KR100898518B1 - Printing paste composition using in gravure off-set printing for making electro wave shielding mash filter - Google Patents

Abstract

The present invention relates to a printing paste composition used to prepare a mesh filter for shielding electromagnetic waves using a gravure offset printing method.

The printing paste composition according to the present invention is particularly suitable for gravure offset printing capable of directly forming a fine pattern, and reprocessing of materials generated when manufacturing an electrode pattern or an electromagnetic shielding fine electrode of a plasma display panel using a conventional photolithography method. The problem can be solved at the source, and at the same time, in order to exhibit proper offset printing characteristics, each of the various required properties of the paste composition required for the printing process procedure can be satisfied.

Paste, Gravure Offset

Description

Printing paste composition used for manufacturing electromagnetic shielding mesh filter by gravure offset printing method {PRINTING PASTE COMPOSITION USING IN GRAVURE OFF-SET PRINTING ELECTRO WAVE SHIELDING MASH FILTER}

The present invention relates to a printing paste composition used to prepare an electromagnetic shielding mesh filter using a gravure offset printing method, and more particularly, is particularly suitable for gravure offset printing capable of directly forming a fine pattern, and conventional photolithography It is possible to fundamentally solve the problem of reprocessing of materials generated in manufacturing electrode patterns or electromagnetic shielding fine electrodes of plasma display panels using the method, and at the same time, it is necessary to solve the problem The present invention relates to a printing paste composition capable of meeting various required physical properties.

In recent years, in the display devices, as the demand for larger size, higher density, higher precision, and higher reliability increases, various pattern processing techniques have been developed, and various fine electrode formations suitable for such various pattern processing techniques have been made. There is an active research into the composition for use.

Plasma display panels (hereinafter referred to as 'PDP') are used in various fields at present because they have a faster response speed and easier size than those of liquid crystal panels. Conventionally, as a method of forming an electrode on such a PDP, a patterning method of electrode materials using a screen printing method has been generally used. However, the conventional screen printing method requires a high degree of skill, and the viscosity is low when screen printing is performed, so that the paste can flow down on the substrate, and the accuracy of the screen is reduced. It is difficult to obtain a high precision large screen pattern. In addition, the conventional screen printing method has a disadvantage in that short-circuit or disconnection may occur due to the screen during printing.

On the other hand, in recent years, the photolithography method using the photosensitive resin composition was developed in order to form the high precision electrode circuit suitable for a large area. This uses a photosensitive resin composition in which fine conductive powder is dispersed to form a uniform thick film through a printing method, expose the formed thick film using a mask having a desired shape, and then implement a necessary pattern using an alkaline developer. It is a way.

However, when the pattern is formed using the photolithography method as described above, reprocessing of the material removed during the development process is required to reduce the manufacturing cost, and many discussions have been made.

In order to solve the above problems, researches on a method of directly forming a desired pattern on a substrate, such as a gravure offset printing method or an inkjet printing method, which are widely used in the conventional printing industry, are being conducted.

In order to solve the problems of the prior art as described above, the present invention is particularly suitable for gravure offset printing that can directly form a fine pattern, when manufacturing the electrode pattern of the plasma display panel using a conventional photolithography method or the fine electrode for shielding electromagnetic waves It is an object of the present invention to provide a printing paste composition and an electrode forming method of an electromagnetic shielding mesh filter using the paste composition which can fundamentally solve a problem of reprocessing of materials.

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In order to achieve the above object, the present invention provides a printing paste composition,

a) 20 to 50% by weight of methacrylic acid, ii) 10 to 30% by weight of benzyl methacrylate, and v) 20 to 60% by weight of 2-hydroxyethyl (meth) acrylate or methyl (meth) acrylate. 5 to 30% by weight of an acrylate polymer resin having a weight average molecular weight of 10,000 to 100,000 prepared by polymerization in a solvent;

b) a crosslinkable oligomer having at least two or more ethylenic double bonds selected from the group consisting of trimethylpropanetriacrylate, a diacrylate derivative containing a urethane bond, and dipentaerythritol polyacrylate; weight%;

c) 0.1 to 5% by weight of photoinitiator selected from the group consisting of 2,2-dichloro-4-phenoxyacetophenone, 2,2'-diethoxyacetophenone, and 2,2'-dibutoxyacetophenone ; And

d) 50-85 wt% silver powder

It provides a printing paste composition used to manufacture a mesh filter for shielding electromagnetic waves using a gravure offset printing method comprising a.

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In another aspect, the present invention provides a method for forming an electrode of the mesh filter for electromagnetic shielding comprising the step of forming a pattern by a gravure offset printing method using the printing paste composition.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have shown that acrylates of the appropriate molecular weight can be used to demonstrate the appropriate elastic properties of the composition required in the off process in order to produce a gravure offset printing paste composition that can meet the various required physical properties of the composition required for each printing process procedure. Printing paste composition which is particularly suitable for gravure offset printing as a result of using a polymer and using a crosslinkable oligomer in place of the organic solvent present in the printing paste composition in order to minimize the swelling of the blanket generated during the set process. It was confirmed that can be prepared, based on this it was to complete the present invention.

The printing paste composition used to prepare the electromagnetic wave shielding mesh filter using the gravure offset printing method of the present invention comprises a) iii) 20 to 50% by weight of methacrylic acid, ii) 10 to 30% by weight of benzyl methacrylate, 5 to 30% by weight of an acrylate polymer resin having a weight average molecular weight of 10,000 to 100,000 prepared by polymerizing 20 to 60% by weight of 2-hydroxyethyl (meth) acrylate or methyl (meth) acrylate in a solvent;
b) a crosslinkable oligomer having at least two or more ethylenic double bonds selected from the group consisting of trimethylpropanetriacrylate, a diacrylate derivative containing a urethane bond, and dipentaerythritol polyacrylate; weight%;
c) 0.1 to 5% by weight of photoinitiator selected from the group consisting of 2,2-dichloro-4-phenoxyacetophenone, 2,2'-diethoxyacetophenone and 2,2'-dibutoxyacetophenone ; And
d) 50-85 wt% silver powder
Characterized in that it comprises a printing paste composition used to prepare a mesh filter for shielding electromagnetic waves using a gravure offset printing method comprising a.

The acrylate polymer resin of a) used in the present invention can be used a common acrylate polymer resin, of course, preferably the acrylate polymer resin used in the present invention is unsaturated carboxylic acid monomer, aromatic monomer, and other It can be prepared by polymerizing monomers.

The unsaturated carboxylic acid monomer acts to increase the elasticity of the polymer through hydrogen bonding in the polymer, specifically, methacrylic acid may be used.

The unsaturated carboxylic acid monomer is preferably included in 20 to 50% by weight in the total monomer used in the production of the acrylate polymer resin, when the content is in the above range, the elastic properties of the polymer, prevention of gelation during polymerization, and control of the degree of polymerization It is good to be able to satisfy all.

The aromatic monomer functions to form adhesion with the substrate and a stable pattern, and specifically, benzyl methacrylate may be used.

The aromatic monomer is preferably included in 10 to 30% by weight, more preferably 15 to 20% by weight in the total monomer used in the production of the acrylate polymer resin. When the content is within the above range, the adhesion to the substrate, the adhesion of the pattern, the linearity of the formed pattern, the stable pattern can be implemented, it can be satisfactorily all the organic matters removed during the firing process.

In addition to the unsaturated carboxylic acid monomer and the aromatic monomer, other monomers used in the production of the acrylate polymer resin serve to control the glass transition temperature and polarity of the polymer.

The other monomers may be used 2-hydroxyethyl (meth) acrylate, methyl (meth) acrylate, the content of which is in consideration of the glass transition temperature of the polymer, heat resistance, intimacy with the substrate, etc. It is preferably included in 20 to 60% by weight in the total monomers used in the preparation.

The acrylate polymer resin prepared by polymerizing such monomers may be prepared by polymerizing in a solvent to prevent gelation of unsaturated carboxylic acid monomers, aromatic monomers, and other monomers, and to control proper volatility during the offset printing process. .

The solvent is propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, ethyl ether propionate, terpinol, propylene glycol monomethyl ether acetate, dimethylamino formaldehyde, methyl ethyl ketone , Butyl carbitol, butyl carbitol acetate, gamma butyrolactone or ethyl lactate may be used alone or in combination of two or more thereof.

The acrylate polymer resin obtained by polymerizing such monomers in the presence of a solvent preferably has a weight average molecular weight of 10,000 to 100,000, more preferably 20,000 to 50,000. If the weight average molecular weight is within the above range, the glass transition temperature of the polymer resin is low, which increases the flow characteristics of the polymer, which makes it difficult to transfer the pattern from the gravure groove to the blanket during the off process and the gravure due to the excessive elasticity of the polymer resin. At the same time, it is possible to solve the problem that it is difficult to add the composition into the groove.

The acrylate polymer resin is preferably contained in 5 to 30% by weight in the printing paste composition of the present invention. When the content is less than 5% by weight, there is a possibility that a problem may occur during the off process due to the decrease in elasticity of the composition, and when the content exceeds 30% by weight, there is a problem that the electrical resistance of the formed pattern is increased.

The crosslinkable oligomer of b) used in the present invention preferably has at least two or more ethylenic double bonds, specifically 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene Glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, diacryl containing urethane bonds A late derivative, trimethyl propane triacrylate, dipentaerythritol polyacrylate, these methacrylates, etc. can be used individually or in mixture of 2 or more types.

The crosslinkable oligomer is preferably included in the printing paste composition of the present invention at 5 to 30% by weight, more preferably at 5 to 15% by weight. If the content is less than 5% by weight, there is a problem in that the pattern is difficult to implement due to an increase in the viscosity of the printing paste composition. When the content is more than 30% by weight, the off characteristic is decreased due to the decrease in elasticity of the printing paste composition, and the straightness of the pattern is reduced. There is a problem of worsening.

The photopolymerization initiator of c) used in the present invention may be used by mixing one or more kinds of compounds such as triazine, benzoin, acetophenone, imidazole or tanthone. Specifically, the photopolymerization initiator is 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s- Triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2, 2-dichloro-4-phenoxyacetophenone, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone , 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,2'-bis-2 -Chlorophenyl-4,5,4 ', 5'-tetraphenyl-2'-1,2'-biimidazole, 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer, 2 -(o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenyl imidazole dimer, 2- (o- Chlorophenyl) -4,5-diphenyl di Dazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl imidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenyl imidazole dimer, 2- (2 Compounds such as 4-dimethoxyphenyl) -4,5-diphenyl imidazole dimer or 2- (p-methylmercaptophenyl) -4,5-diphenyl imidazole dimer alone or two or more It can be mixed and used.

The photopolymerization initiator is preferably included in the printing paste composition of the present invention in 0.1 to 5% by weight, more preferably 0.1 to 3% by weight. If the content is less than 0.1% by weight, there is a problem in that the adhesion of the formed pattern is lowered. When the content is more than 5% by weight, there is a problem in that solubility of the photopolymerization initiator may occur.

The metal powder of d) used in the present invention is not particularly limited as long as it is a metal powder that can be used for forming a PDP electrode or a metal powder that can be used for an electrode of an electromagnetic shielding mesh filter, and specific examples include silver, copper, nickel or Alloys containing these and the like can be used.

The metal powder is preferably included in the printing paste composition of the present invention in 50 to 85% by weight. If the content is less than 50% by weight, there is a problem that the performance as a required electrode or the electromagnetic shielding performance may be lowered due to an increase in the electrical resistance of the formed pattern. When the content exceeds 85% by weight, the viscosity of the printing paste composition is increased. And it is difficult to disperse, there is a problem that the printing characteristics can be reduced.

The printing paste composition of the present invention comprising the above components may optionally have a dispersant for dispersing the metal powder, a black pigment for controlling contrast, and a glass powder for increasing adhesion to glass during firing. ) May be further included, and the content thereof is preferably used in an amount of 0.01 to 10% by weight, and more preferably 0.1 to 3% by weight, based on the printing paste composition of the present invention.

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In another aspect, the present invention provides a method for forming an electrode of the electromagnetic wave shielding mesh filter comprising the step of forming a pattern by a gravure offset printing method using the printing paste composition, the electrode forming method of the electromagnetic wave shielding mesh filter of the present invention A method of forming an electrode of an electromagnetic shielding mesh filter using silver printing paste, the printing paste composition of the present invention is used in place of the conventional paste composition, and a gravure offset printing method is adopted. It is a matter of course that the mesh filter electrode for electromagnetic wave shielding can be formed with other known methods.

The manufacturing method of the electromagnetic wave shielding mesh filter using the printing paste composition of the present invention is excellent in printing characteristics, excellent in straightness and stability of the formed pattern, and in particular, since it takes a direct printing method, it is more economical than using the photolithography method. There is a significant improvement.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

Methacrylic acid (MA): benzyl methacrylate (BM): 2-hydroxyethyl (meth) acrylate (2-HEMA): methyl (meth) acrylate (MMA) = 30: 20 15% by weight of polymer resin (weight average molecular weight 25,000) polymerized at a weight ratio of 10:40, M310 (provided by Miwon Corporation) as a crosslinking oligomer: DPHA (provided by Nippon Kayaku): U-108A (provided by Shinnakamura Chemical) = 1 : 10% by weight of crosslinkable oligomer mixed at a weight ratio of 2: 1, 2% by weight of I-907 (provided by Ciba Special Chemical) as a photopolymerization initiator, 71% by weight of silver as metal powder, and an organic dispersant comprising an amine group as a dispersant 2 The wt% was mixed and stirred at room temperature, and finally a desired printing paste composition was prepared using a 3-roll mill.

Examples 2-3 and Comparative Examples 1-2

Except for using the composition ratio shown in Table 1 in Example 1 was carried out in the same manner as in Example 1 to prepare a printing paste composition.

The unit in Table 1 below is weight percent.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Acrylate polymer resin 15 10 14 22 - Crosslinkable oligomer 10 15 9 3 25 I-907 2 2 4 2 2 silver 71 71 71 71 71 Dispersant 2 2 2 2 2

Gravure offset printing was performed using the printing paste compositions prepared in Examples 1 to 3 and Comparative Examples 1 or 2 to evaluate printing characteristics, minimum line width, and straightness of the pattern, and the results are shown in Table 2 below. .

In the gravure offset printing, the printing paste compositions prepared in Examples 1 to 3 and Comparative Examples 1 or 2 are applied to the gravure plate, respectively, and then the compositions are uniformly applied to the gravure plate using a blade, followed by a blanket The composition of the gravure plate was transferred (off process) using. Then, the pattern transferred to the blanket was first cured using a UV lamp, and then the substrate was transferred to the pattern transferred to the blanket (set process). The pattern transferred to the substrate was subjected to a second curing step using a UV lamp.

In addition, the evaluation of the printing characteristics was evaluated by observing with an optical microscope at the level of the composition remaining on the blanket without transferring to the substrate during the set-set process. The case where the printing composition is usually on the blanket during the process is represented by Δ, and the case where the printing composition is excessively left on the blanket during the three process and the pattern transfer is not possible on the substrate are represented by ×. The minimum line width measured the minimum size of the pattern that can be formed by gravure offset printing. The smaller the size, the better. In addition, the pattern straightness was observed with an optical microscope to the degree of the straightness of the pattern formed on the substrate after printing, it was shown as "good" if the pattern is excellent, and "bad" if it is poor.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Printing characteristics ○ ○ ○ × △ Line width 15 μm 20 μm 20 μm - 100 μm Pattern Straightness Good Good Good - Bad

As shown in Table 2, Examples 1 to 3, the pattern was formed by the gravure offset printing method using the printing paste composition according to the present invention is excellent in printing characteristics compared to Comparative Example 1 and Comparative Example 2, The minimum line width was narrow to 20 μm or less, and it was confirmed that the pattern straightness was excellent. In the case of Comparative Example 1, the printing was not performed, and thus the pattern was not formed.

The printing paste composition according to the present invention is particularly suitable for gravure offset printing capable of directly forming a fine pattern, and reprocessing of materials generated when manufacturing an electrode pattern or an electromagnetic shielding fine electrode of a plasma display panel using a conventional photolithography method. The problem can be solved at the source, and at the same time, in order to exhibit appropriate offset printing characteristics, there is an effect that each can satisfy various requirements of the paste composition required for the printing process procedure.

Claims (12)

a) 20 to 50% by weight of methacrylic acid, ii) 10 to 30% by weight of benzyl methacrylate, i) 20 to 60% by weight of 2-hydroxyethyl (meth) acrylate, or methyl (meth) acrylate 5 to 30% by weight of an acrylate polymer resin having a weight average molecular weight of 10,000 to 100,000 prepared by polymerization in a solvent; b) a crosslinkable oligomer having at least two or more ethylenic double bonds selected from the group consisting of trimethylpropanetriacrylate, a diacrylate derivative containing a urethane bond, and dipentaerythritol polyacrylate; weight%; c) 0.1 to 5% by weight of photoinitiator selected from the group consisting of 2,2-dichloro-4-phenoxyacetophenone, 2,2'-diethoxyacetophenone and 2,2'-dibutoxyacetophenone ; And d) 50-85 wt% silver powder Printing paste composition used to prepare a mesh filter for electromagnetic shielding using a gravure offset printing method comprising a. delete delete delete delete delete delete delete delete The method of claim 1, The printing paste composition is used to prepare a mesh filter for electromagnetic shielding using a gravure offset printing method, characterized in that it further comprises 0.01 to 10% by weight of an additive consisting of a dispersant, a black pigment, and a glass powder. Printing paste composition. delete An electrode forming method of an electromagnetic shielding mesh filter comprising forming a pattern by a gravure offset printing method using the printing paste composition of claim 1.