KR20210062231A - Etching resist ink composition - Google Patents

Abstract

The present invention relates to an eco-friendly etching resist ink composition that can be peeled off by water, and specifically, to an ink composition that is selectively peeled off by water. The etching resist ink composition includes: polyvinylpyrillidone (PVP) having a weight average molecular weight of 39,000 - 1,590,000 g/mol and an inorganic filler that is barium sulfate.

Description

Etching resist ink composition TECHNICAL FIELD

The present invention relates to an eco-friendly etching resist ink composition capable of being peeled off by water.

The printed etching resist ink is generally peeled off using a strongly alkaline stripper. However, the strongly alkaline stripping solution has a limitation in that there is a concern of environmental pollution when the waste solution is discarded after stripping, and an additional waste solution treatment step is required. Patent Laid-Open Publication No. 2017-0095661 uses a stripping solution containing 20 to 30% of a strongly alkaline alkanol amine compound. In this case, when the stripping waste solution is discarded, there are still problems of harmfulness to the human body and environmental pollution. do.

In addition, Patent Publication No. 2017-0123050 describes providing an eco-friendly aqueous stripper composition containing cyclodextrin or a derivative thereof in order to solve the problem of harmfulness to the human body and environmental pollution. The liquid is used as a stripper by adding additional substances to water.

Patent Publication No. 2017-0095661 Patent Publication No. 2017-0123050

The present invention relates to an etching resist ink composition, and an object thereof is to provide an eco-friendly etching resist ink composition that is selectively peeled off by water.

The present invention relates to an etching resist ink composition comprising polyvinylpyrlidone (PVP) having a weight average molecular weight of 39,000 to 1,590,000 g/mol and an inorganic filler of barium sulfate.

The weight average molecular weight of the polyvinylpyrlidone (PVP) may be 40,000 to 80,000 g/mol.

The barium sulfate may be included in an amount of 0.1 to 60% by weight.

The barium sulfate may be included in an amount of 30 to 60% by weight.

The barium sulfate may not be surface-treated.

The etching resist ink composition may include a diluent.

The etching resist ink composition may further include at least one or more of an antifoaming agent, a leveling agent, and a dispersing agent as an additive, and at least one or more of the antifoaming agent, leveling agent, and dispersing agent may be included in an amount of 0.1 to 5% by weight.

The etching resist ink composition of the present invention is a composition that is peeled off by water.

The etching resist ink composition of the present invention is excellent in peelability by water. Further, the etching resist ink composition of the present invention does not require a strong alkaline general stripper, and can be stripped by water, thereby preventing the generation of harmful substances by a strong alkaline general stripper, and is eco-friendly.

In addition, the etching resist ink composition of the present invention has low fluidity, less bleeding, and less air bubbles on the printing surface, so it has excellent foamability and leveling properties, and thus has excellent printability.

1 shows the results of printing on a glass substrate using the etching resist ink compositions of Examples 4 to 6.
2 shows the results of printing the etching resist ink compositions of Examples 4 to 6 on a glass substrate, and peeling them _{with H 2 O at 50°C.}

The etching resist ink composition according to the present invention may include an inorganic filler such as polyvinylpyrlidone (PVP) and barium sulfate.

Next, each component of the etching resist ink composition of the present invention will be described.

[(A) Polyvinylpyrlidone (PVP)]

In one embodiment of the present invention, the weight average molecular weight of polyvinylpyrlidone (PVP) included in the etching resist ink composition may be 39,000 to 1,590,000 g/mol, preferably 40,000 to 80,000 g/mol. have. When the weight average molecular weight of polyvinylpyrlidone (PVP) is within the above range, the etching resist ink composition is suitable for screen printing and has excellent peelability by water. On the other hand, when the weight average molecular weight of polyvinylpyrlidone (PVP) is out of the above range, it may be unsuitable for screen printing, and peelability in water may be deteriorated. If the weight average molecular weight of polyvinylpyrlidone (PVP) is less than 39,000 g/mol, it may be unsuitable for screen printing, and if the weight average molecular weight of polyvinylpyrlidone (PVP) exceeds 1,590,000 g/mol, in water The peeling property of may be deteriorated.

The weight average molecular weight can be defined by test methods such as NMR spectroscopy, chromatography, light scattering measurement, and osmotic pressure measurement. The K-Value of the polyvinylpyrlidone (PVP) resin including polyvinylpyrlidone (PVP) may be 27 to 100, more preferably 27 to 33. In general, it can be calculated using the following general formula 1.

[General Formula 1]

,

,

(c = concentration of the g-concentration solution of the resin dissolved in 100 ml, n = solution viscosity/solvent viscosity)

The pH may be 3 to 10, preferably 3 to 7.

The glass transition temperature (Tg) is preferably 100 to 190°C, and more preferably 150 to 180°C.

In one embodiment of the present invention, polyvinylpyrlidone (PVP) is selected from ASHLAND's PVP K-30, K-60, K-90; Polyvynylpyrrolidone K-30, K-85, K-90, K-30W, K-85W, K-90W from NIPPON SHOKUBAI; Polyvinylpyrrolidone K 30, K 60, K 90 from Tokyo Chemical Industry; JH Nanhang Life Sciences' PVP-P Grade USP28, NF23, PVP K30, K85, K90; BASF's LUVITEC K 30, K 85, K 90, K 90HM, K 90S, K 90 CQ; It can be Boai NKY Pharmaceuticals' KoVidone K 25, K 30, K 90, VA64, XL, XL-10, etc., and can include all types of solid or solid content of each product dissolved in a liquid solvent.

[(B) Barium sulfate]

In one embodiment of the present invention, the inorganic filler included in the etching resist ink composition is barium sulfate. By including barium sulfate in the etching resist ink composition, the fluidity of the etching resist ink composition can be adjusted, bleeding is eliminated, and so on, the printability is excellent, and the peelability to water is excellent.

When barium sulfate is used as an inorganic filler with polyvinylpyrrolidone (PVP), since barium sulfate has a greater specific gravity than other inorganic fillers, it is rapidly desorbed from the surface of the substrate under water-based peeling conditions and the etching resist ink composition is peeled off. You can improve the speed.

In one embodiment of the present invention, barium sulfate, which is an inorganic filler, may be included in an amount of 0.1 to 60% by weight based on the total weight of the etching resist ink composition. Preferably, the barium sulfate may be included in an amount of 30 to 60% by weight.

When the content of barium sulfate contained in the etching resist ink composition is within the above range, the fluidity of the etching resist ink composition can be adjusted, bleeding is eliminated, and excellent printability and releasability to water can be realized. On the other hand, when the content of barium sulfate contained in the etching resist ink composition is less than 30% by weight, there is a disadvantage of spreading the coating film after printing, and when it exceeds 60% by weight, there is a disadvantage that the peelability is deteriorated due to insufficient resin content.

In one embodiment of the present invention, as barium sulfate, a commercially available product may be used, preferably barium sulfate without surface treatment, preferably having a diameter of 0.7 to 10 μm.

Barium sulfate is commonly used from those having a diameter of 0.7 µm or more, and when the diameter of barium sulphate contained in the etching resist ink composition exceeds 10 µm, printability and printing interface are deteriorated.

The average particle diameter and particle size distribution of barium sulfate can be defined by laser diffraction and scattering (measuring instrument: Mastersizer 3000, Malvern Panalytical).

In one embodiment of the present invention, barium sulfate is selected from Koch's KCB-01, KCB-02, KCB-03, KCB-07, KCB-8000, BSB-8000; Barium sulfate from Nippon-chem; SAKAI CHEMICAL INDUSTRY's BARIUM SULFATE 100, 110, 200, 270, 300, B-54, B-55; It may be Gemme Fine GM-80, BSP-L, GM-F, BSP-X of Gemme.

In one embodiment of the present invention, the barium sulfate contained in the etching resist ink composition may not be surface-treated. Examples of the surface treatment component include SiO ₂ -Al ₂ O ₃ , silicon oxide, and aluminum oxide. If barium sulfate without surface treatment is used, it is rapidly desorbed from the surface of the substrate under water-based peeling conditions, thereby improving the peeling speed of the etching resist ink.

In one embodiment of the present invention, the etch resist ink composition may include a diluent.

Although there is no restriction|limiting in particular as a diluent, For example, ketone, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbon petroleum solvents, etc. are mentioned. More specifically, ketones, such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cerosorubu, Methyl Cellosolve, Butyl Cellosolve, Carbitol, Methyl Carbitol, Butyl Carbitol, Ethylene Glycol Mono Methyl Ether, Ethylene Glycol Mono Ethyl Ether, Ethylene Glycol Mono Butyl Ether, Propylene Glycol Mono Methyl Ether, Dipropylene Glycol Glycol ethers such as monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethanol, propanol, 2-methoxy propanol, n-butanol, isobutyl alcohol, isopentyl alcohol, ethylene glycol, propylene glycol Alcohols such as; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; N,N-dimethyl formamide (DMF), tetrachloroethylene, vegetable oil, and the like.

In addition, Maruzen Petrochemical Company's Suwasol 1000, Suwasol 1500, Standard Petroleum Osaka Sales Office Company's Sorubsso 100, Sorubeso 150, Sankyo Chemical Company's Solvent #100, Solvent #150, Shell Chemical Japan Company's Shell Sol A100 , Shell Sol A150, Idemitsu Heungsan's Ipsol No. 100, Ipsol No. 150, etc. organic solvents can be used. Organic solvents may be used alone or in a mixture of two or more.

In one embodiment of the present invention, the etching resist ink composition may further include at least one or more of an antifoaming agent, a leveling agent and a dispersing agent as an additive.

If necessary, the etching resist ink composition may include a silicone-based, fluorine-based, polymer-based antifoaming agent and/or a leveling agent as an additive. All of the antifoaming agent, leveling agent, and dispersing agent may be appropriately selected and used among commercially available products by a person skilled in the art.

In one embodiment of the present invention, at least one or more of the antifoaming agent, leveling agent and dispersing agent may be contained in an amount of 0.1 to 5% by weight. When the content of at least one or more of the antifoaming agent, leveling agent, and dispersing agent contained in the etching resist ink composition is within the above range, the flowability of the etching resist ink composition can be adjusted, and the bleeding phenomenon is eliminated, and the printability is excellent. In addition, when the content of at least one of the antifoaming agent, leveling agent, and dispersing agent included in the etching resist ink composition is less than 0.1% by weight, there is a disadvantage in that the adhesion between the ink coating film and the substrate is lowered after printing, and the foamability and/or leveling property There is a downside to this deterioration. When the content of at least one of the antifoaming agent, the leveling agent and the dispersing agent is more than 5% by weight, there is a disadvantage that phase separation may occur.

The present invention is not limited by the following examples.

Experimental Example 1

The raw materials shown in Table 1 were put in a container, stirred, and visually confirmed that the filler was evenly dispersed, and then softened to three rolls to prepare an ink. The content of the raw materials listed in Table 1 below is described in units of weight %.

The ink compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were screen-printed on a glass substrate and thermally cured at 150° C. for 20 minutes, and the ink composition of Comparative Example 6 was UV 1000 mJ/cm ² photocured.

[Table 1]

PVP Resin: Polyvinylpyrlidone resin (PVP K-30, JH Nanhang Life Sciences)

* PVP content = content of polyvinylpyrlidone (PVP) in PVP resin

F-896 Resin: Phenolic resin (Hwaseong, Gangnam)

UP-039: Polyester acrylate oligomer (ENTIS)

KR-450: Rubber Modified Epoxy Resin (KUKDO)

KSR-177: High Performance Epoxy Resin (KUKDO)

BARIACE B-30 : _{BaSO 4} coated with _{SiO 2} -Al ₂ O ₃

KCB-8000: BaSO ₄ , Purity: 100%

KR-450: Rubber Modified Epoxy Resin (KUKDO)

KSR-177: High Performance Epoxy Resin (KUKDO)

KC-3000: Talc (KOCH company)

SOFTON 1800: CaCO ₃ (BIHOKU FUNKA KOGYO 社)

E+508: Sperical Silicone Resin powder (ABC Nanotech Co.)

The ink compositions of Examples 1 to 6 and Comparative Examples 1 to 6 were screen-printed on a glass substrate and then thermally cured at 150° C. for 20 minutes or UV 1000 mJ/cm ² photocured. Printability was measured by observing the degree of bleeding when printed with the naked eye and a microscope.

Thereafter, the glass substrate on which the ink was printed was immersed in a solvent for 5 minutes, and the residue remaining on the surface of the substrate was visually evaluated. The peelability was visually evaluated for the residue remaining on the surface of the glass substrate after 5 minutes dipping in 50°C H _{2 O / 70°C 3wt% NaOH, respectively.}

Evaluation Item 1: Printability

Printability was evaluated by screen printing the ink compositions of Examples 1 to 6 and Comparative Examples 1 to 6 on a glass substrate and then thermosetting at 150° C. for 20 minutes, and then the size of the bleeding area and/or the blistering property and leveling property.

XX: The bleeding area exceeds 10 μm or there are many air bubbles on the printing surface, so the rupture or leveling properties are poor.

X: The bleeding area is 5 ~ 10 μm

△: Spreading area is 2 ~ 5 μm

○: Spreading area is 2 μm or less

Evaluation Item 2: Peelability

The peelability was evaluated by immersing the ink-printed glass substrate in a solvent for 5 minutes and visually checking the residue remaining on the substrate surface.

X: No peeling

△: Residue can be checked visually

○: No residue

[Table 2]

Compared to Comparative Example 1, Examples 1 to 6 have fewer air bubbles on the printed surface, and thus have excellent foamability and leveling properties.

Compared to Comparative Examples 2 to 6, Examples 1 to 6 are superior in peelability in pure water.

As can be seen from the results of Examples 4 to 6, when the content of barium sulfate is increased, the bleeding phenomenon is reduced and the printability is also excellent.

As can be seen from the results of Examples 1 to 3 and Examples 4 to 6, when barium sulfate without surface treatment was used as the inorganic filler, the bleeding phenomenon was reduced compared to using barium sulfate treated with the surface, and thus printability. This is excellent, and the peelability in pure water is excellent.

Experimental Example 2

An ink was prepared in the same manner as in Experimental Example 1, except that the raw materials shown in Table 3 were used. The content of the raw materials listed in Table 3 below was described in units of weight %.

[Table 3]

PVP K-15: Weight average molecular weight 6,000-15,000 g/mol

PVP K-30: Weight average molecular weight 40,000-80,000 g/mol

PVP K-60: Weight average molecular weight 240,000-450,000 g/mol

PVP K-90: Weight average molecular weight 900,000-1,500,000 g/mol

* PVP content = content of polyvinylpyrlidone (PVP) in PVP resin

After screen printing of the ink compositions of Examples 7 to 9 and Comparative Example 7 on a glass substrate, heat curing was performed at 150° C. for 20 minutes. Thereafter, the ink-printed glass substrate was immersed in a solvent for 5 minutes, and the residue remaining on the substrate surface was visually evaluated.

Evaluation Item 1: Printability

Printability was evaluated by screen printing the ink compositions of Examples 7 to 9 and Comparative Example 7 on a glass substrate, followed by thermal curing at 150° C. for 20 minutes, and then the size of the smeared area.

XX: The bleeding area exceeds 10 μm or there are many air bubbles on the printing surface, so the rupture or leveling properties are poor.

X: The bleeding area is 5 ~ 10 μm

△: Spreading area is 2 ~ 5 μm

○: Spreading area is 2 μm or less

Evaluation Item 2: Peelability

The peelability was evaluated by immersing the ink-printed glass substrate in a solvent for 5 minutes, and visually checking the residue remaining on the substrate surface.

X: No peeling

△: Residue can be checked visually

○: No residue

[Table 4]

Examples 7 to 9 exhibit less bleeding and fewer air bubbles on the printed surface, so that the foaming and leveling properties are excellent, so that the printability is excellent, and the peelability in pure water is excellent.

Among the examples, the foamability, leveling property, printability, and peelability in pure water of Example 7 are very excellent.

On the other hand, Comparative Example 7 has many air bubbles on the printed surface, so that the foamability and leveling properties are poor.

Claims (8)

A weight average molecular weight of 39,000-1,590,000 g/mol of polyvinylpyrlidone (PVP) and an inorganic filler of barium sulfate. The etching resist ink composition according to claim 1, wherein the weight average molecular weight of polyvinylpyrlidone (PVP) is 40,000 to 80,000 g/mol. The etching resist ink composition according to claim 1, comprising 0.1 to 60% by weight of barium sulfate. The etching resist ink composition according to claim 1, comprising 30 to 60% by weight of barium sulfate. The etching resist ink composition according to claim 1, wherein the barium sulfate is not surface-treated. The etching resist ink composition according to claim 1, further comprising at least one or more of an antifoaming agent, a leveling agent, and a dispersing agent. The etching resist ink composition according to claim 6, comprising 0.1 to 5% by weight of at least one of an antifoaming agent, a leveling agent, and a dispersing agent. The etching resist ink composition according to any one of claims 1 to 7, which is peeled off by water.

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