability was also very poor. In addition, in the case of Comparative Example 5 including a cationic photoinitiator, it was confirmed that 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) a heteropolymerization monomer comprising at least one radical curable functional group and at least one cation curable functional group;
(B) a monomer containing a functional group capable of forming a cross-link with the cation-curable functional group of the heteropolymer monomer;
(C) a heat curable compound; and
(D) a monomer containing a polar functional group capable of forming a crosslink with the thermosetting compound
containing
A UV curable inkjet ink composition. According to claim 1,
The radical curable functional group of the heteropolymerization monomer (A) is at least one selected from the group consisting of an ethylenically unsaturated group, an acryloyl group, an acrylate group, a methacrylate group, and a vinyl group,
A UV curable inkjet ink composition. According to claim 1,
The cation-curable functional group of the heteropolymerization 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. more than one,
A UV curable inkjet ink composition. According to claim 1,
The heteropolymerization monomer (A) is 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-hydroxy-3-acryloyloxy Propyl (meth)acrylate, hydroxypivalylhydroxypivalate di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2-methyl-1,3-butylene glycol di(metha)acrylate ) Acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi( meth)acrylate, 3-methyl-1,5-pentanedioldi(meth)acrylate, ethoxylated 1,6-hexanedioldi(meth)acrylate, neopentylglycoldi(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, polypropylene glycol 700 di(meth)acrylate, glycerin di(meth)acrylate, At least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate,
A UV curable inkjet ink composition. According to claim 1,
The functional group of the monomer (B) is at least one 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,
A UV curable inkjet ink composition. According to claim 1,
wherein the monomer (B) is at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound;
A UV curable inkjet ink composition. According to claim 6,
The epoxy compound is at least one selected from the group consisting of an alicyclic epoxy resin, a novolac-type epoxy resin, a phenol-type epoxy resin, a phenol novolak-type epoxy resin, and a naphthalene-type epoxy resin.
A UV curable inkjet ink composition. According to claim 7,
The novolac-type epoxy resin is a cresol novolac-type epoxy resin,
A UV curable inkjet ink composition. According to claim 8,
The cresol novolac-type epoxy resin has a structure of Formula 1 below,
A UV curable inkjet ink composition.
[Formula 1]

(where n is an integer greater than or equal to 1) According to claim 1,
The thermosetting compound (C) is at least one selected from the group consisting of an amine resin, an isocyanate compound, a block isocyanate compound, a cyclocarbonate compound, a multifunctional epoxy compound, a multifunctional oxetane compound, and an episulfide resin,
A UV curable inkjet ink composition. According to claim 10,
The thermosetting compound (C) is a block isocyanate compound,
A UV curable inkjet ink composition. According to claim 11,
The isocyanate compound is an aromatic isocyanate, an aliphatic isocyanate or an alicyclic isocyanate,
A UV curable inkjet ink composition. According to claim 12,
Isocyanate compounds are 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylyl Rendiisocyanate, tetramethyl-1,3-xylene 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, dimeryl diisocyanate, bicycloheptane triisocyanate; adducts, biurets or isocyanurates thereof; And at least one selected from the group consisting of combinations thereof,
A UV curable inkjet ink composition. According to claim 13,
The biuret compound of isocyanate is 1,3,5-tris (6-isocyanatohexyl) biuret,
A UV curable inkjet ink composition. According to claim 1,
The polar functional group of the monomer (D) is at least one selected from the group consisting of a hydroxyl group, a carboxy group, an amino group, an amine group, a carbonyl group, an acryl group, an acryloyl group, a nitrile group, a vinyl group, a halogen group, a urethane group, and an ester group,
A UV curable inkjet ink composition. According to claim 1,
Monomer (D) is 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, 2-hydroxy-3phenoxyethyl (meth)acrylate, 1-4-cyclohexane dimethanol mono (meth) Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate ) acrylate, at least one selected from the group consisting of dipentaerythritol monohydroxy penta (meth) acrylate, and 2-hydroxy propyl (meth) acrylate,
A UV curable inkjet ink composition. According to claim 1,
based on the total weight of the composition
5 to 40% by weight of heteropolymerization monomer (A);
0.05 to 10% by weight of monomer (B);
2 to 30% by weight of a heat curable compound (C); and
1 to 15% by weight of monomer (D)
including,
A UV curable inkjet ink composition. According to claim 17,
based on the total weight of the composition
10 to 30% by weight or 15 to 25% by weight of heteropolymerization monomer (A);
0.1 to 5% or 0.5 to 1.5% by weight of monomer (B) and
5 to 20% by weight or 10 to 20% by weight of a thermosetting compound (C)
including,
A UV curable inkjet ink composition. According to claim 1,
Further comprising at least one of a multifunctional monomer, a radical photoinitiator, a colorant, a dispersant, a thermosetting polymerization inhibitor, and a leveling agent,
A UV curable inkjet ink composition. According to claim 1,
Characterized in that it does not contain a cationic photoinitiator,
A UV curable inkjet ink composition. According to claim 20,
The colorant is rutile-type titanium oxide or anatase-type titanium oxide,
A UV curable inkjet ink composition. According to claim 1,
The inkjet ink composition is for forming a marking after final curing of PSR on a printed circuit board,
A UV curable inkjet ink composition. 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 on a substrate.

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