KR20230075374A - Solventless photocurable composition - Google Patents

Abstract

The present invention relates to a solvent-free photocurable composition that has excellent curing sensitivity, can be easily photocured under atmospheric conditions, and can realize excellent optical density and adhesion after curing. The solvent-free photocurable composition includes a pigment dispersion including a pigment, a dispersant, an oxetane-based compound, an epoxy-based compound, and a vinyl ether-based compound; and a photoinitiator.

Description

Solvent-free photocurable composition {SOLVENTLESS PHOTOCURABLE COMPOSITION}

The present invention relates to a solvent-free photocurable composition.

Metal wiring for driving the device is located around display devices such as TVs and monitors. In the past, a separate bezel structure was assembled to cover it, but recently, in order to achieve weight reduction and thinning, a bezel is placed on a substrate using a printing method such as inkjet. A method of directly printing a shaped light-shielding pattern is used.

In addition, in order to prevent the pattern of recent mobile devices and the bezel pattern from being recognized, a bezel pattern having excellent light blocking characteristics even with a thin thickness is required. To this end, a photocurable composition having excellent curing sensitivity characteristics capable of easily performing UV curing under atmospheric conditions has been developed.

The present invention provides a solvent-free photocurable composition that can be easily photocured under atmospheric conditions due to its excellent curing sensitivity and can realize excellent optical density and adhesion after curing.

However, the problem to be solved by the present invention is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

An exemplary embodiment of the present invention is a pigment dispersion containing a pigment, a dispersant, an oxetane-based compound, an epoxy-based compound and a vinyl ether-based compound; And a photoinitiator; provides a solvent-free photocurable composition comprising a.

The non-solvent type photocurable composition according to an exemplary embodiment of the present invention has excellent curing sensitivity and can be easily photocured under atmospheric conditions.

In addition, the non-solvent type photocurable composition according to an exemplary embodiment of the present invention may have a slow evaporation rate and excellent storage stability.

In addition, the solvent-free photocurable composition according to an exemplary embodiment of the present invention has excellent dispersibility, and can easily dissolve additives such as a photoinitiator and a sensitizer.

In addition, the non-solvent type photocurable composition according to an exemplary embodiment of the present invention may realize excellent optical density and adhesion after curing.

Throughout the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

Throughout the present specification, when a member is said to be located “on” another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members.

Throughout the present specification, "viscosity" may mean a value measured by a Brookfield viscometer with a Cone Spindle (CPA-40Z) at room temperature (25 °C).

Hereinafter, the present invention will be described in more detail.

An exemplary embodiment of the present invention is a pigment dispersion containing a pigment, a dispersant, an oxetane-based compound, an epoxy-based compound and a vinyl ether-based compound; And a photoinitiator; provides a solvent-free photocurable composition comprising a.

The non-solvent type photocurable composition according to an exemplary embodiment of the present invention has excellent curing sensitivity and can be easily photocured under atmospheric conditions. Specifically, the solvent-free photocurable composition is stable without deterioration in curing sensitivity under conditions of a temperature of 18 ° C. or more and 30 ° C. and a relative humidity of 15% or more and 40% in the absence of external stabilization conditions such as nitrogen filling as an atmospheric condition. Photocuring can be performed with

In addition, the non-solvent type photocurable composition according to an exemplary embodiment of the present invention may have a slow evaporation rate and excellent storage stability.

In addition, the solvent-free photocurable composition according to an exemplary embodiment of the present invention has excellent dispersibility, and can easily dissolve additives such as a photoinitiator and a sensitizer.

According to an exemplary embodiment of the present invention, the solvent-free photocurable composition may include a pigment dispersion and a photoinitiator. Specifically, the solvent-free photocurable composition may not contain a solvent. That is, the photocurable composition may be a solvent-free photocurable composition without a solvent. In this case, the solvent is an organic solvent and may mean a reactive diluent for viscosity control generally used in the art. A conventional photocurable composition for forming a bezel pattern includes a solvent. However, the photocurable composition containing a solvent has a fast evaporation rate, poor storage stability, and poor hardness and adhesion of a cured product. On the other hand, since the solvent-free photocurable composition does not contain a solvent, the evaporation rate can be effectively slowed down and storage stability can be improved. In addition, the solvent-free photocurable composition that does not contain a solvent may have excellent hardness (eg, pencil hardness) after curing, and may effectively improve adhesion to a substrate.

According to one embodiment of the present invention, the pigment may include a black pigment (black pigment). As the black pigment, those used in the art may be used. For example, the black pigment may include at least one of carbon black, graphite, metal oxide, and organic black pigment, but the type of the black pigment is not limited.

For example, the carbon black may be Cisto 5HIISAF-HS, Systo KH, Systo 3HHAF-HS, Systo NH, Systo 3M, Systo 300HAFLS, Systo 116HMMAF-HS, Systo 116MAF, Systo FMFEF- HS, Systo SOFEF, Systo VGPF, Systo SVHSRF-HS and Systo SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, #2700, # 2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, # 3030, #3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical Co., Ltd.); PRINTEX-U, PRINTEX-V, PRINTEX140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX35, PRINTEX-25, PRINTEX-200, PRINTEX- 40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Daegu Co., Ltd.); RAVEN-1100ULTRA, RAVEN1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN- 1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 (Colombia Carbon Co.) or mixtures thereof. In addition, as the organic black pigment, aniline black, lactam black, or perylene black may be used, but is not limited thereto.

According to an exemplary embodiment of the present invention, based on 100 parts by weight of the pigment dispersion, the content of the pigment may be 10 parts by weight or more and 20 parts by weight or less. Specifically, the content of the pigment is 12.5 parts by weight or more and 17.5 parts by weight or less, 14 parts by weight or more and 16 parts by weight or less, 10 parts by weight or more and 16.5 parts by weight or less, 12 parts by weight or more and 15 parts by weight based on 100 parts by weight of the pigment dispersion. parts by weight or less, 15 parts by weight or more and 20 parts by weight or less, or 15 parts by weight or more and 18 parts by weight or less. When the content of the pigment included in the pigment dispersion is within the above-described range, the photocured product of the solventless photocurable composition may realize a uniform color without reducing the curing sensitivity of the solventless photocurable composition.

In particular, when the content of the pigment included in the pigment dispersion is within the above-described range, the solvent-free photocurable composition can realize a required level of optical density after curing. In addition, it is possible to effectively suppress the formation of precipitates because the pigment is not dispersed in the solvent-free photocurable composition, and it is possible to prevent process performance deterioration such as nozzle clogging during an inkjet process.

According to an exemplary embodiment of the present invention, the dispersant may include a urethane-based compound. That is, the dispersant may include a compound containing a urethane bond. Specifically, the dispersant included in the pigment dispersion may be a polyurethane-based dispersant. By adding a dispersant containing a urethane-based compound to the pigment dispersion, the dispersibility of the pigment, oxetane-based compound, epoxy-based compound, vinyl ether-based compound, photoinitiator, and additives included in the solvent-free photocurable composition is improved, resulting in a homogeneous A non-solvent type photocurable composition having a composition can be provided. Through this, the photocured product of the solvent-free photocurable composition can effectively improve hardness and adhesion to the substrate. In addition, since the solvent-free photocurable composition includes a polyurethane-based dispersant, the pigment can be evenly dispersed in the solvent-free photocurable composition, and even color distribution can be implemented while improving curing efficiency.

According to an exemplary embodiment of the present invention, as the urethane-based compound included in the dispersant, those used in the art may be used. For example, Disperbyk 160 to 167 and 182 series of urethane-based dispersants may be used as the dispersant, but the type of the urethane-based dispersant is not limited.

According to an exemplary embodiment of the present invention, the dispersant may not include an acrylic dispersant. In the case of including an acrylic dispersant as the dispersant, a problem in that the hardness (eg, pencil hardness) and adhesion of the photocured product of the non-solvent type photocurable composition may decrease. On the other hand, the non-solvent type photocurable composition according to an exemplary embodiment of the present invention may effectively improve hardness and adhesion after curing by including a urethane-based compound as a dispersant.

According to an exemplary embodiment of the present invention, based on 100 parts by weight of the pigment dispersion, the content of the dispersant may be 1.5 parts by weight or more and 8.5 parts by weight or less. Specifically, the content of the dispersant is 2.5 parts by weight or more and 7.5 parts by weight or less, 3.5 parts by weight or more and 6 parts by weight or less, 4 parts by weight or more and 5 parts by weight or less, 1.5 parts by weight or more and 5 parts by weight, based on 100 parts by weight of the pigment dispersion. parts by weight or less, 3.5 parts by weight or more and 4.5 parts by weight or less, or 4 parts by weight or more and 8.5 parts by weight or less. By adjusting the content of the dispersant included in the pigment dispersion within the above range, the dispersibility of the pigment dispersion is improved so that the solvent-free photocurable composition may have a homogeneous composition. In addition, the pigment can be evenly dispersed in the solvent-free photocurable composition, and even color distribution can be implemented while improving curing efficiency. In addition, the photocured product of the solvent-free photocurable composition can effectively improve hardness and adhesion to a substrate.

According to an exemplary embodiment of the present invention, the pigment dispersion may include an oxetane-based compound. Specifically, the oxetane-based compound may include one or more oxetane rings in a molecule. More specifically, the number of oxetane rings contained in the molecule of the oxetane-based compound may be 1 or more and 4 or less, 1 or more and 3 or less, 1 or more and 2 or less, or 1. By using an oxetane-based compound containing an oxetane ring within the above range, the curing sensitivity, storage stability and dispersibility of the non-solvent type photocurable composition can be improved. In addition, the optical density, hardness and adhesion of the photocured product of the solvent-free photocurable composition can be effectively improved.

According to an exemplary embodiment of the present invention, the oxetane-based compound may include at least one of an aliphatic oxetane-based compound and an aromatic oxetane-based compound. Specifically, the oxetane-based compound may include at least one of a compound represented by Formula 1-1 below and a compound represented by Formula 1-2 below. More specifically, the oxetane-based compound may be a compound represented by Formula 1-1 below.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1, R ₁ and R ₄ may each independently be a linear or branched chain alkyl group having 1 to 10 carbon atoms, and R ₂ and R ₃ may each independently be a linear or branched chain having 1 to 5 carbon atoms. It may be alkylene, and n1 may be 0 or an integer from 1 to 4. Specifically, R ₁ and R ₄ may each independently be a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 6 carbon atoms, or an alkyl group having 5 to 10 carbon atoms. In addition, R ₂ and R ₃ may each independently be a straight-chain or branched-chain alkylene having 1 to 3 carbon atoms or an alkylene having 1 to 2 carbon atoms. The n1 may be 0 or an integer from 1 to 2, 1, or 0.

In Formula 1-2, R ₅ and R ₁₀ may each independently be a linear or branched chain alkyl group having 1 to 10 carbon atoms, and R ₆ to R ₉ may each independently be a linear or branched chain having 1 to 5 carbon atoms. It may be alkylene, Ar ₁ may be arylene having 6 to 20 carbon atoms, and n2 may be an integer of 1 to 4. Specifically, R ₅ and R ₁₀ may each independently be a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 6 carbon atoms, or an alkyl group having 2 to 4 carbon atoms. In addition, R ₆ to R ₉ may each independently be a straight-chain or branched-chain alkylene having 1 to 3 carbon atoms or an alkylene having 1 to 2 carbon atoms. Also, Ar ₁ may be 6 to 18 arylene, 6 to 15 arylene, 6 to 10 arylene, or benzene.

By using an oxetane-based compound including at least one of the compound represented by Formula 1-1 and the compound represented by Formula 1-2, the solvent-free photocurable composition having excellent curing sensitivity, storage stability and dispersibility can be implemented. can In addition, the solvent-free photocurable composition may have excellent optical density, hardness and adhesion after curing.

The oxetane-based compound may include at least one of Compound 1-1 to Compound 1-3. Specifically, the oxetane-based compound may be the following compound 1-1.

[Compound 1-1]

[Compound 1-2]

[Compound 1-3]

In the above compound 1-3, n is an integer of 1 to 4.

In addition, the oxetane-based compound is 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxane) Cymethyl)oxetane, di[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-cyclohexyloxy It may contain at least one of methyl oxetane and phenol novolac oxetane. As the oxetane compound, for example, "Alonoxetane OXT-101", "Allonoxetane OXT-121", "Allonoxetane OXT-211", "Allonoxetane OXT-221" or "Allonoxetane OXT-221" manufactured by Toagosei Co., Ltd. Alonoxetane OXT-212” etc. can be used. These can be used individually or in combination of 2 or more types.

According to an exemplary embodiment of the present invention, based on 100 parts by weight of the pigment dispersion, the content of the oxetane-based compound may be 10 parts by weight or more and 25 parts by weight or less. Specifically, the content of the oxetane-based compound is 12.5 parts by weight or more and 22.5 parts by weight or less, 15 parts by weight or more and 20 parts by weight or less, 10 parts by weight or more and 22.5 parts by weight or less, 10 parts by weight or more based on 100 parts by weight of the pigment dispersion. 20 parts by weight or less, 10 parts by weight or more and 17.5 parts by weight or less, 10 parts by weight or more and 15 parts by weight or less, 15 parts by weight or more and 25 parts by weight or less, or 17 parts by weight or more and 20 parts by weight or less. By adjusting the content of the oxetane-based compound included in the pigment dispersion within the above range, the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition may be improved. In addition, the optical density, hardness and adhesion of the photocured product of the solvent-free photocurable composition can be effectively improved. In particular, when the content of the oxetane-based compound is within the above-described range, it is possible to prevent the curing sensitivity of the non-solvent type photocurable composition from deteriorating, and to effectively prevent the coating property from being deteriorated due to the increase in viscosity of the non-solvent type photocurable composition. can do.

According to one embodiment of the present invention, the pigment dispersion may include an epoxy-based compound. Specifically, the epoxy-based compound may include an ester bond in a molecule. Specifically, the number of ester bonds included in the molecule of the epoxy-based compound may be 1 or more and 4 or less, 1 or more and 3 or less, 1 or more and 2 or less, or 1. By using an epoxy-based compound containing an ester bond within the above range, the solvent-free photocurable composition having excellent curing sensitivity, storage stability and dispersibility may be implemented. In addition, the solvent-free photocurable composition may have excellent optical density, hardness and adhesion after curing.

According to one embodiment of the present invention, the epoxy-based compound may include an alicyclic epoxy group at the terminal. The "alicyclic epoxy group" may refer to an aliphatic ring group in which a cycloalkyl group having 5 to 10 carbon atoms and an epoxy are fused and two rings are fused and epoxidized. At this time, the hydrogen atom constituting the cycloalkyl group may be optionally substituted with a substituent such as an alkyl group. For example, the alicyclic epoxy group is a 3,4-epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, a 3,4-epoxycyclopentylmethyl group, a 3,4-epoxycyclohexylmethyl group, a 2-(3 ,4-epoxycyclopentyl)ethyl group, 2-(3,4-epoxycyclohexyl)ethyl group, 3-(3,4-epoxycyclophenyl)propyl group or 3-(3,4-epoxycyclohexyl)propyl group. there is.

The epoxy-based compound may contain 1 or more and 4 or less, or 1 or more and 2 or less alicyclic epoxy groups. By using an epoxy-based compound containing an alicyclic epoxy group within the above range, the solvent-free photocurable composition having excellent curing sensitivity, storage stability and dispersibility may be implemented. In addition, the solvent-free photocurable composition may have excellent optical density, hardness and adhesion after curing.

According to an exemplary embodiment of the present invention, the epoxy-based compound includes at least one of a first epoxy-based compound containing two alicyclic epoxy groups and a second epoxy-based compound containing one alicyclic epoxy group and one vinyl group. can do. Specifically, the epoxy-based compound may include at least one of a compound represented by Chemical Formula 2-1 and a compound represented by Chemical Formula 2-2 below. More specifically, the epoxy-based compound may be a compound represented by Formula 2-1 below.

[Formula 2-1]

[Formula 2-2]

In Formula 2-1, R ₁₁ and R ₁₃ may each independently be a single bond or a straight or branched chain alkylene having 1 to 5 carbon atoms, and R ₁₂ is a straight or branched chain alkylene having 1 to 5 carbon atoms. and n3 may be 0 or an integer from 1 to 3. Specifically, R ₁₁ and R ₁₃ may each independently represent a single bond, a straight or branched chain alkylene having 1 to 3 carbon atoms, or an alkylene having 1 to 2 carbon atoms. Also, n3 may be 0 or an integer from 1 to 2, 1, or 0.

In Formula 2-2, R ₁₄ may be a single bond or a linear or branched alkylene having 1 to 5 carbon atoms.

By using an epoxy-based compound containing at least one of the compound represented by Formula 2-1 and the compound represented by Formula 2-2, the solvent-free photocurable composition having excellent curing sensitivity, storage stability and dispersibility can be implemented. can In addition, the solvent-free photocurable composition may have excellent optical density, hardness and adhesion after curing.

In addition, the compound represented by Chemical Formula 2-1 may be more specifically a compound represented by Chemical Formula 2-1a.

[Formula 2-1a]

In Formula 2-1a, R ₁₁ to R ₁₃ and n3 may be the same as those defined in Formula 2-1.

The epoxy-based compound may include at least one of Compound 2-1 to Compound 2-3. Specifically, the epoxy-based compound may be Compound 2-1 or Compound 2-2.

[Compound 2-1]

[Compound 2-2]

[Compound 2-3]

In addition, the epoxy-based compound is a bisphenol-type epoxy compound, a novolac-type epoxy compound, a glycidyl ester-type epoxy compound, a glycidyl amine-type epoxy compound, a linear aliphatic epoxy compound, a biphenyl-type epoxy compound, and an alicyclic epoxy compound. It may contain at least one.

For example, the epoxy-based compound is dicyclopentadiene dioxide, cyclohexene oxide, 4-vinyl-1,2-epoxy-4-vinylcyclohexene, vinylcyclohexene dioxide, limonene monooxide, limonene dioxide, (3 ,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate, 3-vinylcyclohexene oxide, bis(2,3-epoxycyclopentyl) ether, bis(3,4-epoxycyclohexylmethyl) Adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, (3,4-epoxycyclohexyl)methylalcohol, (3,4-epoxy-6-methylcyclohexyl)methyl-3 ,4-epoxy-6-methylcyclohexanecarboxylate, ethylene glycol bis(3,4-epoxycyclohexyl)ether, 3,4-epoxycyclohexenecarboxylic acid ethylene glycol diester, (3,4-epoxycyclo Hexyl)ethyltrimethoxysilane, Celloxide 8000 from Daicel Corporation, and the like can be used. These can be used individually or in combination of 2 or more types.

According to an exemplary embodiment of the present invention, based on 100 parts by weight of the pigment dispersion, the content of the epoxy-based compound may be 15 parts by weight or more and 30 parts by weight or less. Specifically, the content of the epoxy-based compound is 17.5 parts by weight or more and 27.5 parts by weight or less, 20 parts by weight or more and 25 parts by weight or less, 15 parts by weight or more and 25 parts by weight or less, 18 parts by weight or more based on 100 parts by weight of the pigment dispersion. 23 parts by weight or less, 20 parts by weight or more and 30 parts by weight or less, or 22 parts by weight or more and 26 parts by weight or less. By adjusting the content of the epoxy-based compound included in the pigment dispersion within the above range, the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition may be improved. In addition, the optical density, hardness and adhesion of the photocured product of the solvent-free photocurable composition can be effectively improved. In particular, when the content of the epoxy-based compound included in the pigment dispersion is within the above-described range, it is possible to suppress the increase in viscosity of the non-solvent type photocurable composition and effectively prevent a decrease in curing sensitivity.

According to an exemplary embodiment of the present invention, the pigment dispersion may include a vinyl ether-based compound. Specifically, the vinyl ether compound may be one in which a vinyl ether group is bonded to a cycloalkylene having 5 to 10 carbon atoms. By using the vinyl ether-based compound having a cyclic alkyl skeleton in the molecule, the solvent-free photocurable composition having excellent curing sensitivity, storage stability and dispersibility can be implemented. In addition, the solvent-free photocurable composition may have excellent optical density, hardness and adhesion after curing.

According to an exemplary embodiment of the present invention, the vinyl ether-based compound may contain at least one vinyl ether group. Specifically, the number of vinyl ether groups contained in the vinyl ether compound may be 1 to 3, 1 to 2, or 2. The vinyl ether compound may include a compound represented by Chemical Formula 3-1 below.

[Formula 3-1]

In Formula 3-1, R ₂₁ and R ₂₂ may each independently be a single bond or a linear or branched alkylene having 1 to 5 carbon atoms, R ₂₃ may be a vinyl ether group or a hydroxyl group, and n4 is 0 Or it may be an integer of 1 to 2, and Cy1 may be a cycloalkylene having 5 to 10 carbon atoms. Specifically, R ₂₁ and R ₂₂ may each independently be a single bond, linear or branched alkylene having 1 to 3 carbon atoms or alkylene having 1 to 2 carbon atoms. n4 may be 0 or 1, and Cy1 may be cycloalkylene having 5 to 8 carbon atoms, cycloalkylene having 5 to 6 carbon atoms, or cyclohexylene.

By using the vinyl ether-based compound including the compound represented by Chemical Formula 3-1, the solvent-free photocurable composition having excellent curing sensitivity, storage stability and dispersibility can be implemented. In addition, the solvent-free photocurable composition may have excellent optical density, hardness and adhesion after curing.

In addition, the compound represented by Chemical Formula 3-1 may be more specifically a compound represented by Chemical Formula 3-1a.

[Formula 3-1a]

In Formula 3-1a, R ₂₁ to R ₂₃ may be the same as those defined in Formula 3-1, and n4 may be 0 or 1.

According to an exemplary embodiment of the present invention, the vinyl ether compound includes a first vinyl ether compound containing one vinyl ether terminal group and a second vinyl ether compound containing two or more vinyl ether terminal groups. can do. Specifically, the second vinyl ether compound may contain 2 to 5, 2 to 3, or 2 vinyl ether end groups. When the pigment dispersion includes the first vinyl ether-based compound and the second vinyl ether-based compound, the curing sensitivity, storage stability, and dispersibility of the solvent-free photocurable composition may be improved. In addition, the optical density, hardness and adhesion of the photocured product of the solvent-free photocurable composition can be effectively improved. In particular, the curing sensitivity of the non-solvent type photocurable composition can be further improved.

According to an exemplary embodiment of the present invention, the vinyl ether-based compound may include at least two of the following compounds 3-1 to 3-3. Specifically, the vinyl ether-based compound may include the following compound 3-1 as the first vinyl ether-based compound and the following compound 3-2 as the second vinyl ether-based compound.

[Compound 3-1]

[Compound 3-2]

[Compound 3-3]

According to an exemplary embodiment of the present invention, the content of the second vinyl ether-based compound included in the pigment dispersion may be greater than the content of the first vinyl ether-based compound. Specifically, the weight ratio of the first vinyl ether-based compound and the second vinyl ether-based compound included in the vinyl ether-based compound may be 1:1.1 to 1:2.5. More specifically, the weight ratio of the first vinyl ether-based compound to the second vinyl ether-based compound is 1:1.1 to 1:2.3, 1:1.1 to 1:2, 1:1.1 to 1:1.7, 1:1.1 to 1:1.1 1:1.5, 1:1.4 to 1:2, 1:1.8 to 1:2.5, or 1:1.8 to 1:2. By adjusting the weight ratio of the first vinyl ether-based compound and the second vinyl ether-based compound included in the pigment dispersion to the above range, the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition can be improved. there is. In addition, the optical density, hardness and adhesion of the photocured product of the solvent-free photocurable composition can be effectively improved.

According to an exemplary embodiment of the present invention, based on 100 parts by weight of the pigment dispersion, the content of the vinyl ether-based compound may be 20 parts by weight or more and 55 parts by weight or less. Specifically, the content of the vinyl ether compound is 25 parts by weight or more and 52.5 parts by weight or less, 30 parts by weight or more and 50 parts by weight or less, 35 parts by weight or more and 48 parts by weight or less, 40 parts by weight based on 100 parts by weight of the pigment dispersion. 45 parts by weight or less, 20 parts by weight or more and 50 parts by weight or less, 27.5 parts by weight or more and 50 parts by weight or less, 32.5 parts by weight or more and 50 parts by weight or less, 37.5 parts by weight or more and 50 parts by weight or less, 42 parts by weight or more and 48 parts by weight or less , 40 parts by weight or more and 55 parts by weight or less, or 42 parts by weight or more and 50 parts by weight or less.

By adjusting the content of the vinyl ether compound included in the pigment dispersion within the above range, the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition may be improved. In addition, the optical density, hardness and adhesion of the photocured product of the solvent-free photocurable composition can be effectively improved. In particular, it is possible to effectively suppress the non-curing of the solvent-free photocurable composition or the decrease in curing sensitivity under high humidity conditions.

According to an exemplary embodiment of the present invention, based on 100 parts by weight of the pigment dispersion, the content of the first vinyl ether compound is 10 parts by weight or more and 25 parts by weight or less, 12.5 parts by weight or more and 22.5 parts by weight or less, 14 parts by weight or more. 20 parts by weight or less, 10 parts by weight or more and 15 parts by weight or less, or 20 parts by weight or more and 25 parts by weight or less. When the amount of the first vinyl ether-based compound included in the pigment dispersion is within the above range, the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition may be improved. In addition, the optical density, hardness and adhesion of the photocured product of the solvent-free photocurable composition can be effectively improved. In particular, it is possible to effectively suppress the non-curing of the solvent-free photocurable composition or the decrease in curing sensitivity under high humidity conditions.

According to an exemplary embodiment of the present invention, based on 100 parts by weight of the pigment dispersion, the content of the second vinyl ether compound is 20 parts by weight or more and 40 parts by weight or less, 25 parts by weight or more and 35 parts by weight or less, 25 parts by weight or more. 30 parts by weight or less, 20 parts by weight or more and 30 parts by weight or less, or 27.5 parts by weight or more and 40 parts by weight or less. By adjusting the content of the second vinyl ether-based compound included in the pigment dispersion within the above range, the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition may be improved. In addition, the optical density, hardness and adhesion of the photocured product of the solvent-free photocurable composition can be effectively improved. In particular, it is possible to effectively suppress the non-curing of the solvent-free photocurable composition or the decrease in curing sensitivity under high humidity conditions.

According to an exemplary embodiment of the present invention, the weight ratio between the oxetane-based compound and the epoxy-based compound included in the pigment dispersion may be 1:1.1 to 1:2. Specifically, the weight ratio of the oxetane-based compound to the epoxy-based compound may be 1:1.3 to 1:2, 1:1.5 to 1:1.8, 1:1.1 to 1:1.5, or 1:1.7 to 1:2. . When the weight ratio of the oxetane-based compound and the epoxy-based compound included in the pigment dispersion is within the above range, the solvent-free photocurable composition having excellent curing sensitivity, storage stability and dispersibility can be implemented. In addition, the cured product of the solvent-free photocurable composition may have excellent optical density, hardness and adhesion.

According to an exemplary embodiment of the present invention, the weight ratio of the oxetane-based compound and the first vinyl ether-based compound included in the pigment dispersion is 1:0.5 to 1:2, 1:0.8 to 1:1.8, 1:1 to 1:1. 1:1.5, 1:0.5 to 1:1.5, 1:0.7 to 1:1, 1:1.3 to 1:2, or 1:1.5 to 1:1.8. By adjusting the weight ratio of the oxetane-based compound and the first vinyl ether-based compound included in the pigment dispersion to the above range, it is possible to improve the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition. The solvent-free photocurable composition may have excellent optical density, hardness and adhesion after curing.

According to an exemplary embodiment of the present invention, the weight ratio of the first vinyl ether-based compound and the epoxy-based compound included in the pigment dispersion is 1:1.1 to 1:2, 1:1.1 to 1:1.8, 1:1.1 to 1:1.1 1:1.6, 1:1.1 to 1:1.5, 1:1.1 to 1:1.3, 1:1.5 to 1:2, or 1:1.6 to 1:1.8. By adjusting the weight ratio of the first vinyl ether-based compound and the epoxy-based compound included in the pigment dispersion to the above range, it is possible to improve the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition. The solvent-free photocurable composition may have excellent optical density, hardness and adhesion after curing.

According to an exemplary embodiment of the present invention, the photoinitiator is a cationic photopolymerization initiator, and may be a compound that forms a cation species or a Bronsted acid by light (eg, ultraviolet) irradiation. The photoinitiator may include a sulfonic acid salt having an asymmetric structure. Specifically, the photoinitiator may include a phenyl-based sulfonic acid salt containing two sulfur (S) atoms in a molecule and having an asymmetric structure. For example, the photoinitiator may include Compound 4-1 below.

[Compound 4-1]

By using the photoinitiator containing the sulfonate having an asymmetric structure, it is possible to improve the curing sensitivity, storage stability and dispersibility of the solvent-free photocurable composition, and the solvent-free photocurable composition has excellent optical density and hardness after curing. and adhesion. When a sulfonic acid salt having a symmetrical structure, a sulfonic acid salt having 1 or 3 or more sulfurs contained in the molecule, or an iodine salt is used as the photoinitiator, the curing sensitivity and storage stability of the solvent-free photocurable composition are reduced, and the Problems such as hardness, adhesion, and optical density of the photocured product of the non-solvent type photocurable composition may be inferior.

According to an exemplary embodiment of the present invention, the amount of the photoinitiator may be 2.5 parts by weight or more and 6.5 parts by weight or less based on 100 parts by weight of the pigment dispersion. Specifically, with respect to 100 parts by weight of the pigment dispersion, the content of the photoinitiator is 3.5 parts by weight or more and 5.5 parts by weight or less, 4 parts by weight or more and 5 parts by weight or less, 3.5 parts by weight or more and 5 parts by weight or less, or 4 parts by weight or more 6.5 parts by weight or more. It may be less than parts by weight. When the content of the photoinitiator is within the above range, the photocuring reaction of the solvent-free photocurable composition can be stably performed, and the formation of precipitates of the photoinitiator in the solvent-free photocurable composition can be suppressed, and the solvent-free photocurable composition can be prevented from forming. It is possible to prevent a decrease in coating properties due to an increase in the viscosity of the photocurable composition.

According to an exemplary embodiment of the present invention, the solvent-free photocurable composition may further include an additive. Specifically, the additive may include at least one of a sensitizer, an adhesion enhancer, a surfactant, and an antioxidant.

According to an exemplary embodiment of the present invention, the solvent-free photocurable composition may include a sensitizer as an additive. The sensitizer may be used as a photosensitizer that is used in the art. For example, the sensitizer may include anthracene-based compounds such as anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl 9,10-dimethoxyanthracene; Benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3 - Benzophenone compounds such as dimethyl-4-methoxybenzophenone and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; acetophenone; ketone compounds such as dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and propanone; perylene; fluorenone compounds such as 9-fluorenone, 2-chloro-9-fluorenone, and 2-methyl-9-fluorenone; thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone (ITX), diisopropyl thioxanthone, etc. thioxanthone-based compounds; xanthone-based compounds such as xanthone and 2-methylxanthone; anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane, etc. acridine-based compounds; dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, and 9,10-phenanthrenequinone; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4- amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 - Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo coumarin compounds such as pyrano[6,7,8-ij]-quinolizin-11-one; chalcone compounds such as 4-diethylamino chalcone and 4-azidbenzalacetophenone; 2-benzoylmethylene; and 3-methyl-b-naphthothiazoline.

According to an exemplary embodiment of the present invention, the content of the sensitizer may be 1.5 parts by weight or more and 4.5 parts by weight or less based on 100 parts by weight of the pigment dispersion. By adjusting the content of the sensitizer within the above-mentioned range, curing sensitivity may be prevented from being lowered, thereby improving coating properties of the photocured film of the solvent-free photocurable composition. In addition, it is possible to prevent the sensitizer from precipitating in the non-solvent type photocurable composition and impairing stability.

According to one embodiment of the present invention, the solvent-free photocurable composition may include a surfactant as an additive. By adding a surfactant, the surface tension of the solvent-free photocurable composition is lowered, so that the solvent-free photocurable composition may exhibit a small taper angle. As the surfactant, those used in the art may be used. For example, the surfactant is DIC (DaiNippon Ink & Chemicals) Megafack F444, F-475, F-478, F-479, F-484, F-550, F-552, F-553, F-555 , F-570, RS-75; Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141 and S-145 from Asahi Glass; Fluorad FC93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-4430 from Sumitomo 3M; Zonyl FS-300, FSN, FSN-100 and FSO from DuPont and BYK-306, BYK-310, BYK-320, BYK-330, BYK-331, BYK-333, BYK-342, BYK-350, BYK from BYK -354, BYK-355, BYK-356, BYK-358N, BYK-359, BYK-361N, BYK-381, BYK-370, BYK-371, BYK-378, BYK-388, BYK-392, BYK-394 , BYK-399, BYK-3440, BYK-3441, BYKETOL-AQ, BYK-DYNWET 800, BYK-SILCLEAN 3700 and BYK-UV 3570; Alternatively, one selected from the group consisting of Rad 2100, Rad 2011, Glide 100, Glide 410, Glide 450, Flow 370, and Flow 425 manufactured by Tego may be used.

According to an exemplary embodiment of the present invention, the content of the surfactant may be 0.1 parts by weight or more and 5 parts by weight or less, or 0.2 parts by weight or more and 3 parts by weight or less, based on 100 parts by weight of the pigment dispersion. By adjusting the content of the surfactant within the above-mentioned range, the surface tension of the non-solvent type photocurable composition can be effectively lowered to effectively coat the substrate with the non-solvent type photocurable composition. In addition, it is possible to prevent a decrease in compatibility and defoaming properties of the non-solvent type photocurable composition due to excessive use of a surfactant.

According to an exemplary embodiment of the present invention, the solvent-free photocurable composition may include an adhesion enhancer as an additive. By adding an adhesion enhancer, peeling of the photocured product of the solvent-free photocurable composition from the substrate can be effectively prevented. The adhesion enhancer may include a silane-based compound. The silane-based compound that can be used as the adhesion enhancer is, for example, any one of an alkoxy silane-based compound, an epoxy silane-based compound, an aminophenyl silane-based compound, an amino silane-based compound, a mercapto silane-based compound, and a vinyl silane-based compound. can include Specifically, the adhesion promoter is 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxy It may include at least one of propyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, and 3-methacryloxypropyl trimethoxysilane. However, the type of the adhesion enhancer is not limited, and the adhesion enhancer may include a phosphate-based acrylate compound.

According to an exemplary embodiment of the present invention, the content of the adhesion promoter may be 0.1 parts by weight or more and 5 parts by weight or less, or 0.5 parts by weight or more and 3.5 parts by weight or less, based on 100 parts by weight of the pigment dispersion. When the content of the adhesion enhancer is within the above-described range, peeling of the photocured product of the solvent-free photocurable composition from the substrate can be effectively prevented. In addition, it is possible to suppress an increase in viscosity and a decrease in dispersibility of the non-solvent type photocurable composition.

According to an exemplary embodiment of the present invention, the solvent-free photocurable composition may include an antioxidant as an additive. As the antioxidant, those used in the art may be used without limitation. The amount of the antioxidant may be 0.01 parts by weight or more and 0.2 parts by weight or less, or 0.05 parts by weight or more and 0.1 parts by weight or less, based on 100 parts by weight of the pigment dispersion. By adjusting the content of the antioxidant within the above range, oxidation of the photocured product of the solvent-free photocurable composition can be effectively prevented, thereby improving long-term reliability.

On the other hand, the types of additives included in the solvent-free photocurable composition are not limited to those described above, and may further include other additives used in the art within a range in which required physical properties are not impaired.

According to an exemplary embodiment of the present invention, the solvent-free photocurable composition may have a viscosity of 10 cP or more and 40 cP or less at 25 °C. Specifically, the solvent-free photocurable composition may have a viscosity at 25° C. of 10 cP or more and 35 cP or less, 10 cP or more and 30 cP or less, 10 cP or more and 25 cP or less, or 10 cP or more and 20 cP or less. The non-solvent type photocurable composition having a viscosity within the aforementioned range may have excellent coating properties, excellent inkjet discharge properties, and excellent processability. Specifically, when the viscosity of the non-solvent type photocurable composition is within the above range, it may be suitable for an inkjet process and discharge at a process temperature may be good. The process temperature means a temperature at which the viscosity of the non-solvent type photocurable composition is lowered, and may be 10 °C or more and 100 °C or less, or 20 °C or more and 70 °C or less.

According to an exemplary embodiment of the present invention, the solvent-free photocurable composition may be an ink for pattern formation. Specifically, the solvent-free photocurable composition may be an ink for forming a black pattern. The black pattern prepared from the solvent-free photocurable composition can be applied to various fields. For example, the black pattern may be used as a bezel pattern and applied to a display substrate. Also, the black pattern may be applied to a camera lens. However, the use to which the black pattern is applied is not limited.

According to one embodiment of the present invention, the solvent-free photocurable composition may be an ink for forming a Bezel pattern. Since the solvent-free photocurable composition has the above-described composition, it has good applicability when forming a Bezel pattern, and after photocuring, it may have excellent light blocking properties even at a thin thickness. In addition, the solvent-free photocurable composition has excellent curing sensitivity, so that a bezel pattern can be easily formed through UV photocuring under atmospheric conditions without external stabilization conditions such as nitrogen filling, and surface wrinkles occur on the formed bezel pattern. It is possible to implement a high-quality bezel pattern by effectively suppressing the

One embodiment of the present invention provides a pattern including a cured product of the solvent-free photocurable composition. Specifically, the pattern may be a black pattern including a cured product of the solvent-free photocurable composition. The black pattern can be applied to various fields, and for example, the black pattern can be used as a bezel pattern and applied to a display substrate. Also, the black pattern may be applied to a camera lens. However, the use to which the black pattern is applied is not limited.

One embodiment of the present invention provides a bezel pattern including a cured product of the solvent-free photocurable composition.

In order to form the bezel pattern using the solvent-free photocurable composition, it may be performed through a method used in the art. For example, forming a bezel pattern by inkjet printing the solvent-free photocurable composition on a substrate; and curing the bezel pattern by irradiating ultraviolet rays. The bezel pattern may be formed using the solvent-free photocurable composition.

According to an exemplary embodiment of the present invention, the solvent-free photocurable composition can be spread within a short time immediately after inkjet printing, exhibiting excellent film properties, and cured to exhibit excellent adhesive properties. Accordingly, when forming a bezel pattern using the solvent-free photocurable composition, it may be preferable to install a light source (eg, UV-lamp) directly behind the inkjet head so that curing is possible simultaneously with inkjet printing.

According to an exemplary embodiment of the present invention, in order to photocur the solvent-free photocurable composition, light having a wavelength range of 250 nm or more and 450 m or less is 500 mJ/mm ² or more and 5,000 mJ/mm ^{2 or less} with a total exposure amount of can be investigated Specifically, the solvent-free photocurable composition may be photocured by irradiating light having a wavelength range of 360 nm to 410 nm with a total exposure amount of 500 mJ/mm ² or more and 5,000 mJ/mm ² or less.

According to an exemplary embodiment of the present invention, the Bezel pattern including the photocured material of the solvent-free photocurable composition may exhibit a pencil hardness of 1B or more as a result of a pencil hardness test. Specifically, the bezel pattern may exhibit a pencil hardness of 1H or more. In addition, the bezel pattern including the photocured material of the solvent-free photocurable composition may exhibit an adhesive force of 4B or higher as a result of a cross-cut test. That is, the bezel pattern including the photocured material of the solvent-free photocurable composition may have excellent hardness and adhesion to a substrate.

One embodiment of the present invention provides a display substrate including the bezel pattern. As described above, the bezel pattern including the photocured product of the solvent-free photocurable composition has excellent surface quality, excellent adhesion (adhesion) to the substrate, and excellent optical density even at a thin thickness, A display substrate containing a pattern can have excellent quality. Accordingly, a display device having excellent image quality and the like can be implemented using the display substrate.

Hereinafter, examples will be described in detail to explain the present invention in detail. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present invention to those skilled in the art.

compound

1) Black pigment: CB-1, CB-22

2) Dispersant

- Urethane type: Disperbyk160 (manufactured by Big Chemie)

- Acrylic type: Disperbyk2000 (manufactured by Big Chemie)

3) Oxetane-based compound: Compound 1-1 (bis[1-ethyl(3-oxetanyl)]methyl ether; OXT-221; manufactured by Toagosei)

4) Epoxy-based compounds:

-Compound 2-1 ((3',4'-epoxycyclohexane)methyl-3,4-epoxycyclohexyl carboxylate; Celloxide 2021P; manufactured by Daicel)

- Compound 2-2 (bis(3,4-epoxycyclohexylmethyl) adipate; UVR 6128; manufactured by Daicel)

5) Vinyl ether compounds:

- Compound 3-1 (cyclohexyl vinyl ether; CHVE; manufactured by BASF)

- Compound 3-2 (1,4-cyclohexanedimethanol divinyl ether; CHDMDVE; manufactured by BASF)

6) Photoinitiators:

- Compound 4-1 (4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate; CPI-210S; manufactured by SanApro)

- Compound 4-2 (Bis-(4-t-butylphenyl)-Iodonium hexafluorophosphate; SpeedCure 938; manufactured by SARTOMER)

[Compound 4-2]

- Compound 4-3 (Omnicat 250; manufactured by IGM Resins)

[Compound 4-3]

- Compound 4-4 (Speedcure 992; manufactured by Lamberti)

[Compound 4-4]

- Compound 4-5 (Omnicat 550; manufactured by IGM Resins))

[Compound 4-5]

7) Sensitizer

- UVS-1331 (9,10-dibutoxy anthracene; manufactured by Kawasaki Chemical)

- ITX (manufactured by IGM Resin)

8) Adhesion enhancer: KBM-403 (3-glycidoxypropyl trimethoxysilane; manufactured by Shinetsu)

9) Surfactant: F-554 (manufactured by DIC)

10) Antioxidant: BHT (manufactured by Junsei)

11) Solvent: BC (Ethylene Glycol Monobutyl Ether; manufactured by TCI)

Example

Preparation Example 1

Preparation of Pigment Dispersion

CB-1 as a black pigment, Disperbyk160 of urethane type as a dispersant, Compound 1-1 (OXT-221) as an oxetane-based compound, Compound 2-1 (2021P) as an epoxy-based compound, and Compound 3-2 (as a vinyl ether-based compound) CHDMDVE) was stirred at room temperature for 5 hours to prepare a pigment dispersion.

At this time, based on 100 parts by weight of the pigment dispersion, the content of the black pigment is 20 parts by weight, the content of the dispersant is 5 parts by weight, the content of the oxetane-based compound is 19 parts by weight, the content of the epoxy-based compound is 18 parts by weight, and the vinyl ether-based The content of the compound was 38 parts by weight.

Preparation Example 2 and Comparative Preparation Example 1

A pigment dispersion was prepared in the same manner as in Preparation Example 1, except that the composition of the pigment dispersion was adjusted as shown in Table 1 below.

Preparation Example 1 Preparation Example 2 comparison
Preparation Example 1 pigment
dispersion black pigment CB-1 20 20 20 dispersant Urethane type 5 5 5 Oxetane-based compound OXT-221 19 19 75 Epoxy system
compound 2021P 18 - - UVR-6128 - 18 - vinyl ether
compound CHDMDVE 38 38 -

Example 1

Preparation of Pigment Dispersion

CB-1 as a black pigment, Disperbyk160 of urethane type as a dispersant, Compound 1-1 (OXT-221) as an oxetane-based compound, Compound 2-1 (2021P) as an epoxy-based compound, Compound 3- as a first vinyl ether-based compound 1 (CHVE) and compound 3-2 (CHDMDVE) as a second vinyl ether compound were stirred at room temperature to prepare a pigment dispersion.

At this time, based on 100 parts by weight of the pigment dispersion, the content of the black pigment is 15 parts by weight, the content of the dispersant is 4 parts by weight, the content of the oxetane-based compound is 17 parts by weight, the content of the epoxy-based compound is 22 parts by weight, the first vinyl The content of the ether-based compound was 14 parts by weight, and the content of the second vinyl ether-based compound was 28 parts by weight.

Preparation of solvent-free photocurable composition

The pigment dispersion prepared above, Compound 4-1 (CPI-210S) as a photoinitiator, UVS-1331 as a sensitizer, KBM-403 as an adhesion promoter, F-554 as a surfactant, and BHT as an antioxidant were mixed at room temperature for 6 hours. While stirring to prepare a solvent-free photocurable composition.

At this time, with respect to 100 parts by weight of the pigment dispersion, the content of the photoinitiator is 4 parts by weight, the content of the sensitizer is 3 parts by weight, the content of the adhesion promoter is 3 parts by weight, the content of the surfactant is 0.2 parts by weight, and the content of the antioxidant is 3 parts by weight. It was 0.05 part by weight.

Example 2 and Example 3

A pigment dispersion and a solvent-free photocurable composition were prepared in the same manner as in Example 1, except that the composition was adjusted as shown in Table 2 below.

Solvent-free photocurable composition Example 1 Example 2 Example 3 pigment
dispersion black pigment CB-1 15 - 15 CB-22 - 15 - dispersant Urethane type 4 4 4 Oxetane-based compound OXT-221 17 17 11 Epoxy system
compound 2021P 22 22 - UVR-6128 - - 22 vinyl ether based
compound CHVE 14 14 20 CHDMDVE 28 28 28 photoinitiator CPI-210S 4 4 4 additive sensitizer UVS-1331 3 3 3 Adhesion enhancer KBM-403 3 3 3 Surfactants F-554 0.2 0.2 0.2 antioxidant BHT 0.05 0.05 0.05

Comparative Examples 1 to 8

A pigment dispersion and a solvent-free photocurable composition were prepared in the same manner as in Example 1, except that the composition was adjusted as shown in Table 3 below.

At this time, in Comparative Example 1, a solvent was included during the preparation of the pigment dispersion, and thus the prepared photocurable composition corresponds to a solvent type.

In Tables 1 to 3, the contents (parts by weight) of the black pigment, dispersant, oxetane-based compound, epoxy-based compound, and vinyl ether-based compound are based on 100 parts by weight of the pigment dispersion, and in Tables 2 and 3, the photoinitiator, The content (parts by weight) of the sensitizer, adhesion promoter, surfactant and antioxidant is based on 100 parts by weight of the pigment dispersion.

Experimental example

viscosity measurement

Regarding the non-solvent type photocurable composition prepared in Example 1, the viscosity of the composition was measured using a Brookfield viscometer with a Cone Spindle (CPA-40Z) at room temperature (25 ° C), and the results are shown in Table 5 below. was

The viscosity of the non-solvent type photocurable compositions prepared in Examples 2 and 3 was measured in the same manner and is shown in Table 5 below.

The viscosity of the non-solvent type photocurable compositions prepared in Comparative Examples 1 to 8 was measured in the same manner and is shown in Table 6 below.

Cure sensitivity evaluation

The solvent-free photocurable composition prepared in Example 1 was applied to a glass substrate (5X5 cm) with a pipette, and spin coating was performed at a rotational speed of about 2,500 rpm to a thickness of 3 μm. Then, ultraviolet rays were irradiated with a total exposure amount of 2000 mJ/cm 2 using a UV irradiation device (395 nm UV LED) to cure the solvent-free photocurable composition. The exposure amount was measured and calculated using an illuminometer.

When the non-solvent type photocurable composition is touched to the touch after 1 minute after UV irradiation, when the liquid film is not completely cured and comes out as a liquid, it is judged as uncured and indicated by X, and if the liquid film is not completely cured and remains sticky (tack property If there is), it was evaluated as △, and when the film was completely cured and there was no stickiness, it was evaluated as ○, and the results are shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Examples 2 and 3 were evaluated in the same manner, and the results are shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Comparative Examples 1 to 8 were evaluated in the same manner, and the results are shown in Table 6 below.

Evaporation rate evaluation

After storing the non-solvent type photocurable composition prepared in Example 1 at room temperature for a certain period of time, the evaporation rate was observed. Specifically, the evaluation of the evaporation rate was calculated as the ratio of residue compared to the initial amount by measuring the weight of the composition remaining after 1g of the solvent-free photocurable composition was put in an aluminum dish using a micro balance, and after time had elapsed under room temperature storage. After 2 hours had elapsed after the start of evaporation, when the residual amount ratio was 85% or more, it was evaluated as ○, and when it was less than 85%, it was evaluated as X, and the results are shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Examples 2 and 3 were evaluated in the same manner, and the results are shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Comparative Examples 1 to 8 were evaluated in the same manner, and the results are shown in Table 6 below.

Storage stability evaluation

The storage stability of the non-solvent type photocurable composition prepared in Example 1 was measured. Specifically, after about 15 ml of the composition was injected into a 20 ml brown glass bottle, storage stability at room temperature (25° C.) was evaluated. The viscosity of the composition in each vessel was measured at 25° C. using a Viscometer DV-2 (Brookfield). After 1 month at room temperature, the viscosity change rate {(viscosity increase/initial viscosity value) X 100} of the composition is evaluated as X if it is 200% or more, △ if it is between 100 and 200%, and ○ if it is less than 100% And the results are shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Examples 2 and 3 were evaluated in the same manner, and the results are shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Comparative Examples 1 to 8 were evaluated in the same manner, and the results are shown in Table 6 below.

In addition, the pigment dispersions prepared in Preparation Example 1, Preparation Example 2 and Comparative Preparation Example 1 were evaluated in the same manner at room temperature (25 ° C), low temperature (7 ° C) and high temperature (45 ° C), The results are shown in Table 4 below.

Pencil hardness evaluation

A bezel specimen was prepared by curing the solvent-free photocurable composition prepared in Example 1 in the same manner as in the “curing sensitivity evaluation”. Thereafter, according to the measurement standard JIS K5400 using a pencil hardness meter, a total of 3 measurements per pencil with a load of 200 gf were measured, and then the hardness was confirmed by measuring the degree of scratching and pressing, and the results are shown in Table 5 below. .

The non-solvent type photocurable compositions prepared in Examples 2 and 3 were evaluated in the same manner, and the results are shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Comparative Examples 1 to 8 were evaluated in the same manner, and the results are shown in Table 6 below.

Adhesion evaluation

A bezel specimen was prepared by curing the solvent-free photocurable composition prepared in Example 1 in the same manner as in the “curing sensitivity evaluation”. A cross-cut test was performed on the prepared bezel specimen in accordance with the standard of ASTM D3359, which is a cross-cut standard. Specifically, the specimen was cut with a knife in 10 lines each in the horizontal and vertical directions at intervals of 1 mm to make 100 square grids each of 1 mm in width and length. After that, when Nichiban's CT-24 adhesive tape was attached to the cutting surface and then peeled off, the state of the falling surface was measured with an optical microscope.

- Criteria for evaluating cross-cut adhesion

5B: When there is no change from the initial contrast of the fallen surface

4B: When the fallen area is less than 5% of the total area

3B: When the fallen surface is 5% or more and less than 15% of the total area

2B: When the fallen surface is 15% or more and less than 35% of the total area

1B: When the fallen surface is 35% or more and less than 65% of the total area

0B: When the fallen surface is 65% or more and less than 100% of the total area

X: When the bezel specimen is not attached (100% of the total area is the separated side)

The test results for Examples 1 to 3 are shown in Table 5 below, and the results of tests for Comparative Examples 1 to 8 based on the evaluation criteria are shown in Table 6 below.

Evaluation of solubility and precipitation

In the preparation of the solvent-free photocurable composition prepared in Example 1, the properties of whether the photoinitiator and the sensitizer were dissolved were evaluated. Specifically, when no precipitate was observed with the naked eye, it was evaluated as ○, when a little precipitate was formed or it was difficult to judge visually, and when a large amount of precipitate was formed, it was evaluated as X.

In addition, the non-solvent type photocurable composition prepared in Example 1 was cured in the same manner as in the “curing sensitivity evaluation” to prepare bezel specimens. The manufactured bezel specimens were inspected and evaluated through an optical microscope to determine whether or not phenomena such as surface protrusions due to precipitation occurred. When it was good without precipitation (protrusions and craters, etc.), it was marked as ○, and when precipitation (protrusions and craters, etc.) occurred, it was marked as X.

Optical density/thickness (OD/㎛) evaluation of bezel film

A bezel specimen was prepared by curing the solvent-free photocurable composition prepared in Example 1 in the same manner as in the "curing sensitivity evaluation". After that, the optical density of the bezel specimen was measured through an OD measuring instrument from X-rite, and the thickness of the bezel specimen in the same area as the optical density (OD) measuring part was measured using a Dektak thickness measuring instrument. Then, OD/㎛ was calculated through the measured data and shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Examples 2 and 3 were evaluated in the same manner, and the results are shown in Table 5 below.

The non-solvent type photocurable compositions prepared in Comparative Examples 1 to 8 were evaluated in the same manner, and the results are shown in Table 6 below.

Dispersion evaluation

With respect to the pigment dispersion prepared in Preparation Example 1, dispersibility was evaluated through a dynamic light scattering particle size analysis method, and the results are shown in Table 4 below. Specifically, the degree of particle size distribution change was analyzed using a Particle Size Analyzer (Microtech), and the case where the particle size change rate (%) was 0% or more and less than 5% compared to the initial measurement value when stored for 1 month at room temperature "O" was evaluated, and cases of 5% or more were evaluated as "X".

In addition, the evaluation was conducted in the same way for the pigment dispersions prepared in Preparation Example 2 and Comparative Preparation Example 1, and the results are shown in Table 4 below.

Preparation Example 1 Preparation Example 2 Comparative Preparation Example 1 storage stability room temperature (25℃) O O X Low temperature (7℃) O O X high temperature (45℃) O O X dispersibility O O X

Referring to Table 4, it was confirmed that the pigment dispersions prepared in Preparation Examples 1 and 2 were excellent in storage stability and dispersibility, but the pigment dispersions prepared in Comparative Preparation Example 1 were inferior in both storage stability and dispersibility. did

Example 1 Example 2 Example 3 Viscosity (cP) 18.3 19.7 17.7 curing sensitivity O O O evaporation rate O O O storage stability
(25℃) △ O △ pencil hardness 1H 1H 1B adhesion 4B 5B 4B solubility O O O precipitation O O O OD/μm 0.76 0.74 0.73 Thickness (㎛) 3 3 3

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Viscosity (cP) 18.7 27.5 18.3 X 23.0 X 22.4 15.8 curing sensitivity X O O O X X △ O evaporation rate X O O O O O O △ storage stability
(25℃) △ X O
X
X
X
O O pencil hardness 2B 2H 1B X X X 4B 2H adhesion 3B OB 0B X X X 3B 0B solubility O O O △ O X O O precipitation O O O X O X O O OD/μm 0.77 0.72 0.75 0.45 0.75 0.41 0.76 0.77 Thickness (㎛) 3 3 3 5 3 5 3 3

Referring to Table 5, the non-solvent type photocurable compositions prepared in Examples 1 to 3 of the present invention have appropriate viscosity, curing sensitivity, evaporation rate, storage stability, pencil hardness, adhesion, solubility and precipitation, optical It was confirmed that all of the density/thickness evaluation results were excellent.

On the other hand, referring to Table 6, in the case of Comparative Example 1, although the solvent is included in the photocurable composition, the viscosity is low, but the curing sensitivity and evaporation rate evaluation results are inferior as the solvent is included. Furthermore, storage stability and adhesion evaluation results were also inferior.

Comparative Examples 3 and 8 were very inferior in adhesion evaluation results, and Comparative Examples 2 and 4 to 6 were very inferior in pencil hardness and adhesion evaluation results. In particular, Comparative Example 5 and Comparative Example 6 were also very inferior in curing sensitivity and storage stability evaluation results.

In Comparative Example 7, when CHDMDVE was in excess of a certain amount in the ink compared to CHVE, the viscosity increased and the curing sensitivity during atmospheric curing decreased, resulting in unfavorable results in terms of surface hardness and adhesive strength.

Through this, the solvent-free photocurable composition according to an exemplary embodiment of the present invention has excellent curing sensitivity and can be easily photocured in the absence of external stabilization conditions such as nitrogen filling as an atmospheric condition, and has storage stability and dispersibility. It is excellent, and it can be seen that the optical density, hardness and adhesion of the photocured product of the non-solvent type photocurable composition are excellent.

The foregoing detailed description is intended to illustrate and explain the present invention. In addition, the foregoing merely represents and describes preferred embodiments of the present invention, and as described above, the present invention can be used in various other combinations, modifications, and environments, and the scope of the inventive concept disclosed herein, the foregoing Changes or modifications are possible within the scope equivalent to the disclosure and / or within the scope of skill or knowledge in the art. Accordingly, the above detailed description of the invention is not intended to limit the invention to the disclosed embodiments. Also, the appended claims should be construed to cover other embodiments as well.

Claims (10)

a pigment dispersion containing a pigment, a dispersant, an oxetane-based compound, an epoxy-based compound, and a vinyl ether-based compound; and
Photoinitiator; solvent-free photocurable composition containing a.
According to claim 1,
The pigment includes a black pigment,
A solvent-free photocurable composition in which the content of the pigment is 10 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the pigment dispersion.
According to claim 1,
The dispersant is a solvent-free photocurable composition comprising a urethane-based compound.
According to claim 1,
Based on 100 parts by weight of the pigment dispersion,
The content of the dispersant is a solvent-free photocurable composition of 1.5 parts by weight or more and 8.5 parts by weight or less.
According to claim 1,
Based on 100 parts by weight of the pigment dispersion,
A solvent-free photocurable composition in which the content of the oxetane-based compound is 10 parts by weight or more and 25 parts by weight or less.
According to claim 1,
Based on 100 parts by weight of the pigment dispersion,
The content of the epoxy-based compound is a solvent-free photocurable composition of 15 parts by weight or more and 30 parts by weight or less.
According to claim 1,
Based on 100 parts by weight of the pigment dispersion,
The content of the vinyl ether-based compound is a solvent-free photocurable composition of 20 parts by weight or more and 55 parts by weight or less.
According to claim 1,
The vinyl ether compound,
A first vinyl ether compound containing one vinyl ether terminal group and a second vinyl ether compound containing two or more vinyl ether terminal groups,
The weight ratio of the first vinyl ether-based compound and the second vinyl ether-based compound is 1: 1.1 to 1: 2.5 solvent-free photocurable composition.
According to claim 1,
The content of the photoinitiator is 2.5 parts by weight or more and 6.5 parts by weight or less based on 100 parts by weight of the pigment dispersion.
According to claim 1,
A non-solvent type photocurable composition further comprising an additive including at least one of a sensitizer, an adhesion promoter, a surfactant and an antioxidant.