JP5531380B2 - Ink for printing and method for producing coating film using the ink - Google Patents

Description

  The present invention relates to a printing ink suitable for use in intaglio offset printing for forming a fine and highly accurate electrode pattern on a semiconductor device and a method for producing a coating film using the ink.

  Conventionally, a photolithography method has been used to form electrodes and the like in semiconductor devices such as electronic circuit boards and display devices. However, this photolithography method has a complicated manufacturing process and has a lot of material loss, so that pattern formation can be performed. There is a problem that the manufacturing cost becomes extremely high because a huge amount of cost is required for manufacturing equipment such as an exposure apparatus. Furthermore, the cost of processing the waste liquid generated in the development process at the time of pattern formation is high, and the waste liquid has a problem from the viewpoint of environmental protection.

  Thus, various researches have been conducted on pattern formation methods that are low in cost and do not generate harmful waste liquids. In particular, the intaglio offset printing method is attracting attention as an alternative to the photolithography method because it can form a fine pattern with high accuracy.

  In the intaglio offset printing method, 100% of the printing ink is transferred from the printing blanket to a transfer medium such as a glass substrate. Therefore, a silicone rubber sheet is used for the printing blanket surface, and the silicone rubber on the blanket surface is used for the printing ink. For example, a solvent is added, this solvent is dissolved in silicone rubber, and the interfacial tension at the interface between the printing ink and the silicone rubber is reduced to make it easier to peel the printing ink from the silicone rubber. The image is transferred from the blanket onto the transfer object. As solvents that are easily dissolved in silicone rubber, alcohols such as α-terpineol and alkyl ethers such as butyl carbitol acetate have been used. However, if continuous printing is performed for a long time, the solvent contained in the printing ink gradually permeates into the silicone rubber sheet on the blanket surface, and the silicone rubber sheet swells. There is a problem that the reproducibility of the image quality decreases.

As a measure for solving the above problem, a method of heating the blanket surface after transferring the conductive ink composition from the printing blanket surface to the surface of the glass substrate and then cooling the blanket surface is disclosed ( For example, see Patent Document 1.) Also, the surface of the printing blanket that uses a silicone elastomer is used, and the ink that contains low molecular weight polysiloxane is used as the printing ink, and the printing ink is transferred from the printing blanket to the transfer target. A method of heating the blanket surface after the transfer to the surface to evaporate the solvent of the printing ink absorbed by the blanket and then cooling the blanket surface is disclosed (for example, see Patent Document 2). By the methods disclosed in Patent Documents 1 and 2, the problem that the blanket swells due to the solvent of the ink can be solved.
JP 2002-245931 A (Claim 1) JP 2004-66804 A (Claim 1)

  However, in the methods shown in Patent Documents 1 and 2, the heating and cooling steps are added to the normal offset printing, and the steps are complicated, and the solvent in the ink is applied to the silicone rubber sheet on the blanket surface by printing. It has not been possible to prevent the penetration of, and it has not solved the fundamental problem.

  An object of the present invention is to provide a printing ink capable of reducing the shape variation of a printed pattern in continuous printing by offset printing, and a method for producing a coating film using the ink.

  Another object of the present invention is to provide a printing ink and a method for producing a coating film using the ink, which can solve the problem of stickiness of a line pattern caused by a specific liquid resin component.

According to claim 1 invention, the inorganic Powder that consists powder component, a resin component and a solvent component filled with ink containing at least a printing plate having a concave pattern, the silicone rubber sheet filled ink to the surface The printing ink used in the intaglio offset printing method in which the ink is transferred from the printing blanket to the transfer medium after being transferred to the printing blanket having the above.

The characteristic structure is that the inorganic powder is a silver powder and a Bi ₂ O ₃ —B ₂ O ₃ glass powder, the inorganic powder is a silver powder and a Bi ₂ O ₃ —B ₂ O ₃ glass powder, the resin component a acrylic - a styrene copolymer or a urethane acrylate, and wherein a solvent component is diethylene glycol monobutyl ether or ethylene glycol monobutyl ether, in the ink, the monomer capable of crosslinking reaction with the resin component As a trifunctional monomer of ethoxylated trimethylolpropane triacrylate and a carboxylic acid dispersant as a dispersant .

  In the invention according to claim 1, the enumerated resin component has a high cohesive force and can suppress cohesive failure inside the ink at the time of transfer to a transfer medium, and the enumerated solvent component is used for printing. It is possible to dissolve the resin component in the ink, and when transferred to the printing blanket, a part of the solvent component is absorbed into the silicone rubber sheet on the surface of the printing blanket, and the solvent is rich between the ink and the blanket. In order to form a boundary layer (Weak Boundary Layer (hereinafter referred to as WBL) that weakens the adhesion between the ink and the blanket), the ink can be transferred without leaving the blanket, and the blanket is heated. The solvent absorbed from the blanket surface volatilizes and the shape variation of the printed pattern is reduced in continuous printing by offset printing. You can. Moreover, the problem of the adhesiveness of the line pattern resulting from these specific resin components can be eliminated by including the monomer which can carry out a crosslinking reaction with the resin component enumerated above.

  The invention according to claim 2 is 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 obtained by mixing these.

  The invention according to claim 3 is the printing ink according to claim 1, wherein the inorganic powder is silver powder.

  The invention according to claim 4 is the invention according to claim 1, wherein the monomer is a printing ink containing one or more polyfunctional monomers or polyfunctional urethane acrylates having two or more acrylic groups or methacrylic groups. It is.

  The invention according to claim 5 is the invention according to claim 1, further comprising a polymerization initiator that promotes a crosslinking reaction by decomposing the ink with light or heat to produce a reactive intermediate. Ink.

  In the invention according to claim 6, as shown in FIG. 1, a printing plate having a concave pattern is filled with printing ink containing at least a powder component composed of an inorganic powder or an organic powder, a resin component, and a solvent component. This is an improvement of the method for producing a coating film using an intaglio offset printing method in which the filled ink is transferred to a printing blanket having a silicone rubber sheet on the surface and then the ink is transferred from the printing blanket to the transfer target.

The characteristic structure is that the inorganic powder is silver powder and Bi ₂ O ₃ —B ₂ O ₃ glass powder, the resin component is an acrylic-styrene copolymer or urethane acrylate , and the solvent component is diethylene glycol monobutyl ether. Or ethylene glycol monobutyl ether , and the ink contains a trifunctional monomer of ethoxylated trimethylolpropane triacrylate as a monomer capable of crosslinking reaction with the resin component, and a carboxylic acid-based dispersant as a dispersant , The resin component and the monomer in the ink transferred to the transfer medium are crosslinked to cure the transferred ink.

  The invention according to claim 7 is the invention according to claim 6, wherein the crosslinking reaction between the resin component and the monomer is performed by radiating heat to the ink.

  The invention according to claim 8 is the method according to claim 6, wherein the crosslinking reaction between the resin component and the monomer is performed by irradiating the ink with light.

  The invention according to claim 9 is the manufacturing method according to claim 6, wherein the inorganic powder is a metal powder, a metal oxide, a metal nitride, or a mixed powder obtained by mixing these.

  The invention according to claim 10 is the method according to claim 6, wherein the inorganic powder is silver powder.

  The invention according to claim 11 is the method according to claim 6, wherein the monomer comprises one or more polyfunctional monomers or polyfunctional urethane acrylates having two or more acrylic groups or methacrylic groups. is there.

  The invention according to claim 12 is the invention according to claim 6, further comprising a polymerization initiator that promotes a crosslinking reaction by decomposing the ink with light or heat to produce a reactive intermediate. It is.

Printing ink of the present invention, inorganic Powder that consists powder component, at least containing a resin component and a solvent component, the inorganic powder is silver powder and Bi ₂ O ₃ -B ₂ O ₃ based glass powder, resin component acrylic - a styrene copolymer or a urethane acrylate, and the solvent component is diethylene glycol monobutyl ether or ethylene glycol monobutyl ether, ethoxylated trimethylol propane as a monomer capable of crosslinking reaction with the ink in the resin component It contains a trifunctional monomer of triacrylate and a carboxylic acid dispersant as a dispersant .

Upper Bark fat component has a high cohesive force, it is possible to suppress the cohesive failure in the ink inside during transfer to the transfer member, the upper Ki溶 component dissolves the resin component in the printing ink When transferred to the printing blanket, part of the solvent component is absorbed into the silicone rubber sheet on the surface of the printing blanket, forming a WBL between the ink and the blanket, so that the ink is placed on the blanket. Transfer can be performed without leaving, and since the solvent absorbed from the blanket surface volatilizes without heating the blanket, there is an advantage that variation in the shape of the printed pattern can be reduced in continuous printing by offset printing . Also, a trifunctional monomer ethoxylated trimethylolpropane triacrylate as a monomer capable of crosslinking reaction with the above Bark fat ingredients, by including each a carboxylic acid dispersant as a dispersing agent, these specific The problem of the stickiness of the line pattern due to the resin component can be solved.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

As a result of diligent investigations on the resin component and solvent component used in printing ink, the resin component and the solvent component, and the effect of the solvent on the silicone rubber sheet on the surface of the printing blanket, the resin component acrylic as - styrene copolymer or a urethane acrylated bets have high cohesive force, it is possible to suppress the cohesive failure in the ink inside during transfer to the transfer member, and generally used as a solvent component Alternatively alcohols and alkyl ethers which are, by the use of diethylene glycol monobutyl ether or ethylene glycol monobutyl ether, it is possible to dissolve the Bark fat component on the printing in the ink, printing blankets When transferred to the Absorbed into the sheet and forms a WBL between the ink and the blanket, so the ink can be transferred without leaving it on the blanket, and the solvent absorbed from the blanket surface volatilizes without heating the blanket It was confirmed.

  However, the line pattern transferred to the transfer medium using the ink containing the resin component and the solvent component listed above is an adhesive that the printing ink before offset printing has after the drying process at 100 to 200 ° C. Sex is maintained. This is because even if the solvent component in the pattern is volatilized in the drying process, the resin component having adhesiveness remains in the pattern. In this way, the line pattern after the drying process has adhesiveness, and when foreign matter adheres to the line pattern before baking, the line pattern after baking is separated or bonded. It also has problems due to the ingredients.

  Therefore, when the resin components listed above are included as components constituting the ink, the printing ink contains a monomer capable of crosslinking reaction with the resin component, and the printing ink is used for transfer. Before firing, by radiating heat or irradiating light to the line pattern transferred to the body to cause the resin component and the monomer to crosslink and harden the surface of the line pattern, thereby eliminating the adhesiveness of the line pattern surface. Even if foreign matter comes into contact with the line pattern, no foreign matter is attached, and it was confirmed that a good line pattern could be obtained after firing, and the present invention was achieved.

  The printing ink of the present invention fills a printing plate having a concave pattern with an ink containing at least a powder component composed of an inorganic powder or an organic powder, a resin component and a solvent component, and the filled ink has a silicone rubber on the surface. This is an improvement of the printing ink used in the intaglio offset printing method in which the ink is transferred from the printing blanket to the transfer medium after being transferred to the printing blanket having the sheet.

The characteristic structure is that the inorganic powder is silver powder and Bi ₂ O ₃ —B ₂ O ₃ glass powder, the resin component is an acrylic-styrene copolymer or urethane acrylate , and the solvent component is diethylene glycol monobutyl ether. Or ethylene glycol monobutyl ether , wherein the ink contains a trifunctional monomer of ethoxylated trimethylolpropane triacrylate as a monomer capable of undergoing a crosslinking reaction with a resin component, and a carboxylic acid dispersant as a dispersant. It is in.

  When it is set as 100 mass% of ink, it is preferable to mix | blend in the ratio of 5-20 mass% of resin components, 7.5-30 mass% of solvent components, and 1-30 mass% of monomers. The solvent components listed above can dissolve the resin component in the printing ink, and when transferred to the printing blanket, a part of the solvent component is absorbed into the silicone rubber sheet on the surface of the printing blanket, and the ink Since the WBL is formed between the blanket and the blanket, the ink can be transferred without leaving it on the blanket, and the solvent absorbed from the blanket surface volatilizes without heating the blanket. By using, there is an advantage that the variation in the shape of the print pattern can be reduced in continuous printing by offset printing.

  The powder component contained in the printing ink of the present invention is an inorganic powder or an organic powder. Specific examples include organic pigments, inorganic pigments, glitter 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 a conductive pattern. Of these, silver powder is particularly preferable. Examples of organic pigments include azo, polyazo, anthraquinone, quinacridone, isoindoline, isoindolinone, phthalocyanine, perylene, DPP, and fluorescent pigments. Examples of inorganic pigments include carbon powders such as acetyl carbon, carbon nanotubes, fullerene, graphite, synthetic silica, chromium oxide, iron oxide, titanium oxide, titanium black, calcined pigment, zinc sulfide, ruthenium oxide, cobalt oxide, manganese oxide, Examples thereof include copper oxide. Examples of glitter pigments include pearl pigments, flake pigments, aluminum pigments and bronze pigments. Examples of organic dyes 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 is an acrylic-styrene system obtained by copolymerizing polyacrylic acid ester such as polymethyl acrylate, polymethacrylic acid ester such as polymethyl methacrylate, and polystyrene, polyurethane, or epoxy resin. Copolymers, acrylic-urethane copolymers, acrylic-epoxy copolymers, urethane acrylates and epoxy acrylates in which a part of polyacrylic acid ester or polymethacrylic acid ester is substituted with urethane or epoxy are included. Moreover, the molecular weight of these resin components is suitably used in the range of hundreds to millions of oligomers to polymers. The low molecular weight resin component is effective for suppressing drying of the ink, and the high molecular weight resin component can suppress cohesive failure inside the ink. That is, it is effective for improving transferability. Therefore, by containing a resin having a low molecular weight to a high molecular weight and a wide molecular weight in the ink, it is possible to satisfy the ink drying suppression and the transferability improvement at the same time. Acrylic-styrene copolymer, acrylic-urethane copolymer, acrylic-epoxy copolymer, urethane acrylate or epoxy acrylate has a high cohesive force, and is used in the ink at the time of transfer to the transfer target. Cohesive failure can be suppressed. You may use the said acrylic styrene-type copolymer etc. individually or in mixture of 2 or more types.

  Among the solvent components contained in the printing ink of the present invention, polyester polyol [aliphatic polybasic acid having 2 to 12 carbon atoms / aliphatic polyhydric alcohol having 2 to 12 carbon atoms] may be poly [(1 , 9-nonanediol) -alt- (adipic acid)], poly [(3-methyl-1,5-pentanediol; trimethylolpropane) -alt- (adipic acid)], poly [(3-methyl-1 , 5-pentanediol) -alt- (sebacic acid)]. Polyester polyol [aromatic polybasic acid having 8 to 15 carbon atoms / aliphatic polyhydric alcohol having 2 to 12 carbon atoms] may be poly [(3-methyl-1,5-pentanediol) -alt-. (Terephthalic acid)] and poly [(3-methyl-1,5-pentanediol) -alt- (isophthalic acid)]. Furthermore, examples of the hydroxyl group-containing liquid acrylic resin include poly 2-hydroxyethyl acrylate, poly 2-hydroxypropyl acrylate, poly 2-hydroxybutyl acrylate, and poly 2-hydroxy methacrylate.

  The monomer contained in the printing ink of the present invention is a component capable of undergoing a crosslinking reaction with the resin components listed above. The monomer contains one or more polyfunctional monomers having two or more acrylic groups or methacryl groups. As the polyfunctional monomer, a monomer having 2 to 6 functional groups is preferable. The reason why the functional group is an acryl group or a methacryl group is that it is easily cross-linked with the terminal of the resin component. The polyfunctional urethane acrylate is preferably a urethane acrylate having 2 to 10 functional groups. The number of functional groups of the monomer to be used is preferably selected in consideration of the reaction rate with the resin component and the combustibility during firing.

  Examples of the bifunctional monomer having an acrylic group include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonanediol. Diacrylate (1,9-Nonanediol Diacrylate), 1,10-decanediol diacrylate (1,10-Decanediol Diacrylate), alkoxylated hexanediol diacrylate (Alkoxylated Hexanediol Diacrylate), ethoxylated 2-methyl-1,3- Propanediol diacrylate (2-Methyl-1,3-propanediol Ethoxy Acrylate), Diethyleneglycol Diacrylate, Triethyleneglycol Diacrylate, Tetraethyleneglycol Diacrylate, Dipropyleneglycol diacrylate Acrylate ( Dipropyleneglycol Diacrylate, Tripropyleneglycol Diacrylate, 1,3-Butyleneglycol Diacrylate, Neopentylglycol Diacrylate, Alkoxylated Neopentylglycol Diacrylate Neopentyl Glycol Diacrylate, Propoxylated Neopentyl Glycol Diacrylate, Cyclohexane Dimethanol Diacrylate, Alkoxylated Cyclohexane Dimethanol Diacrylate, Tricyclodecane Dimethanol Diacrylate Acrylate (Tricyclodecane Dimethanol Diacrylate), Ethoxylated Bisphenol A Diacryla te), Propoxylated Ethoxylated Bisphenol A Diacrylate, 2-Hydroxy 1-Acryloxy 3-Methadryloxy Propane, Acrylate Ester, An alkoxylated aliphatic diacrylate (Alkoxylated Aliphatic Diacrylate) is mentioned.

  Examples of the bifunctional monomer having a methacryl group include 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol. Dimethacrylate (1,6-Hexanediol Dimethacrylate), 1,9-Nonanediol Dimethacrylate, 1,12-Dodecanediol Dimethacrylate, 2-Methyl-1 , 8-Octanediol dimethacrylate (2-Methyl-1,8-octanediol Dimethacrylate), Ethyleneglycol dimethacrylate, Diethyleneglycol Dimethacrylate, Triethyleneglycol dimethacrylate, Tetraethylene glycol The Tacrylate (Tetraethyleneglycol Dimethacrylate), Tripropyleneglycol Dimethacrylate, 1,3-Butyleneglycol Dimethacrylate, Neopentylglycol Dimethacrylate, Ethoxylated Bisphenol A Dimethacrylate ( Ethoxylated Bisphenol A Dimethacrylate), glycerin dimethacrylate (2-Hydroxy 1-3 dimethacryloxy Propane), cyclohexane dimethanol dimethacrylate, and tricyclodecane dimethanol dimethacrylate.

  Examples of the trifunctional monomer having an acrylic group include ethoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate (Pentaerythritol). Triacrylate), Propoxylated Trimethylolpropane Triacrylate, Trimethylolpropane Triacrylate, Tris (2-hydroxyethyl) isocyanurate triacrylate (Tris (2-Hydroxyethyl) Isocyanurate Triacrylate) It is done.

  Examples of the trifunctional monomer having a methacrylic group include trimethylol propane trimethacrylate (Trimethylol Propane Trimethacrylate) and ethoxylated trimethylol propane trimethacrylate (Ethoxylated Trimethylol Propane Trimethacrylate).

  Examples of tetrafunctional monomers and pentafunctional monomers include ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate. Examples include Pentaacrylate, propoxylated pentaerythritol tetraacrylate, Pentaacrylate Ester, and Pentaerythritol Tetraacrylate.

  Moreover, in order to accelerate | stimulate a crosslinking reaction, it is preferable to make the printing ink of this invention further contain a polymerization initiator. With this polymerization initiator, the crosslinking reaction can be promoted by decomposing with light or heat to produce a reactive intermediate. When the ink is 100% by mass, it is preferably blended at a ratio of 20 parts by mass or less of the polymerization initiator.

  The polymerization initiator contained in the printing ink of the present invention that decomposes by light, generates a reaction intermediate, and promotes the crosslinking reaction includes benzyldimethyl ketal, α-hydroxyketone, benzophenone, aminoketone, bisacylphosphine oxide And metallocene. The polymerization initiator contained in the printing ink of the present invention is decomposed by heat to generate a reaction intermediate and accelerate the crosslinking reaction. Examples of the polymerization initiator include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, Examples include diacyl peroxide, peroxyester, and peroxydicarbonate.

  The printing ink of the present invention may further contain a dispersant. By further containing a dispersant, an effect of smoothing the coated layer surface can be obtained. When the ink is 100% by mass, the dispersant is preferably blended in a proportion of 3 to 10% by mass. In addition, the sharpness at the edge portion of the line to be formed is increased. As the dispersant, carboxylic acid type or polycarboxylic acid type polymer anion, allyl ether copolymer, polyamine-fatty acid condensate, polymer surfactant, polymer fatty acid, phosphate ester, fatty acid ester condensate, etc. are used. Is preferred.

  Next, the manufacturing method of the coating film using the printing ink of this invention is demonstrated.

  In the production method of the present invention, printing ink is printed by the intaglio offset method. First, as shown in FIG. 1A, a flat 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 flat intaglio 10. The supplied printing ink 11 is embedded in the concave pattern 10 a by sliding the squeegee 12 against the surface of the flat intaglio 10. Next, as shown in FIG. 1B, a blanket roll 13 having a silicone rubber sheet 13a attached to the surface is prepared as a printing blanket, and the blanket roll 13 is a plane in which the ink 11 is embedded in the concave pattern 10a. The blanket roll 13 is pressed against the intaglio 10, and the blanket roll 13 is rotated in this state and slid on the flat intaglio 10. Transfer to the surface of the sheet 13a. The transfer rate at this time is approximately 20 to 60%, although it varies depending on the concave pattern of the plane intaglio, the components contained in the ink, the ratio thereof, and the pressure of the blanket. A part of the solvent component contained in the transferred ink 11 of the present invention is absorbed in the silicone rubber sheet 13a on the surface of the blanket roll 13, and a boundary layer (WBL) rich in solvent is formed between the ink and the silicone rubber sheet 13a. Therefore, in the subsequent process, the ink can be transferred to the transfer medium without leaving it on the blanket. Next, as shown in FIG. 1 (c), the blanket roll 13 to which the ink 11 has been transferred is pressed against a transfer medium such as a glass substrate 14, and the blanket roll 13 is rotated in this state, By sliding, the desired pattern 11 is transferred to the surface of the glass substrate 14 as shown in FIG. A silicone resin sheet may be attached to the surface of the blanket roll instead of the silicone rubber sheet. In the printing ink 11 of the present invention, the resin component has a high cohesive force and can suppress cohesive failure inside the ink at the time of transfer to the transfer target, and the solvent component is a resin component in the printing ink. When it is transferred to the printing blanket, part of the solvent component is absorbed in the silicone rubber sheet on the surface of the printing blanket, and the ink is blanketed to form a WBL between the ink and the blanket. The transfer can be performed without leaving it on, and the solvent absorbed from the blanket surface volatilizes without heating the blanket, so that the variation in the shape of the printed pattern can be reduced in continuous printing.

  In addition, after diethylene glycol monobutyl ether or ethylene glycol monobutyl ether as a solvent component transfers a part of the ink 11 shown in FIG. 1B to the surface of the silicone rubber sheet 13a of the blanket roll 13, it is shown in FIG. It is preferable to change the blending ratio according to the interval until the desired pattern is transferred to the surface of the glass substrate 14 shown. That is, when it takes a long time to transfer the ink to the transfer medium after transferring the ink to the roll, for example, when used in a large apparatus, diethylene glycol monobutyl ether having a high boiling point is used alone or the ratio of diethylene glycol monobutyl ether When the time from the transfer of the ink to the roll to the transfer of the ink to the transfer material is short, for example, for use in a small apparatus, ethylene glycol monobutyl ether having a low boiling point is used alone or A large proportion of ethylene glycol monobutyl ether is used.

  Next, the pattern 11 transferred to the surface of the glass substrate 14 is held at 100 to 200 ° C. for 10 to 30 minutes to dry the pattern.

Even after the pattern 11 transferred to the surface of the glass substrate 14 has undergone the drying step, the adhesiveness of the printing ink before offset printing is maintained. Therefore, as shown in FIG. 1 (d), the pattern transferred from the ultraviolet lamp 17 covered by the lamp house 16 except for the irradiated portion is irradiated with ultraviolet rays. By irradiating the transferred pattern 11 with ultraviolet rays, the resin component and the monomer contained in the printing ink of the present invention undergo a crosslinking reaction to form a pattern 11a whose surface is cured. Since the cured pattern 11a has lost its adhesiveness on the surface, even if foreign matter comes into contact with the line pattern before firing, the foreign matter will not adhere. Therefore, a good line pattern can be obtained after firing. Ultraviolet irradiation conditions are high-pressure mercury lamp or metal halide lamp (center wavelength: 365 nm) and a condensing type mirror, the ultraviolet peak intensity is 300 to 10000 mW / cm ² , the irradiation distance is the focal length of the mirror, and conveyance It is preferable that the speed is 0.1 to 10 m / min. When the ultraviolet peak intensity is less than the lower limit value, the crosslinking reaction does not proceed sufficiently, and the adhesiveness of the pattern surface remains. If the ultraviolet peak intensity exceeds the upper limit value, the temperature rise in the irradiation area becomes too large locally, which causes problems such as pattern swelling. Further, when the irradiation distance deviates from the focal distance of the mirror, a predetermined ultraviolet peak intensity cannot be obtained, and the pattern surface may not be sufficiently cured.

  In the present embodiment, an example by ultraviolet irradiation is shown, but the same effect can be obtained even if a crosslinking reaction between the resin component and the monomer is caused by radiating heat to the line pattern. As for the heat irradiation conditions, it is preferable to use a heater coil or an ultraviolet lamp and heat at 150 to 250 ° C. for 1 to 30 minutes.

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

<Example 1>
The powder component, the resin component, the solvent component, the monomer and the dispersant shown in the following Table 1 were mixed with a mixer, and further kneaded for about 5 to 10 Pa · s using a three-roll mill to obtain a printing ink.

A metal plate intaglio having a plurality of concave patterns with a line width of 100 μm, a depth of 25 μm, and a pitch of 360 μm was prepared as a printing plate used for offset printing, and a glass substrate was prepared as a transfer target. A blanket roll having a 0.3 mm thick silicone rubber sheet attached to the surface was used as a printing blanket. First, a predetermined amount of the printing ink obtained on the surface of the intaglio plate was supplied, and the ink was embedded in the indentation pattern of the intaglio plate using a SUS blade. Next, the blanket roll was rotated in a state of being pressed against the flat intaglio and slid on the flat intaglio to transfer a part of the ink embedded in the concave pattern of the flat intaglio onto the silicone rubber sheet surface of the blanket roll. . Finally, the blanket roll was rotated while being pressed against the glass substrate, and slid on the glass substrate to obtain a printed substrate having a predetermined pattern on the glass substrate surface. The obtained substrate was held at 120 ° C. for 10 minutes to dry the printed pattern. The dried printed pattern was irradiated with ultraviolet rays to cure the film. The irradiation conditions were as follows: a high-pressure mercury lamp with a central wavelength of 365 nm and a condensing mirror were used, the ultraviolet intensity was 700 mW / cm ² , the irradiation distance was 8 cm, and the substrate was transferred at a transfer speed of 3 m / min.

<Example 2>
Ink for printing by mixing the powder component, resin component, solvent component, monomer, polymerization initiator and dispersant shown in the following Table 1 with a mixer and further kneading about 5 to 10 Pa · s using a three-roll mill. Got.

  Using this printing ink, a printed substrate having a predetermined pattern on the glass substrate surface was obtained in the same manner as in Example 1. The obtained substrate was held at 120 ° C. for 10 minutes to dry the printed pattern. The dried printed pattern was irradiated with ultraviolet rays under the same irradiation conditions as in Example 1 to cure the film.

<Example 3>
Ink for printing by mixing the powder component, resin component, solvent component, monomer, polymerization initiator and dispersant shown in the following Table 1 with a mixer and further kneading about 5 to 10 Pa · s using a three-roll mill. Got.

  Using this printing ink, a printed substrate having a predetermined pattern on the glass substrate surface was obtained in the same manner as in Example 1. The obtained substrate was held at 120 ° C. for 10 minutes to dry the printed pattern. The printed substrate having the dried printed pattern was held at 230 ° C. for 1 minute in an infrared heating furnace to cure the film.

<Comparative Example 1>
The powder component, the resin component, the solvent component and the dispersant shown in the following Table 1 were mixed with a mixer and further kneaded for about 5 to 10 Pa · s using a three-roll mill to obtain a printing ink.

  Using this printing ink, a printed substrate having a predetermined pattern on the glass substrate surface was obtained in the same manner as in Example 1. The obtained substrate was held at 120 ° C. for 10 minutes to dry the printed pattern. The dried printed pattern was irradiated with ultraviolet rays under the same irradiation conditions as in Example 1 to cure the film.

<Comparison test 1>
Tacking property evaluation was performed on the print patterns obtained in Examples 1 to 3 and Comparative Example 1. The evaluation of tackiness was performed by the powder shake-off method. Specifically, the substrate was placed horizontally so that the printed pattern was positioned on top, and the resin powder was sprinkled on the printed pattern and allowed to stand for 1 minute. Subsequently, the substrate after standing was made vertical, and the powder sprinkled on the printed pattern was shaken off. The surface state of the printed pattern after the powder was shaken off was confirmed visually. The evaluation was “good” when no resin powder was adhered, and “bad” when much of the resin powder remained adhered. The results are shown in Table 2. Moreover, the printed pattern surface state after shaking off the powder of Example 1 is shown in FIG. 2 (a), and the printed pattern surface state after shaking off the powder of Comparative Example 1 is shown in FIG. 2 (b).

As is clear from Table 2 and FIGS. 2A and 2B, the coating film using the printing ink of Comparative Example 1 has a considerably large amount of the sprinkled powder even after being shaken off. It was confirmed that the powder continued to adhere. From this, it was found that when a specific resin component was used, the coating film had adhesiveness even after drying. On the other hand, it was confirmed that no powder adhered to the coating film using the printing inks of Examples 1 to 3, and the film was cured, so that it did not adhere even when the powder contacted.

Schematic of the offset printing method. (A) The figure which shows the tackiness evaluation result using the printing ink of Example 1. FIG.

            (B) The figure which shows the tackiness evaluation result using the printing ink of the comparative example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Plane intaglio 10a Concave pattern 11 Printing ink 12 Squeegee 13 Blanket roll 13a Silicone rubber sheet 14 Glass substrate 16 Lamp house 17 Ultraviolet lamp

Claims (6)

Inorganic Powder that consists powder component, a resin component and a solvent component filled with ink containing at least a printing plate having a concave pattern, transferred to the printing blanket having a silicone rubber sheet to the filled ink surface Then, in the printing ink used in the intaglio offset printing method for transferring the ink from the printing blanket to the transfer body,
The inorganic powder is silver powder and Bi ₂ O ₃ —B ₂ O ₃ glass powder,
The resin component A acrylic - a styrene copolymer or a urethane acrylate, and wherein the solvent component is diethylene glycol monobutyl ether or ethylene glycol monobutyl ether,
The ink, printing ink, wherein the trifunctional monomer ethoxylated trimethylolpropane triacrylate as a monomer capable of crosslinking reaction with the resin component, to include each a carboxylic acid dispersant as a dispersing agent .   The printing ink according to claim 1, further comprising a polymerization initiator that promotes a crosslinking reaction by decomposing the ink with light or heat to produce a reactive intermediate. Inorganic Powder that consists powder component, printing blanket the printing ink a resin component and a solvent component contained respectively filled into the printing plate having a concave pattern, with a silicone rubber sheet to the filled ink surface In the method for producing a coating film using an intaglio offset printing method for transferring ink from the printing blanket to the transfer target,
The inorganic powder is silver powder and Bi ₂ O ₃ —B ₂ O ₃ glass powder,
The resin component A acrylic - a styrene copolymer or a urethane acrylate, and wherein the solvent component is diethylene glycol monobutyl ether or ethylene glycol monobutyl ether,
The ink contains a trifunctional monomer of ethoxylated trimethylolpropane triacrylate as a monomer capable of undergoing a crosslinking reaction with the resin component, and a carboxylic acid dispersant as a dispersant ,
A method for producing a coating film, wherein the resin component in the ink transferred to the transfer medium and the monomer are subjected to a crosslinking reaction to cure the transferred ink. The production method according to claim 3 , wherein the crosslinking reaction between the resin component and the monomer is performed by radiating heat to the ink. The production method according to claim 3 , wherein the crosslinking reaction between the resin component and the monomer is performed by irradiating the ink with light. The production method according to claim 3 , further comprising a polymerization initiator that promotes a crosslinking reaction by generating a reactive intermediate by decomposing the ink with light or heat.