KR101766210B1 - Cleaning solution composition for offset-printing cliche - Google Patents

Abstract

More particularly, the present invention relates to an offset printing offset cleaning liquid composition comprising: 1 to 20% by weight of an alkali metal hydroxide; 0.1 to 10% by weight of quaternary ammonium compound; 0.5 to 30% by weight of a water-soluble polar solvent; It is possible to simultaneously remove the solidified ink remaining in the intaglio plate, that is, both the ink for RGB and the ink for RGB, uniformly and at a high speed, without damaging the intaglio plate in which the fine pattern is formed, To an offset printing plate precursor cleaning liquid composition capable of securing reproducibility and improving process yield and productivity.

Description

TECHNICAL FIELD [0001] The present invention relates to a cleaning solution composition for offset printing,

The present invention relates to an offset printing plate precursor cleaning composition capable of rapidly removing solidified ink remaining on an intaglio after offset printing.

In the offset printing method, ink is filled in an intaglio plate on which a pattern to be printed is formed, the filled ink is transferred to a cylindrical blanket in a pattern shape, and then the blanket is rotated on the printed body to transfer So that the printed pattern is printed.

Such an offset printing method is advantageous in that it can precisely print fine patterns having a size of several tens to several hundreds of microns at a low cost without generating harmful waste liquid, and has become a technology capable of replacing the photolithography process.

Of the offset printing methods, the intaglio offset printing method has been studied as a technique suitable for forming a fine pattern for wiring which is easy to form a fine pattern having a line width of 200 mu m or less and a relatively high height and is required to have high electrical conductivity.

In the intaglio offset printing method, ink is filled in an engraved part of an intaglio plate engraved with a pattern to be printed on a flat surface of a base material, the transferred ink is transferred to a blanket, and then re-transferred to the blanket . The shape of the fine pattern formed by the intaglio offset printing method is easily influenced by the fluidity of the ink, the pressure applied to the intaglio plate, or the like. When the ink filled in the intaglio plate is not transferred to the blanket, it is deformed. This is disadvantageous in that it is difficult to ensure the reproducibility of the fine pattern.

To solve this problem, a method has been proposed in which residual ink is removed by regularly washing the intaglio plate once or several times after intaglio offset printing. However, the solidified ink is difficult to remove in a short period of time, and the removal rate of the ink is slower than the intaglio offset printing speed, which may cause a decrease in productivity.

Not only the removal rates of the inks for the black matrix (BM) and the algae ratio (RGB) are different, but also the rates at which the red (R), green (G) and blue (B) inks are removed from the intaglio. Therefore, when applying a conventional resist stripping liquid or cleaning liquid to clean the intaglio plate, it is difficult to simultaneously remove each color of the ink, and the problem is that the ink dissolved by cleaning remains on the intaglio plate surface and is reabsorbed Lt; / RTI >

An object of the present invention is to provide an offset printing plate cleaning liquid composition capable of rapidly removing not only BM remaining on the intaglio plate having a fine pattern but also solidified ink for RGB at high speed.

1. 1 to 20% by weight alkali metal hydroxide; 0.1 to 10% by weight of quaternary ammonium compound; 0.5 to 30% by weight of a water-soluble polar solvent; And a remaining amount of water.

2. The composition of claim 1, wherein 1 to 10% by weight of an alkali metal hydroxide; 0.1 to 5% by weight of quaternary ammonium compound; 1 to 20% by weight of a water-soluble polar solvent; And a remaining amount of water.

3. The offset pressure-sensitive adhesive patch cleaning composition according to 1 above, wherein the alkali metal hydroxide is at least one selected from the group consisting of lithium hydroxide, sodium hydroxide and potassium hydroxide.

4. The offset printing plate precursor cleaning composition according to 1 above, wherein the quaternary ammonium compound is a compound represented by the following formula (1)

(Wherein R ₁ to R ₄ are independently a hydrogen atom, a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group).

5. The composition of claim 4, wherein the compound represented by formula (1) is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltripropylammonium hydroxide , (1-hydroxypropyl) trimethylammonium hydroxide, trimethylethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide and (1-hydroxypropyl) trimethylammonium hydroxide.

6. The water-soluble polar solvent as described in 1 above, wherein the water-soluble polar solvent is selected from the group consisting of ether compounds, alcohol compounds, pyrrolidone compounds, amide compounds, imidazolidinone compounds, lactone compounds, sulfoxide compounds, phosphate compounds, A compound and a cresol-based compound.

The offset printing plate cleaning liquid composition according to the present invention can remove the solidified ink remaining on the intaglio plate at a high speed without damaging the intaglio plate having the fine pattern formed thereon so that the reproducibility of the printing pattern can be ensured, The yield and productivity can be improved.

Further, the cleaning liquid composition of the present invention can simultaneously remove both the BM and the RGB inks uniformly and at a high speed, and removes ink by lift-off rather than dissolution, So that it is possible to prevent the intaglio plate from being re-contaminated.

1 is an optical microscope photograph of an offset printing intaglio plate having a fine pattern formed thereon,
2 is an optical microscope photograph of a specimen (BM) cleaned for 60 seconds using the cleaning composition according to Example 1 of the present invention,
3 is an optical microscope photograph of a specimen (BM) cleaned for 60 seconds using the cleaning composition according to Comparative Example 3. Fig.

The present invention relates to an offset printing plate precursor cleaning composition capable of rapidly removing solidified ink remaining on an intaglio after offset printing.

Hereinafter, the present invention will be described in detail.

The offset printing offset cleaning composition of the present invention comprises 1 to 20% by weight of an alkali metal hydroxide; 0.1 to 10% by weight of quaternary ammonium compound; 0.5 to 30% by weight of a water-soluble polar solvent; And water in a remaining amount.

The alkali metal hydroxide is a component for desorbing the residual ink from the surface of the intaglio plate by penetrating the interface between the intaglio plate in which the fine pattern is formed and the ink remaining in the intaglio plate.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide and potassium hydroxide. These alkali metal hydroxides may be used alone or in admixture of two or more.

The alkali metal hydroxide is preferably contained in an amount of from 1 to 20% by weight, more preferably from 1 to 10% by weight, based on 100% by weight of the total amount of the offset printing plate precursor cleaning composition. When the content is less than 1% by weight, the ability to penetrate between the intaglio plate and the residual ink is lowered to deteriorate the ink removing ability. If the content is more than 20% by weight, alkali metal may be precipitated during the cleaning process to cause secondary contamination. Layer separation may occur during long-term storage.

The quaternary ammonium compound penetrates the interface between the intaglio plate and the residual ink together with the alkali metal hydroxide to promote the weakening of the adhesion between the intaglio and the ink so that not only the BM using different resins but also all the inks for RGB can be detached It is an ingredient.

Examples of the quaternary ammonium compound include compounds represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

(Wherein R ₁ to R ₄ are independently a hydrogen atom, a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group).

The compound represented by the general formula (1) has a solubility in the form of a salt in a water-soluble solvent, and is more advantageous in achieving the effect of the present invention. Specific examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltripropylammonium hydroxide, trimethylethylammonium hydroxide, (2 -Hydroxyethyl) tripropylammonium hydroxide, and (1-hydroxypropyl) trimethylammonium hydroxide. These may be used alone or in admixture of two or more. Of these, tetramethylammonium hydroxide is more preferable.

The quaternary ammonium compound is preferably contained in an amount of 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on 100% by weight of the total amount of the offset printing plate precursor cleaning composition. When the content is less than 0.1% by weight, the ability to penetrate between the intaglio and the residual ink is lowered and the ink removing ability may be lowered. If the content is more than 10% by weight, further improvement effect is not obtained.

The water-soluble polar solvent is not particularly limited as long as it is a component that helps dissolve the ink remaining on the intaglio plate and is miscible with other components contained in the offset printing separator cleaning liquid composition and water, Any polar solvent may be used.

Examples of the protonic polar solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether , Diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; And alcoholic compounds such as propanol, butanol, isopropanol, and tetrahydroperfuryl alcohol. Examples of aprotic polar solvents include pyrrolidone compounds such as N-methylpyrrolidone and N-ethylpyrrolidone; Amide compounds such as N-methylformamide and N, N-dimethylformamide; Imidazolidinone compounds such as 1,3-dimethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone; lactone-based compounds such as? -butyrolactone; Sulfoxide compounds such as dimethyl sulfoxide and sulfolane; Phosphate-based compounds such as triethyl phosphate, tributyl phosphate and the like; Carbonate-based compounds such as dimethyl carbonate and ethylene carbonate; cresol compounds such as 慣 -cresol, m-cresol and ρ-cresol, and the like. These may be used alone or in combination of two or more.

The water-soluble polar solvent is preferably contained in an amount of 0.5 to 30% by weight, more preferably 1 to 20% by weight, based on 100% by weight of the total amount of the offset printing plate precursor cleaning composition. If the content is less than 0.5% by weight, the ability to remove not only ink remaining on the intaglio plate but also organic matters on the intaglio surface generated during the process may be deteriorated. If the content exceeds 30% by weight, the resin component contained in the residual ink may be partially dissolved And the molten resin is reabsorbed on the intaglio plate surface, so that the remnant plate can be re-contaminated without being completely removed even after the cleaning is completed.

The kind of water is not particularly limited, but it is preferably deionized distilled water. More preferably, it is deionized distilled water for semiconductor processing and has a resistivity value of 18 M OMEGA. / Cm or more.

Water may be included as the balance except for the content of other components contained in the offset printing offset cleaning liquid composition, and preferably 65 wt% or more, more preferably 65 to 95 wt% or less, in consideration of re- %.

The offset printing plate cleaning liquid composition of the present invention containing such components can simultaneously remove both ink for RGB and ink for RGB remaining in the intaglio plate uniformly and at a high speed. Particularly, it is possible to rapidly remove the solidified ink without any damage to the intaglio plate by desorbing and removing the ink other than dissolving the ink, and when the dissolved ink does not dissolve the ink, Can be prevented. This makes it possible to ensure the reproducibility of the print pattern and improve the process yield and productivity.

The offset printing plate precursor cleaning composition of the present invention can be produced by a conventional method, and the method of using the cleaning composition of the present invention is also not limited.

As a method for cleaning the offset printing intaglio plate using the cleaning liquid composition of the present invention, for example, there are a method of directly dipping the intaglio plate containing the ink remaining in the formed fine pattern into the cleaning liquid composition, a method of spraying the cleaning liquid composition onto the intaglio plate, And a method of brushing after applying the cleaning liquid composition, and these methods may be used in combination. Further, bubbles or ultrasonic waves may be applied to enhance the cleaning effect.

The conditions of use (temperature, time, etc.) of the cleaning liquid composition are not particularly limited. Specifically, it can be selected appropriately according to the content and concentration of the ink remaining on the intaglio plate, and it is preferably carried out within a temperature and time range such that the resin contained in the ink remaining on the intaglio can not be dissolved and can be easily desorbed . for example, 20 to 45 < 0 > C for 15 seconds to 3 minutes.

After the intaglio plate is treated with the cleaning liquid composition of the present invention, a step of rinsing with water or an alcohol-based solvent may be further performed if necessary.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example

Example 1

5 wt% of potassium hydroxide, 2 wt% of tetramethylammonium hydroxide (TMAH), 15 wt% of diethylene glycol monobutyl ether (BDG), and 78 wt% of deionized distilled water for semiconductor processing were mixed and stirred to prepare offset printing An intaglio washing liquid composition was prepared.

Examples 2-11 and 1-4

The cleaning liquid composition was prepared in the same manner as in Example 1 except that the components and the contents as shown in Table 1 below were used. Here, the content represents weight%.

division Alkali metal hydroxide Quaternary ammonium
compound Water soluble polar solvent water KOH NaOH TMAH TEAH BDG THFA NMP Example 1 5 - 2 - 15 - - 78 Example 2 2 - 2 - 15 - - 81 Example 3 15 - 2 - 15 - - 68 Example 4 - 5 2 - 15 - - 78 Example 5 - 5 - 2 15 - - 78 Example 6 5 - 0.5 - 15 - - 79.5 Example 7 5 - 8 - 15 - - 72 Example 8 5 - 2 - - 15 - 78 Example 9 5 - 2 - - - 15 78 Example 10 5 - 2 - 5 - - 88 Example 11 5 - 2 - 25 - - 68 Comparative Example 1 5 - - - 15 - - 80 Comparative Example 2 - - 5 - 15 - - 80 Comparative Example 3 5 - 2 - 60 - - 33 Comparative Example 4 5 - 2 - 0.2 - - 92.8 KOH: Potassium hydroxide
NaOH: sodium hydroxide
TMAH: tetramethylammonium hydroxide
TEAH: tetraethylammonium hydroxide
BDG: diethylene glycol monobutyl ether
THFA: tetrahydroperfuryl alcohol
NMP: N-methylpyrrolidone

Test Example

1. Cleaning ability

In order to evaluate the cleaning ability of the red, green and blue inks used for offset printing and the black ink for BM, as shown in Fig. 1, a color filter having a long side of 130 mu m, a short side of 30 mu m, and a height of 20-30 mu m A pixel-shaped fine pattern was formed on a glass substrate to produce a test board for test evaluation similar to that of an intaglio offset printing intaglio. (PCF-R-001, Dongwoo Fine-Chem), green ink (PCF-G-001, Dongwoo Fine-Chem Co., Ltd.), blue ink (PCF-B- (PCF-BM-001, Dongwoo Fine-Chem Co., Ltd.) were coated in a fine pattern and then dried at 100 ° C for 3 minutes to prepare specimens.

The specimens were immersed in a cleaning composition at room temperature for 30 seconds and 60 seconds. Then, the specimens were taken out and rinsed with deionized distilled water for 20 seconds. After the rinse was completed, the specimen was completely dried using nitrogen.

Optical microscope photographs of the dried specimens were taken and evaluated for their cleaning ability based on the following criteria.

<Evaluation Criteria>

◎: ink is completely removed.

○: Excellent removal of ink.

?: A small amount of ink remained.

X: A large amount of ink remains.

2. Scab injury

The specimens prepared in 1 above were immersed in a cleaning composition at room temperature for a certain period of time (1 hour, 6 hours), and then the specimens were taken out and rinsed with deionized distilled water for 20 seconds. After the rinse was completed, the specimen was completely dried using nitrogen.

Scanning electron microscopy (SEM, Hitach S-4700) photographs of the dried specimens were taken and evaluated for damage to the intact plaques based on the following criteria.

<Evaluation Criteria>

◎: no intaglio damage at all.

○: Almost no intaglio damage.

△: Some scratches damaged.

X: There is a large amount of intaglio damage.

division Cleaning ability Scab injury Red ink Green ink Blue ink Black ink 30 seconds 60 seconds 30 seconds 60 seconds 30 seconds 60 seconds 30 seconds 60 seconds 1 hours 6 hours Example 1 ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ◎ ◎ Example 2 ○ ◎ ○ ◎ ◎ ◎ ○ ○ ◎ ◎ Example 3 ○ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ○ ◎ ○ ◎ ○ ◎ ◎ ◎ Example 5 ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ◎ Example 6 ○ ◎ ○ ○ ○ ◎ ○ ◎ ◎ ◎ Example 7 ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 8 ○ ◎ ◎ ◎ ○ ◎ ○ ◎ ◎ ◎ Example 9 ○ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 10 ○ ◎ ○ ◎ ◎ ◎ ○ ◎ ◎ ◎ Example 11 ○ ◎ ○ ◎ ○ ◎ ○ ◎ ◎ ◎ Comparative Example 1 × △ × △ △ ○ △ ○ ◎ ◎ Comparative Example 2 △ ○ △ ○ ○ ◎ × △ ◎ ◎ Comparative Example 3 × △ × × × △ × × ◎ ◎ Comparative Example 4 × △ × × △ ○ △ ○ ◎ ◎

As shown in Table 2, the cleaning liquid compositions of Examples 1 to 11, in which alkali metal hydroxide, quaternary ammonium compound, water-soluble polar solvent and water were contained in a certain amount in accordance with the present invention, Compared with the ink remaining on the intaglio board, the ink was excellent in removing power over the entire intaglio without damaging the intaglio.

Among the examples, a cleaning liquid composition comprising 1-10 wt% of an alkali metal hydroxide, 0.1-5 wt% of a quaternary ammonium compound, 1-20 wt% of a water-soluble polar solvent, and a residual amount of water, More uniform and fast cleaning ability for blue and black inks was more preferable.

FIG. 2 shows an optical microscope photograph of a specimen cleaned for 60 seconds using the cleaning composition of Example 1 of the present invention. Accordingly, in the case of using the cleaning liquid composition according to the present invention, the black ink present in the specimen, especially in the fine pattern, was removed, and the shape of the specimen as shown in Fig. 1 was clearly confirmed.

FIG. 3 shows an optical microscope photograph of the specimen cleaned for 60 seconds using the cleaning composition of Comparative Example 3. FIG. When the cleaning liquid composition of Comparative Example 3 was used, it was found that not only the inside of the fine pattern of the test piece but also the black ink for BM present outside was removed.

Claims (6)

As cleaning compositions for RGB inks and black inks for black matrix (BM)
1 to 20% by weight of an alkali metal hydroxide; 0.1 to 10% by weight of quaternary ammonium compound; 0.5 to 30% by weight of a water-soluble polar solvent; And a remaining amount of water.
The composition of claim 1, further comprising 1 to 10% by weight of an alkali metal hydroxide; 0.1 to 5% by weight of quaternary ammonium compound; 1 to 20% by weight of a water-soluble polar solvent; And a remaining amount of water.
The offset printing puddle washing liquid composition according to claim 1, wherein the alkali metal hydroxide is at least one selected from the group consisting of lithium hydroxide, sodium hydroxide and potassium hydroxide.
The offset printing plate precursor cleaning composition according to claim 1, wherein the quaternary ammonium compound is a compound represented by the following formula (1)
[Chemical Formula 1]

(Wherein R ₁ to R ₄ are independently a hydrogen atom, a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group).
[Claim 4] The method according to claim 4, wherein the compound represented by Formula (1) is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltripropylammonium hydroxide, Wherein the composition is at least one selected from the group consisting of ethyl ammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, and (1-hydroxypropyl) trimethylammonium hydroxide.
The water-soluble polar solvent according to claim 1, wherein the water-soluble polar solvent is selected from the group consisting of ether compounds, alcohol compounds, pyrrolidone compounds, amide compounds, imidazolidinone compounds, lactone compounds, sulfoxide compounds, phosphate compounds, Cresol-based compound, and a cresol-based compound.

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