TWI441875B - Printing ink and process for producing painted film using the same - Google Patents

Description

Printing ink and manufacturing method of coating film using the same

The present invention relates to a printing ink suitable for use in gravure offset printing in which a fine and high-precision electrode pattern is formed in a semiconductor device, and a method of producing a coating film using the same.

An electrode or the like is formed in a semiconductor device such as an electronic circuit board or a display device, and a photolithography method has been conventionally used. However, this photolithography method is complicated in manufacturing steps and has a large amount of material loss, and an exposure apparatus necessary for forming a pattern. The manufacturing equipment is expensive, and therefore has a problem of extremely high manufacturing costs. Further, the disposal cost of the waste liquid generated by the development process or the like at the time of pattern formation is also high, and there is also a problem with respect to the waste liquid from the viewpoint of protecting the environment.

Then, various studies have been conducted on a pattern forming method which is low in cost and does not generate harmful waste liquid or the like. Among them, since the gravure offset printing method can form a fine pattern with high definition, it is attracting attention as an alternative to the photolithography method. In the gravure offset printing method, in order to transfer the printing ink from the printing felt 100% to the transfer target such as a glass substrate, a ruthenium rubber sheet is used for the surface of the printing felt, and the printing ink is easily dissolved in the printing ink. The rubber on the surface of the felt, such as a solvent, and the solvent is dissolved in the ruthenium rubber. Under the interfacial tension between the printing ink and the ruthenium rubber interface, the printing ink can be easily peeled off from the enamel rubber and the printing ink can be transferred from the felt. Printed on the stencil. As the solvent which is easily soluble in the rubber, an alkyl alcohol such as an α-terpineol alcohol and a butyl carbitol acetate can be used. However, when continuous printing is performed for a long period of time, the solvent contained in the printing ink is gradually permeated on the rubber sheet on the surface of the felt, and the ruthenium rubber sheet is swollen, so that the shape of the printed pattern is changed and the reproduction of the printing is performed. The problem of reduced sexuality.

The countermeasure for solving the above problem is to disclose a method in which the surface of the printing felt is transferred from the surface of the printing felt to the surface of the glass substrate, and then the surface of the felt is heated, and then the surface of the felt is cooled (for example, refer to Patent Document 1 (Specially Open) Publication No. 2002-245931, application 1)). Further, it is disclosed that a material using a polyfluorene-based elastomer is used for the surface of the felt for printing, and a low-molecular-weight polyoxyalkylene is used as an ink for printing, and the printing ink is transferred from the felt for printing to being transferred. After the body, the surface of the felt is heated to evaporate the solvent of the printing ink absorbed by the felt, and then the surface of the felt is cooled (for example, see Patent Document 2 (JP-A-2004-66804, Application No. 1)). According to the methods shown in Patent Documents 1 and 2, the problem of felt swelling is solved by the solvent of the ink.

However, in the methods described in Patent Documents 1 and 2, since the steps of heating and cooling are added to the usual gravure offset printing, the steps are cumbersome, and the rubber sheet on the surface of the felt caused by the printing cannot be prevented from being infiltrated by the solvent in the ink. Did not solve the underlying problem.

An object of the present invention is to provide a printing ink which can reduce the shape of a printing pattern and a manufacturing method of a coating film using the same in continuous printing of gravure offset printing.

(The gist of the invention)

In a first aspect of the present invention, the ink is filled into a printing plate having a concave pattern, and the filled ink is transferred to a printing felt having a ruthenium rubber sheet on the surface, and the ink is transferred to the transferred by the printing felt. Improvement of printing ink used in gravure offset printing of printed matter. It is characterized in that the ink is a powder component composed of at least an inorganic powder or an organic powder, and one or more resin components and solvent components are selected from the group consisting of an acrylic resin and a methacrylic resin, and The solvent component is one or two or more kinds of glycol-based solvents.

In the first aspect of the invention, the diol solvent is a resin component which can dissolve the printing ink, and does not swell the ruthenium rubber sheet on the surface of the printing felt, so that it can be used for printing ink to reduce gravure offset printing. The shape of the printed pattern in continuous printing of printing changes.

The second aspect of the present invention is the invention of the first aspect, wherein the inorganic powder is a printing ink of a metal powder, a metal oxide, a metal nitride or a mixed powder of the mixture.

The third aspect of the present invention is the invention of the first aspect, wherein the resin component is composed of polymethyl acrylate, polyethyl acrylate, poly propyl acrylate, polybutyl acrylate, polybutyl acrylate, polymethacrylic acid. One or more printing inks are selected from the group consisting of methyl ester, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, and copolymers thereof.

According to a fourth aspect of the invention, the diol solvent is a printing ink containing one or more compounds selected from the group consisting of diols having 6 to 12 carbon atoms.

The fifth aspect of the present invention is the invention of the first aspect, wherein the printing plate is a planar intaglio plate having a plurality of concave patterns having a line width W: 10 to 1000 μm, a depth D: 5 to 50 μm, and a pitch P: 10 to 1000 μm. The printing felt is composed of a felt roll having a ruthenium rubber sheet having a surface thickness of 0.1 to 3 mm, and the transfer body is composed of a glass substrate, and the printing ink is filled into the plane intaglio plate, and the filled ink is transferred. After the felt roll, the ink is transferred from the felt roll to the glass substrate, so that the gravure offset printing of the surface of the glass substrate is printed on the surface of the glass substrate, and the printing is performed on 2 to 1000 pieces of the glass substrate. In the printed glass substrate, the average value of the measured values when the line width W of 3 to 12 in the specified position of each glass substrate is measured is in the range of 0.9 W to 1.1 W, and the standard deviation value of the measured value is 1. Printing ink in the range of ~5.

A sixth aspect of the present invention is that the printing ink of any one of the first aspect to the fifth aspect is filled into a printing plate having a concave pattern, and the filled ink is transferred to a surface having a ruthenium rubber After the sheet is printed with a felt, the ink is transferred from the printing felt to a method of producing a coating film characterized by the transfer target.

According to a seventh aspect of the present invention, the ink is filled into a printing plate having a concave pattern, and the filled ink is transferred to a printing felt having a ruthenium rubber sheet, and the ink is transferred to the transferred by the printing felt. Improvement of the printing ink used in the offset printing method of the printing body. The ink is a powder component, a resin component, and a solvent component which are composed of at least an inorganic powder or an organic powder, and the resin component contains an acrylic-styrene copolymer and an acrylate-urethane copolymer. , an acrylic-epoxy copolymer, urethane acrylate or epoxy acrylate, and the solvent component is diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, Γ-butyl lactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl Ether, 3-methoxy-3-methyl-1-butanol, polyester polyol [aliphatic polybasic acid with 2 to 12 carbon atoms. An aliphatic polyol having 2 to 12 carbon atoms], a polyester polyol [an aromatic polybasic acid having 8 to 15 carbon atoms. One or two or more of the group consisting of an aliphatic polyhydric alcohol having 2 to 12 carbon atoms and a liquid acrylic resin having a hydroxyl group are selected.

In the seventh aspect, the resin component described above has a high cohesive force, and can suppress aggregation failure inside the ink when the transfer target is transferred, and the solvent component listed above can dissolve the resin component in the printing ink. For the printing felt, a part of the solvent component is absorbed by the enamel rubber sheet on the surface of the printing felt, and a solvent-rich boundary layer is formed between the ink and the felt (the boundary layer which weakens the adhesion between the ink and the felt: Weak Boundary Layer; hereinafter referred to as WBL), so the oil does not remain on the felt and is transferred, and the solvent absorbed by the felt heating is not volatilized from the surface of the felt, so the printing pattern can be reduced in continuous printing of offset printing. Shape changes.

An eighth aspect of the present invention is the invention of the first aspect, wherein the inorganic powder is a printing ink of a metal powder, a metal oxide, a metal oxide or a mixed powder of the mixture.

The ninth aspect of the present invention is the invention of the first aspect, wherein the printing plate is a planar intaglio having a plurality of concave patterns having a line width W: 10 to 1000 μm, a depth D: 5 to 50 μm, and a pitch P: 10 to 1000 μm or A cylindrical intaglio plate is formed, and the felt for printing is composed of a felt roll having a ruthenium rubber sheet having a surface thickness of 0.1 to 3 mm, and the transfer body is composed of a glass substrate, and the printing ink is filled into a plane intaglio or a cylindrical intaglio plate. After the filled ink is transferred to the felt roller, the ink is transferred from the felt roller to the glass substrate, so that the gravure offset printing of the coating film having the specified pattern on the surface of the glass substrate is continuously printed on the glass substrate from 2 to 1000 pieces, The average value of the measured values when measuring the line width W of 3 to 12 in each of the designated positions of the glass substrates is 1 to 1000 pieces of the printed glass substrate, and the average value of the measured values is in the range of 0.9 W to 1.1 W. The standard deviation of the value is a printing ink in the range of 1 to 5.

According to a tenth aspect of the present invention, the printing ink according to any one of the seventh aspect to the ninth aspect is filled in a printing plate having a concave pattern, and the filled ink is transferred to a surface having a ruthenium rubber sheet. After the printing felt, the ink is transferred from the printing felt to the manufacturing method of the coating film characterized by the transfer body.

Further, of course, the invention of the first state to the sixth state described above may be appropriately combined with the invention of the seventh aspect to the tenth aspect described above.

Next, the best mode for carrying out the invention will be described based on the drawings.

The inventors of the present invention have tried to examine the effect of the solvent on the ruthenium rubber sheet on the surface of the felt for printing, and have confirmed that the diol-based solvent is used instead of the alcohol which is generally used as a solvent. The alkyl ethers can dissolve the resin component in the printing ink without swelling the enamel rubber sheet on the surface of the printing felt, and achieve the present invention.

The printing ink of the present invention is obtained by filling an ink into a printing plate having a concave pattern, and transferring the filled ink to a printing felt having a ruthenium rubber sheet on the surface, and transferring the ink to the transferred printing by the felt for printing. Improvement of the printing ink used in the gravure offset printing method of the body. It is characterized in that the ink is a powder component composed of at least an inorganic powder or an organic powder, and one or more resin components and solvent components are selected from the group consisting of an acrylic resin and a methacrylic resin, and The solvent component is one or two or more kinds of glycol-based solvents. When the ink is regarded as 100% by weight, it is preferably blended in a proportion of 5 to 20% by weight of the resin component and 7.5 to 30% by weight of the solvent component. The diol solvent is a resin component in the ink for printing, and the ruthenium rubber sheet on the surface of the felt for printing is swollen. Therefore, the printing ink of the present invention can be used for continuous printing in which gravure offset printing can be reduced. The advantage of the shape change of the printed pattern. The diol solvent is preferably one or more compounds selected from the group consisting of diols having 6 to 12 carbon atoms. Specific examples thereof include 2-methyl-2,4-pentanediol and 2-ethyl-1,3-hexanediol.

The powder component contained in the printing ink of the present invention is an inorganic powder or an organic powder. Specific examples thereof include organic pigments, inorganic pigments, bright pigments, and organic dyes. Further, metal powder, metal oxide, metal nitride or a mixed powder thereof is particularly suitable because it can be used for printing on a conductive pattern. Examples of the organic pigment include an azo-based, polyazo-based, anthraquinone-based, quinophthalone-based, isoindane-based, isoindolinone-based, phthalocyanine-based, anthracene-based, DPP-based, and fluorescent pigment. Examples of the inorganic pigments include acetonitrile carbon, carbon nanotubes, Furalene, graphite-like carbon powder, synthetic cerium oxide, chromium oxide, iron oxide, titanium oxide, cobalt oxide, titanium black, calcined pigment, and zinc sulfide. Examples of the bright pigment include a pearl pigment, a flake pigment, an aluminum pigment, and a bronze pigment. Examples of the organic dye include alcohol-soluble dyes, oil-soluble dyes, fluorescent dyes, and light-collecting dyes.

The resin component contained in the printing ink of the present invention contains one or more selected from the group consisting of an acrylic resin and a methacrylic resin. Examples of the acrylic resin include polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polybutyl acrylate, and methacrylic resin. Examples include polymethyl methacrylate and polymethacrylic acid. Ester, polypropyl methacrylate, polybutyl methacrylate, polyisobutyl methacrylate. Further, the copolymer of the above-mentioned acrylic resin and methacrylic resin may be used singly or in combination.

Further, the printing ink of the present invention may further contain a dispersing agent. Further, by dispersing a dispersing agent, the effect of smoothing the surface of the applied layer can be obtained. When the ink is regarded as 100% by weight, the dispersant is preferably blended in an amount of from 3 to 10% by weight. Moreover, the acuity in the edge portion of the formed line becomes high. As the dispersant, a carboxylic acid type and a phosphate type, a polycarboxylic acid polymer anionic allyl ether copolymer, a polyamine-fatty acid condensate, a polymer surfactant, a polymer fatty acid, and a fatty acid ester condensate can be suitably used.

A gravure offset printing method using the printing ink of the present invention will be described.

First, as shown in Fig. 1A, a planary intaglio 10 having a desired concave pattern 10a is prepared as a printing plate, and a predetermined amount of the printing ink 11 of the present invention is supplied to the surface of the intaglio plate 10. The supplied printing ink 11 is slid into contact with the surface of the intaglio 10 via the doctor blade 12, and is embedded in the concave pattern 10a. Next, as shown in Fig. 1B, a felt roller 13 having a surface-mounting rubber sheet 13a is prepared as a printing felt, and the felt roller 13 is crimped to the intaglio 10 in which the ink 11 is buried in the concave pattern 10a, and In this state, the felt roller 13 is rotated and slid on the intaglio plate 10, and a part of the ink 11 embedded in the concave pattern 10a of the intaglio plate 10 is transferred to the surface of the polyacetal resin sheet 13a of the felt roller 13. The transfer rate at this time varies depending on the concave pattern of the intaglio plate and the composition and ratio of the ink, and the pressure of the felt, and is about 50 to 60%. Finally, as shown in FIG. 1C, the felt roller 13 of the transfer ink 11 is pressure-bonded to the object to be transferred such as the glass substrate 14, and the felt roller 13 is rotated in this state and slid on the glass substrate 14, The desired pattern can be transferred to the surface of the glass substrate 14 as shown in FIG. 1D. Further, an organic silicone resin sheet may be attached to the surface of the felt roller instead of the silicone rubber sheet. The printing ink 11 of the present invention using a glycol solvent in a solvent makes it difficult for the solvent to impregnate the silicone rubber sheet 13a used on the surface of the felt roller 13, and does not cause the silicone rubber sheet 13a to swell, so that it can be continuously printed. Reduce the shape of the printed pattern.

The printing ink of the present invention is composed of a printing plate which is a concave intaglio having a plurality of concave patterns having a line width W: 10 to 1000 μm, a depth D: 5 to 50 μm, and a pitch P: 10 to 1000 μm, and the printing felt is used. The surface is mounted with a felt roll having a thickness of 0.1 to 3 mm, and the transferred body is composed of a glass substrate. The printing ink is filled into the intaglio plate, and the filled ink is transferred to the felt roll, and the ink is transferred. When the felt roll is transferred to the glass substrate, and the gravure offset printing of the coating film having the specified pattern is printed on the surface of the glass substrate, 2 to 1000 pieces of the glass substrate are continuously printed, and the obtained 1 to 1000 printed glass substrates are respectively measured. The average value of the measured value at the line width W of 3 to 12 in the specified position of each glass substrate is in the range of 0.9 W to 1.1 W, preferably 0.95 W to 1.05 W, and the standard deviation value of the measured value is It is appropriate to range from 1 to 5, preferably from 1 to 3. When the shape of the printed pattern is changed within the above range, it is suitable for long-term continuous printing using gravure offset printing, and an ink excellent in reproducibility of printing can be provided. Here, the continuous printing refers to a case where printing is performed at a speed of 0.5 to 1 piece/minute.

Next, examples and comparative examples of the present invention will be described in detail.

<Examples A1 to A23, Comparative Example A1>

The powder component, the resin component, the solvent component and the dispersing agent shown in the following Tables 1 to 5 are mixed in a mixer, and then mixed by three roller mills to 5 to 10 Pa. Around s, a paste-like printing ink is obtained.

A 42-male intaglio plate having a plurality of concave patterns having a line width of 100 μm, a depth of 25 μm, and a pitch of 360 μm was prepared as a printing plate used in gravure offset printing, and a glass substrate was prepared as a transfer target. Further, a felt roll having an organic resin sheet having a thickness of 0.3 μm was used as a felt for printing. First, a predetermined amount of the printing ink was supplied to the surface of the intaglio plate, and the ink was buried in the concave pattern of the intaglio plate using a SUS doctor blade. Next, by rotating the felt roll in a state of being pressed against the intaglio plate and sliding it on the intaglio plate, a part of the ink embedded in the concave pattern of the intaglio plate can be transferred to the surface of the organic resin sheet of the felt roll. Finally, by rotating the felt roll in a state where the glass substrate is pressed against the glass substrate and sliding on the glass substrate, a printed circuit board having a predetermined pattern on the surface of the glass substrate can be obtained. The gravure offset printing described above was performed for continuous printing on 500 substrates.

<Comparative Test 1>

In each of the 500 printed substrates obtained in Examples A1 to A23 and Comparative Example A1, each of the first, 100th, 200th, 300th, 400th, and 500th substrates was measured. The line width of nine points in the specified position of the substrate was calculated, and the average value and standard deviation value of the measured values were calculated. The results are shown in Tables 6 to 8.

As shown in Tables 6 to 8, in Comparative Example A1, the average value of the line width at nine points in the designated positions of the respective substrates was changed depending on the number of consecutive printings, which was a result of poor printing stability. Moreover, the printing was continuously performed on the 500th, and printing failure occurred. On the other hand, in Examples A1 to A23 using the printing ink of the present invention, the line width average was stable, and it was judged that the use in continuous printing was good.

When the printing ink of the present invention contains at least one or two or more kinds of resin components and solvent components selected from the group consisting of an acrylic resin and a methacrylic resin, The solvent component is characterized by containing one or two or more kinds of glycol solvents. The diol solvent can dissolve the resin component in the printing ink without swelling the ruthenium rubber sheet on the surface of the printing felt, so that the printing ink of the present invention can be used for printing in continuous printing which can reduce gravure offset printing. The advantage of the shape change of the pattern.

Next, the best mode for carrying out the invention will be described based on the drawings.

The inventors of the present invention have evaluated the effect of the dissolution of the resin component on the solvent component and the effect of the solvent on the rubber sheet on the surface of the felt for printing, and confirmed the effect of the resin component and the solvent component on the surface of the felt surface of the printing felt. - a styrene-based copolymer, an acryl-ethyl urethane copolymer, an acrylic-epoxy copolymer, a urethane acrylate or an epoxy acrylate having high cohesive force and inhibiting rotation Aggregation inside the ink during transfer of the ink is destroyed, and via the use of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, γ-butyl lactone, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, two Propylene glycol monobutyl ether, tripropylene glycol monomethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 3-methoxy-3-methyl- 1-butanol, polyester polyol [carbon Of from 2 to 12 aliphatic polycarboxylic acids. An aliphatic polyol having 2 to 12 carbon atoms], a polyester polyol [an aromatic polybasic acid having 8 to 15 carbon atoms. One or more selected from the group consisting of an aliphatic polyhydric alcohol having 2 to 12 carbon atoms and a liquid acrylic resin having a hydroxyl group, and being soluble in place of an alcohol or an alkyl ether which is generally used as a solvent component The resin component listed above in the printing ink is a part of the solvent component that is absorbed into the surface of the printing felt when the printing felt is transferred, and WBL is formed between the ink and the felt, so that the ink does not remain. The transfer is carried out on the felt, and the felt is not heated to volatilize the absorbed solvent from the surface of the felt and to attain the present invention.

The printing ink of the present invention is obtained by filling an ink into a printing plate having a concave pattern, and transferring the filled ink to a printing felt having a ruthenium rubber sheet on the surface, and transferring the ink to the transferred printing by the felt for printing. Improvement of the printing ink used in the offset printing method. The ink is a powder component, a resin component, and a solvent component which are composed of at least an inorganic powder or an organic powder, and the resin component contains an acrylic-styrene copolymer and an acrylate-urethane copolymer. , an acrylic-epoxy copolymer, urethane acrylate or epoxy acrylate, and the solvent component is diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, Γ-butyl lactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl Ether, 3-methoxy-3-methyl-1-butanol, polyester polyol [aliphatic polybasic acid with 2 to 12 carbon atoms. An aliphatic polyol having 2 to 12 carbon atoms], a polyester polyol [an aromatic polybasic acid having 8 to 15 carbon atoms. One or two or more of the group consisting of an aliphatic polyhydric alcohol having 2 to 12 carbon atoms and a liquid acrylic resin having a hydroxyl group are selected. When the ink is regarded as 100% by weight, it is preferably blended in a proportion of 5 to 20% by weight of the resin component and 7.5 to 30% by weight of the solvent component. The solvent component listed above dissolves the resin component in the printing ink, and a part of the solvent component is absorbed into the enamel rubber sheet on the surface of the printing felt when the printing felt is transferred, and WBL is formed between the ink and the felt, so The ink does not remain on the felt and is transferred, and if the felt is not heated, the absorbed solvent is volatilized from the surface of the felt, so that the printing ink of the present invention can be used for printing in continuous printing capable of reducing offset printing. The advantage of changing the shape of the pattern.

The powder component contained in the printing ink of the present invention is an inorganic powder or an organic powder. Specific examples thereof include organic pigments, inorganic pigments, bright pigments, and organic dyes. Further, metal powder, metal oxide, metal nitride or a mixed powder thereof is particularly suitable because it can be used for printing on a conductive pattern. Examples of the organic pigment include an azo-based, polyazo-based, anthraquinone-based, quinophthalone-based, isoindane-based, isoindolinone-based, phthalocyanine-based, anthracene-based, DPP-based, and fluorescent pigment. Examples of the inorganic pigments include acetonitrile carbon, carbon nanotubes, Furalene, graphite-like carbon powder, synthetic cerium oxide, chromium oxide, iron oxide, titanium oxide, cobalt oxide, titanium black, calcined pigment, zinc sulfide, cerium oxide, Cobalt oxide, manganese oxide, copper oxide, and the like. Examples of the bright pigment include a pearl pigment, a flake pigment, an aluminum pigment, and a bronze pigment. Examples of the organic dye include alcohol-soluble dyes, oil-soluble dyes, fluorescent dyes, and light-collecting dyes.

The resin component contained in the printing ink of the present invention contains polyacrylic acid ester such as polymethyl methacrylate or the like, polymethacrylate such as polymethyl methacrylate, and polystyrene or polyaminocarboxylic acid. Ethyl methacrylate, epoxy resin copolymerized acrylic-styrene copolymer, acrylic acid-urethane copolymer, acrylic-epoxy copolymer, polyacrylate and polymethacrylate Ethyl urethane acrylate, epoxy acrylate substituted with ethyl ester or epoxy. Further, the molecular weight of such a resin component is suitably in the range of from several hundreds to several millions of oligomers to a polymer. The low molecular weight resin component is effective for suppressing drying of the ink, and the high molecular weight resin component can suppress aggregation failure inside the ink. That is, it is effective in improving transferability. Therefore, by allowing the resin having a broad molecular weight of a low molecular weight to a high molecular weight in the ink, it is possible to simultaneously suppress the drying of the ink and the improvement of the transfer property. Acrylic-styrene copolymer, acrylic acid-urethane copolymer, acrylic-epoxy copolymer, urethane acrylate or epoxy acrylate have high cohesive force and can inhibit Aggregation damage inside the ink at the time of transfer of the transfer body. Two or more of the above-mentioned styrene-acrylic styrene-based copolymers may be used singly or in combination.

Among the solvent components contained in the printing ink of the present invention, polyester polyol [an aliphatic polybasic acid having 2 to 12 carbon atoms. Examples of aliphatic polyhydric alcohols having 2 to 12 carbon atoms include poly[(1,9-nonanediol)-alt (adipate)], poly[(3-methyl-1,5-pentanediol) ; Trimethylolpropane)-alt-(adipate)], poly[(3-methyl-1,5-pentanediol)-alt (sebacic acid)]. Also, polyester polyol [approximately 8 to 15 aromatic polybasic acids. An aliphatic polyol having 2 to 12 carbon atoms] may be exemplified by poly[(3-methyl-1,5-pentanediol)-alt-(terephthalic acid)]-poly[(3-methyl-) 1,5-pentanediol)-alt-(isophthalic acid)]. Further, the liquid acrylic resin containing a hydroxyl group may, for example, be polyhydroxyethyl acrylate, 2-hydroxypropyl polyacrylate, poly-2-hydroxybutyl acrylate or poly-2-hydroxy methacrylate.

Further, the printing ink of the present invention may further contain a dispersing agent. When a dispersing agent is further contained, the effect of smoothing the surface of the applied layer can be obtained. When the ink is regarded as 100% by weight, the dispersant is preferably blended in a ratio of 3 to 10% by weight. Moreover, the sharpness of the edge portion of the formed line becomes high. As the dispersant, a carboxylic acid-based or polycarboxylic acid-type polymer anion, an olefin-propylene copolymer, a polyamine-fatty acid condensate, a polymer surfactant, a polymer fatty acid, a phosphate ester, or a fatty acid ester condensate can be suitably used.

A gravure offset printing method using the printing ink of the present invention will be described.

First, as shown in Fig. 1A, a planary intaglio 10 having a desired concave pattern 10a is prepared as a printing plate, and a predetermined amount of the printing ink 11 of the present invention is supplied to the surface of the intaglio plate 10. The supplied printing ink 11 is slid into contact with the surface of the intaglio 10 via the doctor blade 12, and is embedded in the concave pattern 10a. Next, as shown in Fig. 1B, a felt roller 13 having a surface-mounting rubber sheet 13a is prepared as a printing felt, and the felt roller 13 is crimped to the intaglio 10 in which the ink 11 is buried in the concave pattern 10a, and In this state, the felt roller 13 is rotated and slid on the intaglio plate 10, and a part of the ink 11 embedded in the concave pattern 10a of the intaglio plate 10 is transferred to the surface of the polyacetal resin sheet 13a of the felt roller 13. The transfer rate at this time varies depending on the concave pattern of the intaglio plate and the composition and the ratio of the ink, and the pressure of the felt, and is about 20 to 60%. A part of the solvent component contained in the ink 11 of the present invention to be transferred is a ruthenium rubber sheet 13a which is absorbed to the surface of the felt 13, and a rich boundary layer (WBL) is formed between the ink and the ruthenium rubber sheet 13a, so In the step, the ink does not remain on the felt and can be transferred to the object to be transferred. Finally, as shown in FIG. 1C, the felt roller 13 of the transfer ink 11 is pressure-bonded to the object to be transferred such as the glass substrate 14, and the felt roller 13 is rotated in this state and slid on the glass substrate 14, The desired pattern can be transferred to the surface of the glass substrate 14 as shown in FIG. 1D. Further, an organic silicone resin sheet may be attached to the surface of the felt roller instead of the silicone rubber sheet. The printing ink 11 of the present invention has a high cohesive force in the resin component, and can suppress aggregation failure inside the ink when the transfer target is transferred, and the solvent component is a resin component which can dissolve the printing ink, and is transferred to the felt for printing. When printing, a part of the solvent component is absorbed into the enamel rubber sheet on the surface of the printing felt, and WBL is formed between the ink and the felt, so that the ink does not remain on the felt and is transferred, and the felt is not heated. The absorbed solvent is volatilized from the surface of the felt, so that the shape change of the printed pattern in continuous printing can be reduced.

Further, the solvent component of diethylene glycol monobutyl ether or ethylene glycol monobutyl ether is transferred to the surface of the rubber sheet 13a of the felt roller 13 according to a part of the ink 11 shown in Fig. 1B until the desired pattern is transferred. The interval between the printing on the surface of the glass substrate 14 shown in Fig. 1C is preferably such that the mixing ratio is changed. That is, after the ink is transferred to the roller, until the time until the ink is transferred to the transfer target is long, for example, in the use of a large-sized apparatus, diethylene glycol monobutyl ether having a high boiling point alone, or a plurality of uses The ratio of diethylene glycol monobutyl ether, and after the ink is transferred to the roller until the time when the ink is transferred to the transfer target is short, for example, less than the use of the device, the lower boiling point of the second The ratio of alcohol monobutyl ether or a number of ethylene glycol monobutyl ethers.

The printing ink of the present invention is composed of a printing plate and a gravure plate or a cylindrical intaglio plate having a plurality of concave patterns having a line width W of 10 to 1000 μm, a depth D of 5 to 50 μm, and a pitch P of 10 to 1000 μm. The felt is composed of a felt roll having a 矽 rubber sheet having a thickness of 0.1 to 3 mm on the surface, and when the transfer target is composed of a glass substrate, the printing ink is filled into a plane intaglio or a cylindrical intaglio plate, and the filled ink is transferred. After printing onto the felt roll, the ink is transferred from the felt roll to the glass substrate, so that the gravure offset printing of the surface of the glass substrate is printed on the surface of the glass substrate by 2 to 1000 consecutive printings, for each of the obtained 1 to 1000 The average value of the measured value when measuring the line width W of 3 to 12 in the designated position of each of the glass substrates is 0.9 to 1.1 W, preferably 0.95 to 1.05 W. Further, it is appropriate that the standard deviation value of the measured value is in the range of 1 to 5, preferably 1 to 3. When the shape of the printed pattern is changed within the above range, it is suitable for long-term continuous printing using gravure offset printing, and an ink excellent in reproducibility of printing can be provided. Here, the continuous printing refers to a case where printing is performed at a speed of 0.5 to 1 piece/minute.

[Examples]

Next, examples and comparative examples of the present invention will be described in detail.

<Examples B1 to B122, Comparative Example B1>

The powder component, the resin component, the solvent component and the dispersing agent shown in the following Tables 9 to 32 are mixed by a mixer, and then mixed by three roller mills to 5 to 10 Pa. About s, get printing ink.

A 42-male intaglio plate having a plurality of concave patterns having a line width of 100 μm, a depth of 25 μm, and a pitch of 360 μm was prepared as a printing plate used in gravure offset printing, and a glass substrate was prepared as a transfer target. Further, a felt roll having a ruthenium rubber sheet having a thickness of 0.3 mm was used as a felt for printing. First, a predetermined amount of the printing ink was supplied to the surface of the intaglio plate, and the ink was buried in the concave pattern of the intaglio plate using a SUS doctor blade. Next, by rotating the felt roller in a state of being pressed against the intaglio plate and sliding it on the intaglio plate, a part of the ink embedded in the concave pattern of the intaglio plate can be transferred to the surface of the rubber sheet of the felt roller. Finally, by rotating the felt roll in a state where the glass substrate is pressed against the glass substrate and sliding on the glass substrate, a printed circuit board having a predetermined pattern on the surface of the glass substrate can be obtained. The gravure offset printing described above was performed for continuous printing on 500 substrates.

[Comparative Test 2]

In each of the 500 printed substrates obtained in Examples B1 to B122 and Comparative Example B1, each of the first, 100th, 200th, 300th, 400th, and 500th substrates was measured. The line width of nine points in the specified position of the substrate was calculated, and the average value and standard deviation value of the measured values were calculated. The results are shown in Tables 33 to 46.

As shown in Tables 33 to 46, in Comparative Example B1, the average value of the line width at nine points in the designated positions of the respective substrates was changed depending on the number of consecutive printings, which was a result of poor printing stability. Moreover, the printing was continuously performed on the 500th, and printing failure occurred. On the other hand, in Examples B1 to B122 using the printing ink of the present invention, the line width average was stable, and it was judged that the use in continuous printing was good.

When the printing ink of the present invention contains at least a powder component, a resin component and a solvent component composed of an inorganic powder or an organic powder, the resin component contains an acryl-styrene copolymer and an acryl-urethane copolymer. Acrylic-epoxy copolymer, urethane acrylate or epoxy acrylate, and the solvent component is diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, γ -butyl lactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, two Propylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether , 3-methoxy-3-methyl-1-butanol, polyester polyol [an aliphatic polybasic acid having 2 to 12 carbon atoms. An aliphatic polyol having 2 to 12 carbon atoms], a polyester polyol [an aromatic polybasic acid having 8 to 15 carbon atoms. One or two or more of the group consisting of an aliphatic polyhydric alcohol having 2 to 12 carbon atoms and a liquid acrylic resin having a hydroxyl group are selected. The resin component described above has a high cohesive force, and can suppress aggregation failure inside the ink when transferred to the transfer target, and the solvent component described above can dissolve the resin component in the printing ink, and is used for transfer of the felt for printing. A part of the solvent component is absorbed by the ruthenium rubber sheet on the surface of the felt for printing, and WBL is formed between the ink and the felt, so that the ink does not remain on the felt and is transferred, and the solvent is absorbed by not heating the felt. Since the surface of the felt is volatilized, it has the advantage of reducing the shape variation of the printed pattern in continuous printing of offset printing.

10. . . Plane intaglio

10a. . . Concave pattern

11. . . Printing ink

12. . . Squeegee

13. . . Felt roll

13a. . .矽 rubber sheet

14. . . glass substrate

1A to 1D are schematic views of a gravure offset printing method.

Claims (9)

A printing ink for filling an ink into a printing plate having a concave pattern, and transferring the filled ink to a printing felt having a ruthenium rubber sheet, and transferring the printing felt toward the transfer body In the printing ink used in the gravure offset printing method of the ink, the ink is characterized in that it contains at least a powder component composed of an inorganic powder or an organic powder, and is selected from the group consisting of an acrylic resin and a methacrylic resin. One or more of a resin component and a solvent component, wherein the solvent component contains one or more glycol solvents, and the glycol solvent is 2-methyl-2,4-pentanediol or 2-B. Base-1,3-hexanediol. The printing ink according to claim 1, wherein the inorganic powder is a metal powder, a metal oxide, a metal nitride or a mixed powder of the mixture. The printing ink of claim 1, wherein the resin component is polymethyl acrylate, polyethyl acrylate, poly propyl acrylate, polybutyl acrylate, polybutyl acrylate, polymethyl methacrylate, One or more selected from the group consisting of polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, and copolymers thereof. The printing ink according to claim 1, wherein the printing plate is composed of a planar intaglio having a plurality of concave patterns having a line width W: 10 to 1000 μm, a depth D: 5 to 50 μm, and a pitch P: 10 to 1000 μm. The felt for printing is a felt roller with a rubber sheet of 0.1 to 3 mm thick on the surface. According to the configuration, the transfer target is composed of a glass substrate, the printing ink is filled into the planar intaglio plate, and the filled ink is transferred to the felt roller, and then the ink is transferred from the felt roller to the glass substrate, so that the surface of the glass substrate is printed. Gravure offset printing with a coating film of a specified pattern When two to 1000 sheets of glass substrates are continuously printed, each of the obtained 1 to 1000 printed glass substrates is measured for 3 to 12 lines in a specified position of each glass substrate. The average value of the measured value at the width W is in the range of 0.9 W to 1.1 W, and the standard deviation value of the measured value is in the range of 1 to 5. A method of producing a coating film, characterized in that the printing ink according to any one of claims 1 to 4 is filled into a printing plate having a concave pattern, and the filled ink is transferred to a surface having a crucible After the felt for printing the rubber sheet, the ink is transferred from the printing felt to the transfer target. A printing ink for filling an ink into a printing plate having a concave pattern, and transferring the filled ink to a printing felt having a ruthenium rubber sheet, and transferring the ink to the transfer by the printing felt In the printing ink used in the offset printing method, the ink is a powder component, a resin component and a solvent component which are composed of at least an inorganic powder or an organic powder, and the resin component contains an acrylic-styrene copolymer. An acryl-ethyl urethane copolymer, an acryl-epoxy copolymer, a urethane acrylate or an epoxy acrylate, and the solvent component contains one or more diol solvents, The diol solvent is 2-methyl-2,4-pentanediol or 2-ethyl-1,3-hexanediol. The printing ink according to claim 6, wherein the inorganic powder is a metal powder, a metal oxide, a metal nitride or a mixed powder of the mixture. The printing ink according to item 6 of the patent application, wherein the printing plate is a plane intaglio or cylinder having a plurality of concave patterns having a line width W: 10 to 1000 μm, a depth D: 5 to 50 μm, and a pitch P: 10 to 1000 μm. The gravure is composed of a felt roll having a ruthenium rubber sheet having a surface thickness of 0.1 to 3 mm, and the transfer body is composed of a glass substrate, and the printing ink is filled in a plane intaglio or a cylindrical intaglio plate, and After the filled ink is transferred to the felt roller, the ink is transferred from the felt roller to the glass substrate, so that the gravure offset printing of the coating film having the specified pattern on the surface of the glass substrate is continuously printed on the glass substrate from 2 to 1000 pieces, For each of the 1 to 1000 printed glass substrates, the average value of the measured values when measuring the line width W of 3 to 12 at the designated position of each glass substrate is in the range of 0.9 W to 1.1 W, and the measured value is The standard deviation value is in the range of 1 to 5. A method of producing a coating film, which is characterized in that a printing ink according to any one of claims 6 to 8 is filled into a printing plate having a concave pattern, and the filled ink is transferred to a surface having a crucible After the felt for printing the rubber sheet, the ink is transferred from the printing felt to the transfer target.