KR102087921B1 - Photo-lithography color ink - Google Patents

Abstract

The present invention relates to a photolithography color ink, comprising: an optical binder in the range of 16.0 to 31.0 wt%; Photoinitiators in the range of 7.5-15.2 wt%; Combined monomers and oligomers in the range of 10.0 to 19.5 wt%; Additives ranging from 0.9 to 1.8 wt%; And a thermosetting ink in the range of 35.0 to 65.6 wt%, wherein the additive is a saturated or unsaturated fatty acid having a carboxyl group and composed of 12 to 24 even dogs.
According to the present invention, the thermosetting ink and the photosensitive portion are included together, whereby the pattern formation by the exposure-development process and the reliability and color implementability of the thermosetting ink can be simultaneously obtained.
In addition, in the present invention, due to the pattern formation by photolithography, since there is very little error in the alignment of fine holes, it is possible to perform printing on several sheets in one printing process, resulting in higher process efficiency and reduced process cost. It is effective.
In particular, the photolithographic color ink of the present invention is characterized by providing a new ink composition capable of precise printing by imparting photosensitive characteristics capable of photolithography without significantly changing the composition of a conventional thermosetting ink composition. have.

Description

Photolithography color ink {PHOTO-LITHOGRAPHY COLOR INK}

The present invention relates to color inks, and more particularly, to color inks that can be printed in an accurate position and shape.

Recently, various kinds of mobile and IT devices (cellular phones, PDAs, PMPs, notebooks, touch screens, etc.) are used a lot.

Such mobile and IT devices are provided with a display window, and a window made of high strength glass or transparent resin is positioned outside the display window to protect the display window. Such a window is generally made larger than the display window, and the printing is performed in the periphery except for the space where the display window is located, thereby decorating the exterior in various colors or displaying a trademark or a logo.

Since the printing on the inner surface of the window is performed in a form except for the inside of the display window, a method of hardening by heating after performing screen printing using a thermosetting ink is mainly used. However, recent mobile and IT devices need to be opened for camera lenses, sensors, and speakers in addition to display windows, and thermosetting inks should not be printed in these open positions. At this time, holes (camera hole, sensor hole, speaker hole, etc.), which are open spaces for the camera lens, the sensor, and the speaker, should be formed in a relatively small size, but due to the nature of screen printing, jig tolerances and printing tolerances are generated. Aligning in the right place is not easy. Therefore, the current screen printing process using the thermosetting ink is performed only one print at a time for precise control, which causes a high manufacturing cost. In addition, the jig is used to implement several to several tens of prints once, and the jig tolerance is added as well as the printing tolerance, making it difficult to proceed with a precise screen printing process.

Patent Publication 10-2016-0124449

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a new kind of printing ink capable of printing a plurality of windows at a time.

Photolithographic color ink according to the present invention for achieving the above object is an optical binder in the range of 16.0 to 31.0 wt%; Photoinitiators in the range of 7.5-15.2 wt%; Combined monomers and oligomers in the range of 10.0 to 19.5 wt%; Additives ranging from 0.9 to 1.8 wt%; And 35.0 to 65.6 wt% of a thermosetting ink, wherein the thermosetting ink comprises at least one selected from pigments, epoxies, acrylics, and urethanes; At least one solvent selected from IPR (Isophorone) and BC (Butyl cabitol), the additive is characterized in that the carboxyl group is a saturated or unsaturated fatty acid composed of 12 to 24 even dogs.

Conventional photo-curable or UV-curable paints use the property of being cured by light, but are not a technique for selectively printing in a desired form through an exposure process using a mask or the like. On the other hand, the photolithography process using a photoresist is a technique of forming a pattern through an exposure process using a mask, but it cannot be applied as a printing ink capable of incorporating color into itself.

The conventional photoresist can be applied only to pattern printing and not to color printing, but in order to impart color to the photoresist, a material such as a pigment must be added, but materials other than the photoresist material can be added for curing. This is because the absorption and the development process are not performed in an accurate pattern due to the absorption of light.

Therefore, in the past, the present invention was applied to use a photosensitive resin to form a three-dimensional pattern, but not for the purpose of color printing.

The photolithography color ink of the present invention can selectively print only necessary portions by an exposure process using a mask like photolithography, and can also perform color printing that displays colors by itself.

In particular, the photolithographic color ink of the present invention has a great feature in providing a new ink composition capable of precise printing by imparting photosensitive characteristics that photolithography is possible without making a large change in the composition of a conventional thermosetting ink composition. have.

The optical binder is preferably one of an acrylic binder, cellulose and an epoxy acrylate.

It is preferable that a monomer is an acryl-type monomer or a urethane-type monomer of the 3-6 functional group range.

It is preferable that an oligomer is a urethane type oligomer or an epoxy type oligomer of 4-6 functional group range.

Photoinitiator is preferably at least one selected from α-Hydroxyketone, Phenylglyoxylate, α-Aminoketone, Mono Acyl Phosphine (MAPO) and oxime system.

It may further include a wax or a surface tension increasing agent, further comprising a dispersant having an amine and an acid group.

It may further include an antifoaming agent, or may further include SiO ₂ or TiO ₂ .

Thermosetting inks include pigments; Thermosetting resins at least one selected from epoxy, acrylic and urethane; Thermosetting agents which are block isocyanates or latent curing agents; And a solvent that is one or more selected from DBE, IPR, and BC.

According to another aspect of the present invention, a color printing method for a back side of a window is performed by using the photolithography color ink described above and performing a process of forming a pattern by performing an exposure process and a developing process to form holes formed in the window. It is characterized by.

The present invention configured as described above includes the thermosetting ink and the photosensitive portion together, whereby the pattern formation by the exposure-development process and the reliability and color implementability of the thermosetting ink can be simultaneously obtained.

In addition, in the present invention, due to the pattern formation by photolithography, since there is very little error in the alignment of the fine holes, it is possible to perform printing on several sheets in one printing process, resulting in higher process efficiency and reduced process cost. It is effective.

1 is a flowchart illustrating a printing process using a photoresist color ink according to an embodiment of the present invention.
2 is a flowchart showing a printing process using a conventional thermosetting ink.

With reference to the accompanying drawings will be described embodiments of the present invention;

The photolithographic color inks according to the invention are optical binders ranging from 16 to 31 wt%, photoinitiators ranging from 7.5 to 15.2 wt%, monomers and oligomers ranging from 10 to 19.5 wt%, additives ranging from 0.9 to 1.75 wt%, and Thermosetting inks in the range of 35 to 65.6 wt%.

At this time, the additive is a saturated or unsaturated fatty acid having a carboxyl group and composed of 12 to 24 even number.

Photolithography of the present invention can be largely divided into a photosensitive portion for giving photosensitivity and a thermosetting ink for giving a raw material, and the photosensitive portion includes an optical binder, a photoinitiator, a monomer and an oligomer, and an additive.

The optical binder is made of acryl binder, cellulose and epoxy acrylate, and has an acid group at its end. When there is a double bond, the binder may also participate in crosslinking between the photoinitiator and the monomer to increase the degree of photocuring. Molecular weight is applied at 2000 ~ 200,000mw level and it affects the sensitivity of photoresist (PR) depending on molecular weight. In detail, when using less than 2000mw at 5000 ~ 600,000mw, the photocurability is low due to the low molecular weight, so that pattern formation is disadvantageous or color dispersion is not good. If it is 200,000mw or more, the viscosity becomes high, and ink manufacture and printability are bad, and when it develops, it falls in the form of a film (lump) and does not obtain a good pattern. Viscosity requires a viscosity of 2000 ~ 10000cp in order to apply to screen printing, which may vary depending on the solid content or molecular weight in the binder synthesis, 5000-8000cp is suitable. The T _g of the resin is changed according to the drying temperature. The higher the T _g , the better the drying characteristics (solvent volatile).

T _g is preferably 30 to 130 ° C, and specifically 80 to 110 ° C. If T _g is low, it is difficult to repeat printing due to tack property, trapped during drying, solvent remains, so proper exposure is difficult due to the change of refractive index of residual solvent during post-processing, exposure, and development speed is increased during development, and pattern dropout may occur. And pattern sharpness is poor.

When perl is applied in the composition of the photoresist color ink, acrylic or cellulose-based resins are suitable for expressing the particle feeling or the mirror feeling (metal pearl_ex: Al). The series above affects the arrangement of pearls due to the structure and printability of the polymer.

The monomer is preferably an acryl-based monomer or a urethane-based monomer having a level of 3 to 6 functional groups. When using less than 2 functional groups, the reactivity is slow, and when more than 7 functional groups are used, it may affect residue after developing process. The selection of the monomer varies depending on the type of the optical binder. For example, the acrylic polymer has excellent matching with acryl and urethane, but the cellulose polymer has good matching with the urethane monomer. When the cellulose polymer and the acrylic monomer are combined, the hydrogen bond affects the stability.

The oligomer is urethane-based, epoxy-based, etc., 4 to 6 functional group level is suitable. At six or more functional groups, developing residues occur and the developing speed is slowed, and at four or less functional groups, the sensitivity is lowered to increase the exposure amount. Although the reaction rate is slower than that of the monomers, it participates in the crosslinking in a wider form and affects the strength of the material and the shape of the pattern. In addition, by increasing the process margin in the development process to suppress the occurrence of surface damage during alkali etching. In particular, if the thermosetting ink is used in a composition to which the monomer is used, wrinkles may be generated because the monomer does not withstand the shrinkage occurring in the photocuring process, but this problem may be solved by using an oligomer together.

The photoresist color ink of the present invention has excellent efficiency of suppressing the occurrence of surface wrinkles after the exposure or development process when the ratio of monomers to oligomers is about 1: 1, and the surface wrinkles when the monomer ratio exceeds 60% of the oligomers. This may occur. The input amount of monomer and oligomer can be applied up to 30 ~ 70% compared to the photosensitive binder, and it is easy to develop by controlling the dry state of the coated coating film by using the property of not drying and curing at low temperature due to the characteristics of the raw material itself.

Photo-initiators are used α-Hydroxyketone, Phenylglyoxylate, α-Aminoketone, Mono Acyl Phosphine (MAPO), oxime type, etc., and can be changed depending on the color of the ink to be implemented according to the absorption wavelength. For example, in the case of producing black ink, since light transmittance is small, short wavelength initiators are mainly used, and a sensitizer is applied simultaneously. In the case of white color, short wavelength and long wavelength initiators are used at the same time, but the sensitivity of the desired material can be adjusted by adjusting the initiator content. And when applied to yellowing or color-sensitive inks, the color and content of the initiator should be adjusted.

The additive uses saturated or unsaturated fatty acids having carboxyl groups and consisting of 12 to 24 even numbers. The number of double bonds with 18 or less carbon atoms is less than 3, and it exists between the materials in the mixture state and lowers the bonding degree between materials, resulting in easier alkali etching in the developing process. Such additives are the main elements that exhibit the effect that the photolithographic color ink of the present invention can be cured except for a camera hole through an exposure process.

In addition, performance can be improved by further including a dispersant having an amine and an acid group in the photosensitive portion of the photolithographic color ink according to the present invention. Such dispersants have wettability due to dispersing force due to electrostatic repulsion by charge and steric hindrance due to the adsorption layer, and increase the rate of wetting during mixing or dispersing between the thermosetting ink and the photosensitive portion. In particular, the wettability enables development by adsorbing a photosensitive element, which is photosensitive or developed in pigments and thermosetting resins, onto the surface and improves residue (local phenomenon). Acid groups affect developability, and amines participate in the reaction as a curing agent in the present drying (thermosetting). As the amine and the acid value, a raw material containing 10 to 100 mg KOH / g may be applied.

By adding a wax or surface tension increasing agent to the photosensitive portion to impart slip properties, the phenomenon of sticking with the plate during the printing process can be improved.

In addition, by adding an antifoaming agent it can remove bubbles generated while passing through the plate during printing.

Furthermore, by adding SiO ₂ or TiO ₂ additionally, scattering due to the inherent refractive index and particle size helps the light move during exposure, so that the sensitivity of the photosensitive portion when applied to black color with strong absorption of light is increased. Can be improved.

And fumed silica can be used as a thickener and used for the purpose of controlling the gloss of the photoresist color ink surface.

Thermosetting inks can be used without any great limitation to the various thermosetting inks currently used. Like a general thermosetting ink, it is composed of a pigment for imparting color, a thermosetting resin, a thermosetting agent and a solvent.

Epoxy, acrylic, urethane, etc. are used for thermosetting resin, and resin type can be selected according to the kind of base material or the purpose of an ink. In particular, in the case of reliability items such as heat desorption, epoxy resins having a low thermal shrinkage rate are applied, and thermosetting resins can be selected according to printability (surface characteristics).

Thermosetting agents cure thermosetting polymers using block isocyanates or latent curing agents in consideration of the stability and workability of the material. Different types of curing agents should be selected depending on the type of thermosetting resin, and curing agents with different dissociation temperatures should be used depending on the drying process.

In the case of the solvent, DBE, IPR, BC, etc. are applied according to the color or workability of the thermosetting ink, and the solvent having low volatility is excluded due to the characteristics of screen printing.

Next, look at the characteristics of the photolithography color ink according to the present invention.

Table 1 shows the results of experiments on the pattern formation characteristics and the color implementation characteristics according to the ratio of the photosensitive portion and the thermosetting ink.

The photosensitive portion was composed of a ratio of 46.05 wt% of an optical binder, 22.37 wt% of a photoinitiator, 28.95 wt% of a monomer and an oligomer, and 2.63 wt% of an additive. The composition ratio represents "photosensitive part: thermosetting ink."

Composition ratio Pattern formation characteristics Color implementation characteristics 20:80 No pattern formation Excellent color implementation 30:70 Pattern is formed but residues occur Excellent color implementation 40:60 Good pattern formation Excellent color implementation 50:50 Good pattern formation Excellent color implementation 60:40 Good pattern formation Excellent color implementation 65:35 Good pattern formation Excellent color implementation 70:30 Good pattern formation Color fades and hides less 80:20 Good pattern formation Color fades and hides less 90:10 Good pattern formation Color fades and hides less

When the content of the thermosetting ink is more than 35wt%, color implementation was excellent, but in the range where the content of the photosensitive portion was 30wt% or less, no pattern was formed or residues occurred even when the pattern was formed.

On the other hand, when the content of the photosensitive portion is more than 40wt%, the pattern was formed well, but in the range of the content of the thermosetting ink is 30wt% or less, it was confirmed that the color was light and the hiding power was difficult to use. In particular, when the thermosetting ink is 10wt% or less, reliability in terms of adhesive force, hot water resistance, and coating film strength is low.

Through these results, it can be seen that the content of the thermosetting ink should be controlled in the range of 35 to 65.6 wt%.

Using the photoresist color ink according to an embodiment of the present invention was performed a printing process for the back of the window of mobile and IT devices.

1 is a flowchart illustrating a printing process using a photoresist color ink according to an embodiment of the present invention.

Silkscreen printing was performed using a 350-neck screen net, and drying was carried out for 10 minutes at a temperature of 70 ° C. in an IR oven. The photoresist color ink according to the embodiment of the present invention was used for the color printing and the shielding printing, and the exposure process was performed with an intensity of 50 to 1000mj / cm ² except for the positions where the holes were formed, and the developing process was 0.1 The location where holes are to be formed is opened by performing with ˜1.0% Na ₂ CO ₃ . The drying was carried out in an IR oven at a temperature of 170 ° C. for 30 minutes.

In the illustrated embodiment, two silkscreen color printings are performed, but the present invention is not limited thereto and may be performed only once or three or more times. In addition, after performing the color printing and the shielding printing, the exposure-development process was performed for each, but only one exposure-development process may be performed if the color layer and the printed layer have the same shape and dimensions.

2 is a flowchart showing a printing process using a conventional thermosetting ink.

Silkscreen printing conditions and temporary drying and the conditions of the present drying are the same as in the case of the present invention described above. However, in case of screen printing thermosetting ink, only one sheet should be printed at a time in order to align holes (camera hole, sensor hole, speaker hole, etc.) by jig tolerance and printing tolerance due to the characteristics of screen printing.

On the other hand, in the case of using the photoresist color ink of the present invention according to FIG. 1, since the alignment of the holes (camera hole, sensor hole, speaker hole, etc.) is performed very accurately, printing for 6 to 8 sheets at a time Can be performed. As a result, although the exposure-developing process is added, there is an excellent effect that the speed and efficiency of the entire process are greatly improved and the defect rate is also reduced.

Table 2 shows the experimental results for the photoresist color ink according to the embodiment of the present invention and the ink of the comparative example.

Example Comparative example One 2 3 One 2 3


Photosensitivity
part Optical binder CBPR-4096C 20.7% 25.3% 29.9% - 13.8% 36.8%
Photoinitiator DETX 3.0% 2.0% 2.5% - 0.4% 1.1% IGR-184 3.0% 3.0% - 1.6% 4.2% OXE-01 7.1% 3.3% - 1.6% 4.2% IGR-819 7.3% 5.7% - 3.2% 8.4% Monomer PETIA 4.3% 6.4% - 4.3% 11.5% DPHA 5.0% 8.0% 3.1% Oligomer PU640 3.7% 8.0% 9.4% - 4.3% 11.6% additive BYK-180 1.2% 1.4% 1.7% - 0.8% 2.1% Thermosetting
ink Suzy KDN-253 25.3% 20.7% 16.1% 55.0% 32.2% 4.6% Thermosetting agent BI-180 2.5% 2.1% 1.6% 5.5% 3.2% 0.5% menstruum DBE 12.2% 7.2% 2.3% 24.5% 19.6% 0.0% Pigment carbon powder 15.0% 15.0% 15.0% 15.0% 15.0% 15.0%
Print results Pattern formation Good Good Good - Unformed Good Pattern sharpness Good Good Good - Bad Good responsibility Good Good Good Good Good Bad Color implementation Good Good Good Good Good Bad Camera hole, sensor hole alignment error ± 0.5㎛ ± 0.5㎛ ± 0.5㎛ ± 80㎛ Measure × ± 0.5㎛

CBPR-4096C: Chembase's acrylic binder, DETX: BASF's photoinitiator, OXE-01: BASF's photoinitiator, IGR-184: BASF's photoinitiator (Irgacure ^® -184), IGR-819: BASF's Abbreviation for photoinitiator (Irgacure ^®- 819), PU640: 6 functional oligomer of Miwon SC, BYK-180: product of BYK, KDN-253: modified epoxy binder of Kukdo Chemical, PETIA: pentaerythritol triacrylate, DPHA: Dipentaerythritol Hexaacrylate, BI-180: Blocked Isocyanate Products

Examples 1 to 3 correspond to 45%, 55% and 65% of the content of the photosensitive portion derived based on Table 1, respectively, and Comparative Example 1 is a conventional thermosetting ink. Comparative Examples 2 and 3 are cases where the content of the photosensitive portion is 30% and 80%, respectively.

Examples 1 to 3 and Comparative Examples 2 to 3 performed the printing process in the order of FIG. 1, and the thermosetting ink of Comparative Example 1 was printed in the order of FIG. 2.

In the case where six simultaneous printings were performed using a jig using a photoresist color ink according to an embodiment of the present invention, the pattern for the camera hole and the sensor hole was well formed by the exposure-development, and the pattern sharpness ( sharpness) is also good, and it can be seen that photolithography by the photosensitive portion was performed well. In addition, the reliability and color implementation are also good, it can be seen that the properties of the thermosetting ink also exhibited good.

On the other hand, in the case of Comparative Example 2, the content of the photosensitive portion was so small that no photolithography was performed, so that no pattern was formed, and only the reliability and color implementation according to the characteristics of the thermosetting ink were good. In the case of Comparative Example 3, photolithography was performed due to the high content of the photosensitive portion, but there was a problem in reliability, such as disadvantages in heat-resistant hot water and cross-cut (adhesive force) experiments due to the low amount of thermosetting ink. There is also a low problem.

On the other hand, silk screen printing using the thermosetting ink of Comparative Example 1 has good reliability and color implementation, but the alignment error between the camera hole and the sensor hole occurs at a level of ± 80 μm, so that the camera hole and the sensor hole can be accurately aligned. The process must be carried out precisely in chapters.

In the case of using the photolithography color ink according to the embodiment of the present invention, the alignment error between the camera hole and the sensor hole is only ± 0.5 μm, and printing is performed on several sheets (for example, 6 to 8 sheets) at one time. Even if the hole alignment does not occur.

While the present invention has been described through the preferred embodiments, the above-described embodiments are merely illustrative of the technical idea of the present invention, and various changes may be made without departing from the technical idea of the present invention. Those of ordinary skill will understand. Therefore, the protection scope of the present invention should be interpreted not by the specific embodiments, but by the matters described in the claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (12)

Color ink that performs color printing on the back of the window of the display window,
Optical binder in the range of 16.0 to 31.0 wt%;
Photoinitiators in the range of 7.5-15.2 wt%;
Combined monomers and oligomers in the range of 10.0 to 19.5 wt%;
Additives ranging from 0.9 to 1.8 wt%; And
Includes a thermosetting ink in the range of 35.0 to 65.6 wt%,
The thermosetting ink is a thermosetting resin which is at least one selected from pigments, epoxy, acrylic and urethane, a thermosetting agent which is a block isocyanate or a latent curing agent, and a solvent which is at least one selected from DBE (Di Basic Ester), IPE (Isophorone) and BC (Butyl cabitol). Including,
The monomer is an acrylic monomer in the range of 3 to 6 functional groups, the oligomer is a urethane oligomer in the range of 4 to 6 functional groups,
The additive is a photolithographic color ink, characterized in that a saturated or unsaturated fatty acid having a carboxyl group and composed of an even number of 12 to 24 carbon atoms.
The method according to claim 1,
And the optical binder is one of an acrylic binder, cellulose and an epoxy acrylate.
delete delete The method according to claim 1,
The photoinitiator is a photolithography color ink, characterized in that at least one selected from α-Hydroxyketone, Phenylglyoxylate, α-Aminoketone, Mono Acyl Phosphine (MAPO) and oxime system.
The method according to claim 1,
A photolithographic color ink, further comprising a dispersant having an amine and an acid group.
The method according to claim 1,
A photolithographic color ink, further comprising a wax or a surface tension increasing agent.
The method according to claim 1,
A photolithographic color ink, further comprising an antifoaming agent.
The method according to claim 1,
A photolithographic color ink further comprising SiO ₂ or TiO ₂ .
The method according to claim 1,
A photolithographic color ink further comprising fumed silica.
delete As a method of color printing on the back of the window,
Using the photolithography color ink of claim 1, in order to form a hole formed in the window, a process of forming a pattern by performing an exposure process and a developing process, characterized in that to perform a process for forming a pattern on the back side of the window.

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