JP2018095885A - Composition for conductive pattern printing and method for manufacturing substrate having conductive pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for conductive pattern printing which corresponds to absorption of a solvent of a composition for conductive pattern printing to a blanket, improves transferability from the blanket to the substrate, and has good transferability even when large and small line widths coexist in one substrate.SOLUTION: A composition for conductive pattern printing contains at least conductive powder, a binder resin and a mixed solvent, and contains 2 mass% or more and 60 mass% or less of a solvent (H) having an SP value of 9.4 or more and 12.1 or less with respect to the total of the mixed solvent, where the mixed solvent contains a solvent (A) having an SP value smaller than that of at least one solvent (H) by 0.3 or more.SELECTED DRAWING: None

Description

  The present invention relates to a conductive pattern printing composition, and more specifically, a conductive pattern printing composition containing a mixed solvent composed of two or more solvents specified by SP values, and a conductive material using the same. The present invention relates to a method for manufacturing a substrate having a conductive pattern.

  Etching methods, printing methods, and the like are known as methods for forming conductive patterns such as wiring, electrodes, and conductive circuits of electronic and electrical components such as touch panels, electronic paper, photovoltaic panels, and multilayer ceramic capacitors. .

When a conductive pattern is formed by etching, a photoresist is applied on a substrate on which a metal film is deposited, a resist pattern is formed by pattern exposure and development processing, and then a portion of the metal where the resist pattern does not exist The film is dissolved and removed, and finally the resist pattern is removed.
However, such an etching method requires many steps as described above, and the steps are very complicated, and there is a material loss due to dissolution and removal of the metal film, resulting in poor mass productivity. ing.

  On the other hand, when a conductive pattern is formed by a printing method, it is possible to mass-produce a desired pattern at a low cost. Further, the conductive pattern can be easily made conductive by drying or curing the printed composition. The conductive pattern can be obtained.

Printing methods used for such printing methods include line width, pattern linearity, thickness, line width accuracy, relative position accuracy, absolute position accuracy, surface smoothness (reduction of surface irregularities), production speed, etc. to be formed. In accordance with the above, flexographic printing, inkjet printing, gravure printing, screen printing (Patent Document 1 etc.), gravure offset printing (Patent Documents 2-5 etc.), screen offset printing (Patent Document 6 etc.), tampo printing (Patent Document 7) Etc.), offset printing (lithographic printing), letterpress printing, rotary screen printing, letterpress reversal printing, dispenser printing, electrostatic discharge ink jet printing, and the like.
Among them, the printing method that once transfers or prints on the blanket and then transfers it again to the substrate allows the pattern to be thinned, the pattern shape to be stabilized, and a certain amount of printing composition to be transferred. Has been attracting attention.

  In gravure offset printing, a printing composition is filled into an intaglio plate having concave portions corresponding to a desired pattern using a doctor blade or the like, and then the printing composition is transferred to a blanket. The pattern is formed on the substrate by transferring again from the substrate to the substrate. This pattern becomes a conductive pattern by being cured or baked by irradiation with light such as heat or UV.

  In screen offset printing, a printing composition is printed on a blanket from a screen plate formed corresponding to a desired pattern, and the pattern is formed on the substrate by transferring the blanket to the substrate. It becomes a conductive pattern by curing or baking by irradiation with light such as heat or UV.

  In tampo printing, a printing composition is filled into an intaglio in which concave portions are formed corresponding to a desired pattern, and then the printing composition is transferred to a blanket called a soft hemispherical or ship-bottom tampo, The pattern is formed on the substrate by pressing the tampo (blanket) against the substrate and transferring the printing composition on the tampo (blanket) to the substrate again. This pattern becomes a conductive pattern by being cured or baked by irradiation with light such as heat or UV.

  However, in any of the printing methods described above, the known conductive pattern printing composition is not excellent in transferability from the plate to the blanket, particularly transferability from the blanket to the substrate, and is excellent in printability. There wasn't.

In recent years, the line width of a pattern has been required to form a high-definition conductive pattern having a line width of 50 μm or less, for example, from the viewpoints of downsizing and high integration of the electronic components. In some cases, a pattern having a line width of several hundred μm coexists in the same substrate, and the formation of the pattern is also required.
In addition, they have to be formed by a single printing, but there is a problem in the known technology (insufficient) to cope with this, and there is room for further improvement with respect to the conductive pattern printing composition. there were.

JP 2009-269976 A JP 2010-159350 A JP 2010-235780 A JP 2014-034589 A JP2015-172103A International Publication No. 2014/050560 JP 2014-226859 A

  The present invention has been made in view of the above-described background art, and the problem is that, in a printing method having a step of once transferring to a blanket, the transferability of a fine line pattern from a plate to a blanket is improved, and conductive pattern printing is performed. Provided is a conductive pattern printing composition having improved transferability from a blanket to a substrate, corresponding to absorption of the composition (hereinafter sometimes simply referred to as “printing composition”) into a blanket of a solvent. In particular, another object is to provide a method of manufacturing a substrate having a conductive pattern using the same.

In the following, the problem relating to “transferability of the printing composition from the blanket to the substrate” will be specifically described.
Compared with the printing method in which the printing composition is directly transferred from the plate to the substrate, the printing method in which the printing composition is once transferred from the plate to the substrate through the blanket can be thinned and used for a certain amount of printing. The composition can be transferred, and the pattern shape can be stably formed.

However, in the printing method in which the printing composition is once transferred from the plate to the substrate via the blanket, there is no printing composition that can withstand practical use.
In the present invention, it has been clarified that the following problem solving is extremely important for the transferability of the printing composition from the blanket to the substrate.
Although the present invention has a problem to provide a printing composition with improved printability (especially improved transferability from a blanket to a substrate), the present invention has found the following problems prior to that. Also exists.

That is, when the width of the pattern to be printed is reduced (for example, when the width is 20 to 30 μm), the amount of the printing composition transferred from the blanket to the substrate is drastically reduced.
In general, the transfer amount of printing using an intaglio is determined by the depth of the intaglio groove. Since the groove depth of the pattern having a line width of 20 μm to 30 μm must be shallow from the plate manufacturing method, the transfer amount is extremely limited.

On the other hand, if the transfer of the printing composition from the blanket to the substrate is not almost the total amount of the printing composition on the blanket, the above-mentioned “printing method having a step of transferring from the plate to the blanket once” can be utilized. Can not.
However, when the width of the printed pattern becomes narrower and the amount of the printing composition on the blanket decreases accordingly, “the surface area per unit volume increases due to the pattern miniaturization, and the evaporation of the solvent from the pattern surface `` Accelerated '' and `` the solvent in the printing composition transferred to the blanket is absorbed by the blanket '', `` the solid content concentration of the printing composition is increased and becomes dry and sticky (hereinafter, “Phenomenon in which“ tack ”is sometimes reduced” is important. That is, when the width of the pattern is narrowed, the total amount of the printing composition on the blanket is reduced, so even if a small amount of solvent is evaporated or absorbed by the blanket, the pattern of the printing composition on the blanket. The reduction in stickiness is not negligible, and the reduction in stickiness deteriorates the transferability of the printing composition from the blanket to the substrate.
This phenomenon occurs in the same manner even when a solvent having a low vapor pressure (a solvent that is difficult to dry, a so-called “slow solvent”) is used.

In order to suppress such a reduction in stickiness, it is conceivable to use a solvent that is not easily absorbed by the blanket.
However, if a solvent that is not easily absorbed by the blanket is used, the solid content concentration of the printing composition on the blanket is hardly increased, and the so-called “wet state” is maintained. Therefore, the adhesion of the printing composition pattern on the blanket to the blanket and the adhesion to the substrate become too high, and the pattern on the blanket contains a lot of solvent, so the composition on the blanket becomes soft. The pattern is divided in the thickness direction of the printing composition on the blanket (the pattern causes bulk destruction (crying)), and a so-called “crying phenomenon” occurs in which transferability to the substrate deteriorates.

Hereinafter, “the solvent in the printing composition is absorbed by the blanket, etc., and the stickiness of the pattern of the printing composition on the blanket is reduced, and the transferability of the printing composition from the blanket to the substrate is reduced. The property of suppressing “a phenomenon that deteriorates” is sometimes abbreviated as “tack maintenance”.
In addition, since the solvent in the printing composition is difficult to be absorbed by the blanket, the pattern of the printing composition on the blanket remains containing a lot of solvent, and the pattern is a printing composition on the blanket. The property of suppressing the phenomenon of being divided between the thickness directions and deteriorating the transferability to the substrate is sometimes abbreviated as “bulk fracture suppressing property”.

  As a result of intensive studies to solve the above problems, the present inventor used two or more kinds of mixed solvents, each SP value of each solvent is in a specific range / relationship, and the content of a specific solvent It was found that the above-mentioned problems can be solved by setting the range to a specific range, and the present invention has been completed.

That is, the present invention is a conductive pattern printing composition containing at least a conductive powder, a binder resin, and a mixed solvent,
A solvent (H) having an SP value of 9.4 or more and 12.1 or less is contained in an amount of 2% by mass or more and 60% by mass or less based on the entire mixed solvent,
And this mixed solvent contains the solvent (A) whose SP value is 0.3 or less with respect to at least 1 sort (s) of solvent (H), and provides the composition for electroconductive pattern printing characterized by the above-mentioned. is there.

  In the present invention, the mixed solvent contains a solvent (L) having an SP value of 7.8 or more and 9.1 or less and a solvent (H) having an SP value of 9.4 or more and 12.1 or less. The conductive pattern printing composition is provided in which the total content of the solvent (L) and the solvent (H) is 70% by mass or more based on the total of the mixed solvent.

  The present invention also relates to a method for printing a substrate having a conductive pattern, wherein the conductive pattern printing composition is used to print a pattern on a substrate, and the conductive pattern composition is used as a printing plate. The present invention provides a method for producing a substrate having a conductive pattern, which comprises a step of transferring from a blanket to a blanket and a step of transferring from the blanket to a substrate.

According to the present invention, it is possible to provide a conductive pattern printing composition that solves the above-mentioned problems and problems and achieves both “tack maintenance” and “bulk breakage suppression”.
That is, in a printing method having a process of once transferring to the blanket, the transferability of the fine line pattern from the plate to the blanket is improved, the solvent of the printing composition is absorbed into the blanket, and the transferability from the blanket to the substrate An object of the present invention is to provide a composition for printing an electrically conductive pattern, and to provide a method for producing a substrate having an electrically conductive pattern using the composition.

In addition, even when patterns with small and large line widths are mixed on a single substrate, both the “tack maintenance” and the “bulk breakdown suppression” are compatible with many line width patterns. An electrically conductive pattern printing composition can be provided.
That is, according to the conductive pattern printing composition of the present invention, “tack maintenance” that tends to be a problem when the pattern has a small line width and a problem when the pattern has a large line width (pattern having a large area). It is possible to achieve both “bulk fracture suppression” that tends to occur.

  If the printing composition of the present invention is used, in the method for producing a substrate having a conductive pattern comprising the steps of transferring the printing composition from a printing plate to a blanket, and transferring the blanket to the substrate, Adapting to “large and small line width patterns in one substrate”, it becomes possible to realize a method for manufacturing a substrate having a conductive pattern that achieves both “tack maintenance” and “bulk breakdown suppression”. .

  Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.

The present invention is a conductive pattern printing composition containing at least a conductive powder, a binder resin, and a mixed solvent,
A solvent (H) having an SP value of 9.4 or more and 12.1 or less is contained in an amount of 2% by mass or more and 60% by mass or less based on the entire mixed solvent,
And this mixed solvent contains the solvent (A) whose SP value is 0.3 or more small with respect to at least 1 sort (s) of solvent (H), It is a composition for conductive pattern printing characterized by the above-mentioned.
Hereinafter, the “conductive pattern printing composition” may be simply abbreviated as “printing composition”.

<Conductive powder>
The printing composition of the present invention contains a conductive powder. The conductive powder contained in the printing composition of the present invention is not particularly limited. Specifically, for example, nickel, copper, gold, silver, aluminum, zinc, tin, lead, chromium, platinum, Powders of metals such as palladium, tungsten, molybdenum, indium, chromium, silicon, germanium; powders of these alloys; powders of these mixtures; powders having good conductivity with compounds of these metals; silver oxide, oxidation Metal oxide powders such as copper, aluminum oxide, nickel oxide and tin oxide; powders in which inorganic or organic particles are covered with a metal film; organic conductive powders such as carbon black, thiophene and aniline; . Among these, powders of metals such as nickel, copper, gold, silver, aluminum, platinum, and palladium; powders of these alloys; and the like are preferable, and silver powder has stable high conductivity, is hardly oxidized, and is thermally conductive. It is particularly preferable because the characteristics are good and the cost is good.

Although there is no limitation in particular as specific silver powder, the following goods can be used as an example.
AG2-1C, AG2-8, AG2-11, FA-D-5 manufactured by DOWA Electronics Co., Ltd .; SPQ03R, SPQ05S, SF-K manufactured by Mitsui Mining & Smelting Co., Ltd .; 050, Sylbest TC905S ("Sylbest" is a registered trademark); K-1631P, AC-4048 manufactured by METALOR.

  The particle diameter of the conductive powder is not particularly limited as long as it is sufficiently smaller than the width of the pattern to be printed, but the median diameter (D50) is preferably 0.01 to 6 μm as the average particle diameter. More preferably, it is 0.03-5 micrometers, and it is especially preferable that it is 0.1-4 micrometers. Further, a flaky powder and a spherical powder can be used in combination. The flaky powder can be expected to have high conductivity because the contact area between the particles can be increased.

If the average particle size is too small, the preparation of the conductive powder may be difficult, the conductivity may be decreased, the dispersion may be difficult, the structural viscosity may be difficult to adjust, and the average particle size may be too large. In some cases, dispersion becomes difficult, dispersion stability deteriorates, pattern shape deteriorates, and the like.
If the average particle size is within this range, the composition of the printing composition has good viscosity, fluidity, structural viscosity, thixotropy (change in time of structural viscosity), etc. due to a synergistic effect with the mixed solvent described later, and gravure offset printing. In a printing method using a blanket (tampo), such as screen offset printing or tampo printing, even when printing is continuously performed on a printing machine, trouble is unlikely to occur and it is easy to obtain a stable conductive pattern.

  The content ratio of the conductive powder described above and the binder resin described later is not particularly limited, but the binder resin is preferably 0.3% by mass or more and 30% by mass or less, preferably 1% by mass or more and 20% by mass per 100 parts by mass of the conductive powder. More preferably, it is more preferably 3% by mass or less and 15% by mass or less.

<Binder resin>
The printing composition of the present invention contains a binder resin. The binder resin forms a resin film on the substrate after printing, and fixes the conductive powder on the substrate. In the present invention, the “binder resin” includes a relatively low molecular weight curing such as an epoxy resin or a polyfunctional acrylic monomer (oligomer) such as a curable compound (curable resin) that is cured to become a resin. A curable compound (curable resin) is also included. Also included are mixtures thereof.
The binder resin may be cured or crosslinked in the presence of a curable compound or a curing agent, or may not be cured or crosslinked.

The binder resin is preferably one that can form a good film on the substrate, forms a good film on the blanket, and allows the film of the printing composition to be completely transferred from the blanket to the substrate.
If it is soluble in a mixed solvent described later having a specific SP value in the present invention and the mixed solvent is used (when dissolved in the mixed solvent), the content and molecular weight of the binder resin are appropriately adjusted. A binder resin capable of improving the above-described “tack maintenance” and “bulk breakage suppression” is preferable.

The binder resin in the present invention is a curable resin (compound) that is cured by heat, light, electron beam, or the like, which increases the hardness of the conductive pattern on the substrate, increases the adhesion to the substrate, and heat resistance. It is preferable from the viewpoint of improving the properties.
When a curable resin or compound is used, it is preferable that a curable functional group is present in the molecular structure of the resin as described above.

  The binder resin is not particularly limited. Specific examples of the binder resin that does not contain a curable functional group include polyester, polycarbonate, polyvinyl chloride, vinyl chloride, and other unsaturated double bond-containing monomers. Copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, homopolymer of (meth) acrylic acid ester, (meth) acrylic acid ester and other unsaturated dicarboxylic acids Copolymer with a monomer containing a heavy bond, polystyrene, a copolymer of styrene with another unsaturated double bond-containing monomer, a ketone-formaldehyde condensate or a hydrogenated product thereof, an epoxy resin, a phenoxy resin, a polyvinyl acetal or its Copolymers, polyurethanes, polyureas, polyamides and the like can be mentioned. These can be used alone or in combination of two or more.

Specific resin names of the polyester and the vinyl chloride-vinyl acetate copolymer are not particularly limited, but the following products can be used as an example.
For polyester, Byron 200 manufactured by Toyobo Co., Ltd., Eritel UE3200 manufactured by Unitika Co., Ltd .; For vinyl chloride-vinyl acetate copolymer, Solvein AL, Solvein TA5R, Solvein TA3 manufactured by Nissin Chemical Industry Co., Ltd .; ) Kaneka Kane Vinyl T555.

  Furthermore, the resin (polymer) etc. which have a curable functional group in the side chain or terminal of said resin (polymer) are mentioned. These may be used alone or in combination of two or more, including those having no functional group.

  As the curable compound (curable resin) conceptually included in the binder resin, those having a functional group are preferable. Polyhydric alcohol having a hydroxyl group as a functional group, epoxy resin (glycidyl compound) having an epoxy group (glycidyl group), polyvalent carboxylic acid having a carboxyl group, (meth) acrylate monomer or oligomer having a (meth) acryl group, etc. Particularly preferred.

  As the epoxy resin, generally used epoxy resins can be used as long as they are polyfunctional epoxy resins having two or more epoxy groups in one molecule. Specifically, for example, bisphenol A Type, AP type, B type, BP type, C type, E type, F type, S type epoxy resin (bisphenol type epoxy resin); novolac type epoxy resin; biphenyl type epoxy resin; naphthalene type epoxy resin; 4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolpropane diglycidyl ether, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolpropane triglycidyl ether, tris ( Hydroxyphenyl) methanetri Polyhydric glycidyl compounds such as glycidyl ether; and the like.

The phenoxy resin is a thermoplastic resin, is excellent in film-forming properties, and is preferable because contact between conductive particles is unlikely to deteriorate even if a large amount of conductive powder is contained in the composition.
The phenoxy resin preferably has a number average molecular weight (Mn) of 3000 or more, more preferably 10,000 or more, preferably 40000 or less, and more preferably 20000 or less. Within this range, the film forming property and the above effects are excellent.

Although there is no limitation in particular as an epoxy resin and a phenoxy resin, the following goods can be used as an example.
Regarding the epoxy resin, EPICLON 830, EPICLON 840, EPICLON 850 manufactured by DIC Corporation; Epoto YD-127, Epototo YD-128 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. jER828 manufactured by Mitsubishi Chemical Corporation; EPOX- manufactured by Printec Co., Ltd. MKR710, EPOX-MKR1710.
About phenoxy resin, Mitsubishi Chemical Corporation jER1256; Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YP-50S; InChem PKHC, PKHB.

Examples of the polyfunctional alcohol include low molecular polyol compounds, and specific examples include bifunctional alcohols such as polyethylene glycol, polypropylene glycol, and butylene glycol; 3 such as trimethylolpropane, glycerin, pentaerythritol, and sorbitol. Examples include alcohols that are functional or higher.
Moreover, for example, polymer polyol compounds such as polyester polyol having a molecular weight of 800 or more, polyether polyol, polycarbonate polyol, polycaprolactone polyol, and the like can be mentioned.

  As the binder resin, it is also preferable to use a combination of two or more of polyester, phenoxy resin, epoxy resin, vinyl chloride-vinyl acetate copolymer resin, and the like.

  In the printing composition of the present invention, the content of the binder resin varies depending on the printing method. For example, any of gravure offset printing, screen offset printing, and tampo printing is 2% by mass with respect to the entire printing composition. It is preferably 30% by mass or less, more preferably 3% by mass or more and 27% by mass or less, and particularly preferably 4% by mass or more and 25% by mass or less.

  When the binder resin content is within this range, the viscosity, fluidity, structural viscosity, thixotropy (change in time of structural viscosity), etc. of the printing composition are good due to a synergistic effect with the mixed solvent described later. Even when printing is continuously performed on the machine, trouble does not easily occur and it becomes easy to obtain a stable conductive pattern.

<Curing agent>
In the printing composition of the present invention, it is also preferable to use a curing agent in combination with the binder resin after making the binder resin curable.

  Specific examples of such a curing agent include oxetane compounds, acid anhydrides, amines, imidazoles, and phenols (resins). The curing agent also includes a latent curing agent (amine adduct, block isocyanate compound, etc.) and a curing accelerator (octylate, etc.). These can be used alone or in combination of two or more.

Although there is no limitation in particular as a latent hardening | curing agent or a hardening accelerator, the following goods can be specifically used as an example.
About block polyisocyanate compound, Nippon Polyurethane Industry Co., Ltd. Coronate AP-M, Coronate 2503, Coronate 2507, Coronate 2513, Coronate 2015; Asahi Kasei Chemicals Corporation Duranate 17B-60P, Duranate TPA-B80E, Duranate MF-K60B Duranate E402-B80B; Mitsui Chemicals, Inc. Takenate B-830, Takenate B-815N, Takenate B-846N, Takenate B-882N.
About Amine Adduct, Ajinomoto Fine Techno Co., Ltd. Amicure PN-23, Amicure PN-H, Amicure PN-40, Amicure PN-F, Amicure MY-24, Amicure MY-25; Shikoku Kasei Kogyo Co., Ltd. Duct P-0505.
For octylate and the like, U-CAT SA1, U-CAT SA102, U-CAT SA102-50, U-CAT SA106 manufactured by San Apro Co., Ltd.

The curing agent contains a functional group capable of reacting with the binder resin for the purpose of curing by covalent bond formation in a pattern baking step after printing, and the adhesion of the conductive pattern to the substrate And from the viewpoint of heat resistance.
The curing agent becomes a solid at 50 ° C. due to integration with the binder resin in the above-described reaction, and develops adhesiveness and heat resistance of the conductive pattern.
In the case of containing a curing agent, there is no particular limitation, but it is preferably 0.1% by mass or more and 100% by mass or less, and particularly preferably 0.3% by mass or more and 50% by mass or less with respect to the entire curable binder resin. .

<Solvent>
The printing composition of the present invention contains at least a conductive powder, a binder resin, and a mixed solvent. Among these, the mixed solvent is:
(1) The solvent (H) having an SP value of 9.4 or more and 12.1 or less is contained in an amount of 2% by mass or more and 60% by mass or less with respect to the entire mixed solvent, and
(2) A solvent (A) having an SP value of 0.3 or more smaller than that of at least one solvent (H) is contained.
Here, the “mixed solvent” refers to the entire mixture of all the solvents contained in the printing composition. In addition, the “relatively low molecular weight curable compound that is cured to become a resin” as described above is conceptually included in the binder resin even if it is liquid at room temperature, and the (mixed) solvent. Is not conceptually included.

Regardless of the SP value, as the solvent that can be contained in the printing composition of the present invention, all known solvents for printing ink can be used. In particular, if the printing composition of the present invention is for gravure offset printing, a known gravure printing or intaglio printing solvent is used; If the solvent is for tampon printing, known tampo printing solvents can be used.
Among these solvents, those satisfying a specific SP value or a relationship of SP values described later are used by mixing (combining) two or more kinds.

Although it does not limit as a solvent, Specifically, the following are mentioned, for example.
Ethylene glycol condensates such as diethylene glycol and triethylene glycol;
Ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, or ethylene glycol mono Phenyl ether;
Ethylene glycol dialkyl ether or ethylene glycol diphenyl ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol dipentyl ether, ethylene glycol dihexyl ether, ethylene glycol diphenyl ether;
And a solvent in which the above “ethylene glycol” is replaced with “diethylene glycol” or “triethylene glycol”.
In addition, a monoacetate of the above-mentioned ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether or triethylene glycol monoalkyl ether;
Ethylene glycol, diethylene glycol or triethylene glycol diacetate;
Furthermore, the solvent etc. which replaced said "ethylene glycol" with "propylene glycol" are mentioned.

  3,5,5-trimethylhexanol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 3-methoxy-3-methyl-1-butanol, polyester polyol, aliphatic Examples thereof include alcohols such as polyhydric alcohols; carboxylic acid esters thereof; cyclic esters such as γ-butyllactone; carbonates such as propylene carbonate, butylene carbonate, and vinyl carbonate; N-methylpyrrolidone;

  Furthermore, acetic acid; tetrahydrofuran; hydrocarbons such as benzene, toluene, cyclohexane, amylbenzene, xylene; esters such as methyl acetate, ethyl acetate, dioctyl phthalate, ethyl formate, and aromatic esters; acetophenone, methyl ethyl ketone, cyclohexanone, acetone, etc. Ketones; chlorine-containing solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, dichloroethane, tetrachloroethane; alcohols or thiols such as octylene glycol, ethanethiol, acetone alcohol, isopropyl alcohol; carbon disulfide; propionitrile pyridine, Nitrogen-containing solvents such as nitroethane and acetonitrile; dioxane; ε-caprolactone; and the like. Moreover, although it overlaps, the solvent of Table 1 and Table 2 is mentioned.

  Two or more of these solvents satisfying a specific SP value or a specific SP value relationship described below are mixed (combined) and used as the (mixed) solvent in the present invention.

  Examples of the solvent having an SP value of 7.8 to 12.1 include diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol dibutyl ether, ethylene glycol monohexyl ether, Ethylene glycol-2-hexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol-n-hexyl ether, diethylene glycol-2-hexyl ether, diethylene glycol dibutyl ether, diethylene glycol monobenzyl ether , Zip Pyrene glycol monomethyl ether, dipropylene glycol monoethyl 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, 3,5,5-trimethylhexanol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 3-methoxy-3-methyl-1-butanol, γ-butyl Lactone, benzene, ethyl acetate, tetrahydrofuran, amylbenzene, xylene, methyl ethyl ketone, dioctyl phthalate, methyl acetate, dioxane, Chlohexane, acetophenone, cyclohexanone, acetone, isopropyl alcohol, carbon tetrachloride, aromatic ester, benzene, chloroform, trichloroethylene, dichloromethane, dichloroethane, carbon disulfide, tetrachloroethane, propionitrile pyridine, nitroethane, acetonitrile, ε-caprolactone Octylene glycol, ethyl formate, ethanethiol, acetone alcohol and the like. Moreover, the solvent as described in Table 1 and Table 2 as a solvent of SP value 7.8-12.1 is mentioned.

<< SP value of solvent >>
“SP value” is a solubility parameter, which is a value defined by the regular solution theory introduced by Hildebrand, and is used as a measure for the polarity of intermolecular forces and physical properties. Is done.
When the heat of evaporation per mole of the liquid is ΔH [cal] and the molar volume is V [cm ³ ], [SP value] = (ΔH / V) ^1/2 [(cal / cm ³ ) ^1/2 ] Is defined.
It is empirically known that the smaller the difference between the SP values of the two components, the greater the affinity and solubility.

  As a result of intensive studies on the effect of (mixed) solvent on the silicone rubber on the blanket surface of the conductive pattern printing composition, the present inventors have found that the SP value is within a predetermined range or is in a predetermined relationship (mixed). ) By using a solvent, it is possible to obtain a printing composition that achieves both “tack maintenance” and “bulk breakage suppression” as described above, and at the same time supports printing of patterns in which fine lines with different widths are mixed. I found out that I can do it.

  In the present invention, the solvent (H) having an SP value of 9.4 or more and 12.1 or less is 2% by mass or more and 60% by mass with respect to the entire “mixed solvent as all solvents of the printing composition”. Contains below. Hereinafter, “solvent (H) having an SP value of 9.4 or more and 12.1 or less” may be simply abbreviated as “solvent (H)”.

  The content of the solvent (H) is essentially 2% by mass or more and 60% by mass or less, preferably 3% by mass or more and 57% by mass or less, more preferably 4% by mass or more and 55% by mass with respect to the entire mixed solvent. % Or less, particularly preferably 5% by mass or more and 53% by mass or less. When two or more solvents (H) are contained, the above value is defined by the total content of all the solvents (H).

When it is at least the above lower limit, effects such as good tack maintainability and reduced influence on the silicone rubber on the blanket surface can be obtained. Moreover, bulk fracture inhibitory property becomes favorable as it is below the said upper limit.
Moreover, when it is within the above range, the effects of the present invention described above can be suitably achieved, and in particular, a printing composition having both tack maintenance and bulk fracture inhibition can be obtained. Even if different patterns are mixed, any pattern can be printed at the same time.

  The content of the solvent (H) depends on the type of binder resin, the concentration of components other than the (mixed) solvent, etc., but when the concentration of components other than the (mixed) solvent is high, the solid content concentration is high It is preferable that the content of the solvent (H) is large.

Furthermore, the mixed solvent in the present invention is characterized by containing a solvent (A) having an SP value of 0.3 or more smaller than that of at least one solvent (H).
When two or more types of solvents (H) are contained, it is only necessary to contain a solvent (A) having an SP value smaller by 0.3 or more than the solvent (H) having a higher SP value.
Moreover, you may contain the solvent whose SP value is smaller by less than 0.3 with respect to at least 1 sort (s) of solvent (H).
Further, the “solvent (A) whose SP value is 0.3 or more smaller than at least one solvent (H)” may be another solvent (H). That is, even if it contains two types of solvents (H) whose SP values are separated by 0.3 or more, they are included in the present invention.
Hereinafter, “a solvent (A) having an SP value of 0.3 or more smaller than that of at least one solvent (H)” may be simply abbreviated as “solvent (A)”.

The solvent (A) is a solvent having an SP value of 0.3 or more smaller than that of at least one solvent (H), more preferably a solvent having an SP value of 0.5 or more, and 0.7 or more. A small solvent is particularly preferred.
Printing in which the difference between the SP values of the solvent (A) and the solvent (H) is as described above, that is, by containing at least two types of solvents having different SP values, both tack maintenance and bulk fracture suppression are compatible. In addition, even if patterns having different widths or areas are mixed, any pattern can be printed at the same time.

  When a solvent (H) having an SP value of 0.3 or more relative to “solvent (H) belonging to solvent (H)” is present in the mixed solvent, the total content of the solvent (H) is It is preferably contained in an amount of 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and more preferably 4% by mass or more. It is particularly preferable. If the amount is too small, the effect of containing the solvent (H) may be reduced.

In the printing composition of the present invention, the solvent having an SP value of 7.8 or more and 12.1 or less is preferably contained in an amount of 90% by mass or more based on the entire mixed solvent. More preferably, it is 95 mass% or more, More preferably, it is 98 mass% or more, Most preferably, it is 100 mass%.
When there are too many SP values less than 7.8 solvent, it may be inferior to tack maintenance property, and when there are too many SP values larger than 12.1, it may be inferior in bulk fracture inhibitory property.
Further, instead of “a solvent having an SP value of 7.8 or more and 12.1 or less”, “a solvent having an SP value of 8.0 or more and 11.0 or less” is more preferable. It is particularly preferable that the solvent is 8.3 or more and 9.6 or less. Moreover, it is still more preferable that content of the solvent of the range of this SP value is the said range at that time.
If too much solvent has an SP value that is too small, tack maintenance may be inferior, and if too much solvent has an SP value that is too large, bulk fracture inhibition may be inferior.

The mixed solvent contained in the printing composition of the present invention includes a solvent (L) having an SP value of 7.8 or more and 9.1 or less, and a solvent (H having an SP value of 9.4 or more and 12.1 or less. ), And the total content of the solvent (L) and the solvent (H) is preferably 70% by mass or more based on the entire mixed solvent.
That is, it is essential that the solvent (H) and the solvent (A) have a SP value of 0.3 or more (preferably 0.5 or more, particularly preferably 0.7 or more). (SP value difference portion) preferably includes a range of SP value 9.1 or more and 9.4 or less. That is, the solvent (A) is preferably a solvent (L).
Hereinafter, the “solvent (L) having an SP value of 7.8 or more and 9.1 or less” may be simply abbreviated as “solvent (L)”.

  By containing the solvent (L) and the solvent (H), that is, by providing at least two types of solvents in the upper and lower directions with an SP value in the range of 9.1 to 9.4, tack maintenance is achieved. In addition, it is possible to more suitably obtain a printing composition having both excellent bulk breakage inhibiting properties, and even if patterns having different widths or areas are mixed, any pattern can be more suitably printed at the same time.

The total content of the solvent (L) and the solvent (H) is preferably 70% by mass or more based on the entire mixed solvent. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is 100 mass%.
By containing the solvent (L) and the solvent (H) in the above range, it is possible to particularly suitably obtain a printing composition having both tack maintaining ability and bulk fracture inhibiting ability, and further, width or area. Even if different patterns are mixed, any pattern can be printed particularly preferably.

In the above case, a solvent that is neither the solvent (L) nor the solvent (H) may be contained in the SP value range of 9.1 to 9.4.
The solvent (A) may be the solvent (H), may be a solvent having an SP value of 9.1 or more and 9.4 or less, or may be a solvent (L). L) is preferred. That is, by containing the solvent (L) (which is also the solvent (A)) and the solvent (H) (by containing a solvent having an SP value of 9.1 or less and a solvent having an SP value of 9.4 or more), Tack maintenance and bulk fracture suppression are compatible, and even patterns with different widths or areas can be printed simultaneously.

The solvent (H) (more preferably all) preferably has a vapor pressure at 20 ° C. of 0.05 hPa or less in order to obtain a printing composition having excellent tack maintenance. It is particularly preferable that the vapor pressure at 20 ° C. is 0.01 hPa or less.
The solvent (H) (more preferably any) has a boiling point of 240 ° C. or higher at normal pressure (1013 hPa), more preferably 250 ° C. or higher, and 260 ° C. or higher. More preferably, it is more preferably 270 ° C. or higher.

  Specific solvent names and examples of the vapor pressure and boiling point of each solvent include triethylene glycol monobutyl ether (vapor pressure 0.0033 hPa, boiling point 271.2 ° C.), tripropylene glycol monobutyl ether (0.01 hPa or less, 274 ° C), diethylene glycol monobutyl ether (0.01 hPa, 230.6 ° C), ethylene glycol monophenyl ether (0.013 hPa, 244.7 ° C), triethylene glycol monomethyl ether (0.08 hPa, 187.2 ° C), ε -Caprolactone (0.0013 hPa, 136.0 ° C), diethylene glycol monomethyl ether (0.26 hPa, 193.0 ° C), acetophenone (0.60 hPa, 201.7 ° C), diethylene glycol monobenzyl ether (0. Less than 1hPa, 302 ℃), 1,3- butylene glycol diacetate (0.00026hPa, there are 232 ° C.) such as but not limited to.

  For example, in the case of gravure offset printing, when the line width becomes as fine as about 20 μm to about 30 μm, the depth of the intaglio becomes about 10 μm, and the printing composition is transferred to the blanket including screen offset printing and tampo printing. The amount (volume) of the product must be reduced, but the (mixed) solvent should have a property that is not easily absorbed by the blanket and a property that is difficult to evaporate in order to improve tack maintenance. Because it is good.

Among the mixed solvents, a solvent having a surface tension (static) of 20 mN / m or more and 40 mN / m or less at 20 ° C. is contained in a total amount of 80% by mass or more based on the whole mixed solvent. It is preferable for improving “pattern linearity (less undulation)” and “pattern width reproducibility (less thickness)”.
The surface tension (static) of the mixed solvent is not particularly limited, but is preferably 20 mN / m or more and 40 mN / m or less, and particularly preferably 25 mN / m or more and 38 mN / m or less at 20 ° C. .
The “solvent having a surface tension (static) of 20 mN / m or more and 40 mN / m or less at 20 ° C.” is preferably contained in an amount of 80% by mass or more, more preferably 90% by mass or more. Especially preferably, it is 95 mass% or more.
The surface tension in the present invention is a value measured by the Wilhelmy method (manufactured by Kyowa Interface Science, model: CBVP-Z) at a measurement temperature of 20 ° C.

When the surface tension is too large, the linearity of the pattern on the blanket or the substrate when observed from the upper surface in the direction perpendicular to the blanket surface or the substrate surface is deteriorated, and a phenomenon (waviness) constricted in a bead shape occurs. Accordingly, there are cases where the “pattern linearity (less undulation)” is inferior or the pattern shape is deformed.
On the other hand, if the surface tension is too small, a phenomenon (thickening) occurs in which the line width of the pattern when observed from the upper surface in the direction perpendicular to the blanket surface or the substrate surface is larger than the line width of the printing plate. In some cases, it is inferior in “width reproducibility (less thick)” or inferior in bulk fracture inhibition.

  Specific solvent names and surface tensions include, for example, diethylene glycol dibutyl ether (23.6 mN / m), triethylene glycol monomethyl ether (25.1 mN / m), triethylene glycol monobutyl ether (27.7 mN / m), Diethylene glycol monobutyl ether (26.2 mN / m), dipropylene glycol monobutyl ether (26.2 mN / m), diethylene glycol monobenzyl ether (36.3 mN / m), other “solvents and surface tension” listed in Table 2, etc. However, it is not limited to these.

  In the printing composition of the present invention, the content of the mixed solvent varies depending on the printing method. For example, in gravure offset printing, it is preferably 3% by mass or more and 50% by mass or less with respect to the entire printing composition. More preferably, the content is greater than or equal to 40% by weight and less than or equal to 40% by weight, particularly preferably greater than or equal to 7% and less than or equal to 35% by weight.

<Other ingredients>
The printing composition of the present invention preferably further contains “other components” as necessary.
Examples of the “other components” include gravure offset printing ink and intaglio printing ink components in the case of gravure offset printing, and known screen printing ink components in the case of screen offset printing. In the case of tampo printing, known tampo printing ink components can be mentioned.
Specifically, for example, fluidity imparting agent, fluidity adjusting fine particles, dispersing (stabilizing) agent, antifoaming agent, release agent, leveling agent, plasticizer, lubricant, structural viscosity imparting agent, thixotropy imparting agent, thermosetting reaction And stabilizers that suppress the above.

The fluidity-adjusting fine particles improve the printability by adjusting the fluidity of the composition according to the oil absorption amount and the specific surface area, and those having a number average particle diameter of 1 μm or less are preferable, and those of 0.5 μm or less Is particularly preferred.
When the fluidity adjusting fine particles are contained, the “fluidity” of the printing composition is improved.

As the fluidity adjusting fine particles, for example, flame method (fumed) silica, colloidal silica, alumina, titania and the like are preferable. It is also preferable that a treatment such as a hydrophobic treatment is performed.
The fluidity adjusting fine particles are not particularly limited, but specifically, the following products can be used as an example.
Fuji Silysia Chemical Co., Ltd., Silysia 310, Silysia 320, Silysia 350; Nippon Aerosil Co., Ltd. AEROSIL200, AEROSIL380.

<Board>
The substrate on which the printing composition of the present invention is printed is not limited. Specifically, for example, plastic (film), ceramic (film), silicon wafer, glass, metal (plate), paper, cloth , Rubber, wood and the like.
The printing composition of the present invention is compatible with both tack maintenance and bulk breakage suppression. In particular, the bulk breakage suppression that is easily deteriorated with a pattern having a line width of 50 μm or more is improved, and the pattern having a line width of 20 μm or less is improved. The tack maintenance which is easy to deteriorate is improved.
Therefore, the substrate on which the printing composition of the present invention is printed is a substrate in which a pattern having a line width of 20 μm or less and a pattern having a line width of 50 μm or more coexist on the same substrate. It is preferable from the point of exhibiting.

In many actual substrates, a thin line width and a thick line width coexist. However, in such a substrate, the printing composition of the present invention has a “tack maintenance property” that tends to cause a problem when the line width is small. In addition, the feature of “excellent compatibility with“ bulk fracture suppression ”, which tends to be a problem when the line width is large, is utilized.
The printing composition of the present invention is preferably for printing on a substrate in which a pattern having a line width of 20 μm or less and a pattern having a line width of 50 μm or more coexist, and the pattern and line width having a line width of 20 μm or less. More preferably for printing on a substrate on which a pattern of 100 μm or more coexists, and for printing on a substrate on which a pattern with a line width of 20 μm or less and a pattern with a line width of 150 μm or more coexist It is particularly preferable that it is for printing on a substrate in which a pattern having a line width of 20 μm or less and a pattern having a line width of 300 μm or more coexist.

The line width defines the line width on the substrate. Thin line width patterns in printing plates may merge to form a thick line width pattern on a blanket or substrate. Alternatively, consciously, the thin line width patterns on the plate may be combined to form a thick line width pattern on the blanket or the substrate.
Since “tack maintenance” and “bulk fracture suppression” in the present invention are characteristics at the time of transfer of the printing composition from the blanket to the substrate, the above line width is not a line width in the plate. , Definition of line width in blankets and / or substrates. That is, the gravure offset printing and the tampo printing do not define the “width of the linear recess” in the intaglio plate, and the screen offset printing does not define the “thickness of the line-shaped missing portion” in the screen plate.

<Application>
Although the printing object of the printing composition of the present invention is not particularly limited, it is a conductive pattern such as a wiring, an electrode, and a conductive circuit of an electronic component such as a touch panel, electronic paper, a photovoltaic power generation panel, and a multilayer ceramic capacitor. However, it is preferable in order to remarkably exhibit the effect of the printing composition of the present invention.
A particularly preferable target of the conductive pattern to be printed is a conductive pattern for a touch panel. That is, the substrate having a conductive pattern to be printed is particularly preferably a substrate having a conductive pattern for a touch panel.

<Printing and manufacturing method of conductive pattern>
The printing composition of the present invention can form a conductive pattern by printing on a substrate by any printing method using a blanket.
Since the printing composition of the present invention has improved transferability from the blanket to the substrate, it is preferably used in a printing method using a blanket.
Another aspect of the present invention is a method for producing a substrate having a conductive pattern, in which a pattern is printed on a substrate using the conductive pattern printing composition of the present invention, and the conductive pattern printing composition A method for producing a substrate having a conductive pattern, comprising: a step of transferring an object from a printing plate to a blanket; and a step of transferring the blanket to the substrate.

Examples of the method for printing the conductive pattern as described above include gravure offset printing, screen offset printing, and tampo printing.
Among them, gravure offset printing is preferable in order to exhibit the effect of the present invention particularly effectively. That is, in the method for producing a substrate having a conductive pattern according to the present invention, it is particularly preferable that the printing method is a method by gravure offset printing, and the printing plate is a gravure plate or an intaglio plate.

The gravure offset printing is also called intaglio offset printing, and is described in, for example, Patent Documents 2 to 5.
In the gravure offset printing, a gravure plate (intaglio) having a recess corresponding to a conductive pattern, a doctor blade for filling the recess of the gravure plate (intaglio) with a printing composition, and the surface is made of, for example, silicone rubber. A blanket is used. The intaglio used for gravure offset printing may have a different form from the normal intaglio used for general-purpose gravure printing. Hereinafter, “gravure plate or intaglio plate” used for gravure offset printing may be abbreviated as “gravure plate (intaglio plate)”.
The printing composition is once transferred to the blanket from the concave portion of the gravure plate (intaglio). A substrate is supplied so as to face this blanket, both are brought into pressure contact, and the pattern on the blanket is transferred again to the substrate, whereby a printed pattern is formed.
This printed pattern becomes a conductive pattern having conductivity by heating and baking.

  According to this printing method, the shape of the printing pattern can be freely set according to the shape of the recess, and the transfer rate of the coating composition film from the blanket to the substrate is also the use of the printing composition of the present invention. Since it can be almost 100%, it is possible to accurately form a printed pattern corresponding to a fine wiring pattern to a large area pattern.

A well-known thing can be used as a gravure plate (intaglio).
Each of the gravure plate (intaglio plate), blanket and substrate may have a flat plate shape (sheet-fed) or a cylindrical shape. The pattern on the blanket may be continuously transferred to the substrate by pressing the blanket against the substrate.

  Moreover, when printing on many substrates using one blanket, it is also preferable to include a step of drying the blanket that has absorbed the solvent after printing. This drying step may be performed every printing cycle, or may be performed every 5 to 20 printing cycles at intervals.

The blanket is preferably made of silicone rubber. A sheet having a silicone rubber layer on the surface is preferable. It is preferably used in a state of being wound around a rigid cylinder called a blanket cylinder.
For example, a silicone blanket in which a silicone rubber layer is formed on a plastic film such as a polyester film can be used in a state of being wound around a blanket cylinder.

Screen offset printing is described in, for example, Patent Document 6.
In screen offset printing, a printing composition is temporarily screen-printed on a blanket using a screen printing plate in which passage holes corresponding to conductive patterns are formed. A substrate is supplied so as to face this blanket, both are brought into pressure contact, and the pattern on the blanket is transferred again to the substrate, whereby a printed pattern is formed. The blanket is preferably made of silicone rubber.
This printed pattern becomes a conductive pattern having conductivity by heating and baking.

Tampo printing is also called stacking printing or pad printing, and is described in, for example, Patent Document 7.
In tampo printing, the printing composition on the intaglio is once transferred to a soft hemispherical or ship-bottom silicone rubber blanket (also referred to as “tampo”), which is then pressed against the substrate. As a result, the printing composition on the blanket (tampo) is transferred to the substrate.
The use of an intaglio, the use of a doctor to fill the recess with a printing composition, and the like are the same as in gravure offset printing. The blanket (tampo) is preferably made of silicone rubber.
As a specific blanket for tampo printing, for example, a silicon pad R-12 (φ70 × 61 mm (bottom × height)) manufactured by Mino Group and a hardness of 40 degrees can be used.

In the method for manufacturing a substrate having the conductive pattern, the substrate to be printed (manufacturing target) is a substrate in which a pattern having a line width of 20 μm or less and a pattern having a line width of 50 μm or more coexist on the same substrate. That is, the printing composition of the present invention makes use of the feature that both “tack maintenance” that is a problem with a thin line width and “bulk fracture suppression” that is a problem with a thick line width can be achieved. Therefore, it is preferable.
More preferably, the substrate has a pattern with a line width of 20 μm or less and a pattern with a line width of 100 μm or more, and the substrate has a pattern with a line width of 20 μm or less and a pattern with a line width of 150 μm or more. Particularly preferred is a substrate in which a pattern having a line width of 20 μm or less and a pattern having a line width of 300 μm or more coexist. In many actual substrates, a thin line width and a thick line width coexist.

In addition, a thin line width pattern in a printing plate may be combined into a thick line width pattern on a blanket or on a substrate, but the above line width defines the line width on the substrate. It is.
In the present invention, “tack maintenance” and “bulk fracture suppression” are characteristics at the time of transfer of the printing composition from the blanket to the substrate. The definition of the line width is not the definition of the line width in the printing plate, but the definition of the line width in the blanket and / or the substrate.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist. Here, “%” and “part” are “% by mass” and “part by mass” unless otherwise specified.

Preparation Example 1
<Preparation of conductive pattern printing composition 1>
“Conductive pattern printing composition 1” for gravure offset printing was prepared with the following composition.

As the conductive powder, 80 parts of silver powder (SPQ03R manufactured by Mitsui Mining & Smelting Co., Ltd.) having an average particle diameter of median diameter (D50) of 0.5 μm;
As a binder resin, 1.5 parts of bisphenol type epoxy resin (DICLON 840 manufactured by DIC Corporation) and 5.0 parts of phenoxy resin (Epototo YP-50S manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.);
As a curing agent, 0.8 part of an amine compound (Amico MY-24 manufactured by Ajinomoto Fine Techno Co., Ltd.);
As fluidity-adjusting fine particles, 0.2 part of flame method silica (Silisia 320 manufactured by Fuji Silysia Chemical Co., Ltd.);

  A composition was prepared using 30 parts of the above and “a mixed solvent comprising the solvents described in Table 2”. The “mixed solvent” is all the solvents contained in the printing composition, and “30 parts” is the total amount of all the solvents.

Preparation Example 2
<Preparation of conductive pattern printing composition 2>
In the preparation of the following “Conductive pattern printing composition 1” in Preparation Example 1, the amount was reduced to 25 parts of the mixed solvent instead of 30 parts of the mixed solvent (the amount of the mixed solvent was reduced to increase the solid content concentration). Prepared “Conductive pattern printing composition 2” for gravure offset printing in the same manner as in Preparation Example 1.
The content ratio of each solvent in the mixed solvent was the same as that of “Conductive pattern printing composition 1”.

When the solid content concentration is increased, the bulk fracture inhibiting property tends to be good. Therefore, “Conductive pattern printing composition 1” is a pattern with any line width and bulk fracture inhibiting property is “x”. Only evaluated.
However, although the “conductive pattern printing composition 2” is realistic as a concentration, the fluidity is lowered by increasing the solid content concentration as compared with the “conductive pattern printing composition 1”. As a result, the gravure plate is insufficiently filled in the recesses, and the conductive pattern printed on the substrate is liable to have defects such as “disconnection” and “pinhole”. Therefore, when “Conductive pattern printing composition 1” is used, the bulk fracture inhibiting property is “x” in any of the line width patterns. Therefore, “Conductive pattern printing composition 2” was also evaluated. For the products, the overall evaluation described later was “△” at best.

Evaluation Example 1
<Method of gravure offset printing>
A pattern in which lines having a width of 20 μm, a width of 50 μm, and a width of 150 μm were mixed was printed by gravure offset printing. The gravure plate (intaglio) used had a plate depth of 10 μm.
In the table, a pattern with a width of 20 μm is abbreviated as “small line width”, a pattern with a width of 50 μm is abbreviated as “medium line width”, and a pattern with a width of 150 μm is abbreviated as “large line width”.

  Blanket with a 0.85 mm thick silicone rubber sheet (silicone rubber / polyester film layer configuration, rubber hardness (JIS A) 45 degrees, surface average roughness Ra: 0.1 μm, surface tension 21 mN / m) on the surface Using a gravure offset printing apparatus having a roll, printing was performed on a PET substrate using the printing composition obtained above. Evaluation was made according to the following evaluation examples.

Evaluation example 2
<Tack maintenance evaluation method>
For each printed sheet, the printed blanket and the substrate were observed with an optical microscope and visually with a pattern remaining on the blanket and a pattern transferred onto the substrate. Judgment was made according to the following criteria.

<Criteria for tack maintenance>
○: In printing 10 sheets, all 10 patterns on the blanket are transferred onto the substrate, and there is no problem.
Δ: With 10 sheets of printing, “all the patterns on the blanket are transferred onto the substrate from the first sheet, but there are patterns that are not transferred onto the substrate from the middle” or “the first sheet is not transferred onto the substrate There is a pattern, but all the pattern is transferred onto the substrate from the middle. "
X: The pattern which is not transcribe | transferred on all the 10 board | substrates by printing 10 sheets exists.

Evaluation Example 3
<Method for evaluating bulk fracture inhibition>
For each printed sheet, the printed blanket and the substrate were observed with an optical microscope and visually with a pattern remaining on the blanket and a pattern transferred onto the substrate. Judgment was made according to the following criteria.

<Criteria for bulk fracture inhibition>
○: In printing 10 sheets, the printing composition does not remain on all 10 blankets, and there is no problem.
Δ: In printing 10 sheets, “the printing composition does not remain on the blanket from the first sheet, but remains on the blanket from the middle” or “the printing composition on the blanket is printed on the first sheet. It will remain, but will not remain on the blanket in the middle. "
X: After printing 10 sheets, the printing composition remains on all 10 blankets.

Evaluation Example 4
<Evaluation method of pattern linearity (with less undulation)>
Using the “50 μm line and space 1: 1 pattern” on the printing plate, using an optical microscope (reflected light), and observing the pattern line width on the substrate by observing at a magnification of 100 and taking a photograph. Then, “pattern linearity (with less undulation)” was determined by the value of the following formula (1). The unit of the value of the following formula (1) is [μm] for both the numerator and the denominator.
100 × [pattern line width (maximum value) −pattern line width (minimum value)] / 50 (1)

<Criteria for pattern linearity (low swell)>
○: The value of the formula (1) is 0% or more and 20% or less. Δ: The value of the formula (1) is larger than 20% and 50% or less. X: The value of the formula (1) is larger than 50%.

Evaluation Example 5
<Evaluation method of pattern width reproducibility (less weight)>
Using the “50 μm line and space 1: 1 pattern” on the printing plate, using an optical microscope (reflected light), and observing the pattern line width on the substrate by observing at a magnification of 100 and taking a photograph. Then, “pattern width reproducibility (less thick)” was determined by the value of the following formula (2). The unit of the value of the following formula (1) is [μm] for both the numerator and the denominator.
100 × [pattern line width on substrate−50] / 50 (2)

<Judgment criteria for pattern width reproducibility (less fat)>
○: The value of formula (2) is 20% or less (including minus%)
Δ: The value of the formula (2) is larger than 20% and 50% or less. X: The value of the formula (2) is larger than 50%.

Evaluation Example 6
<Method of comprehensive evaluation>
Tack maintenance, bulk fracture inhibition, pattern linearity (less undulation), and pattern width reproducibility (less weight) were comprehensively evaluated.
In addition, about the thing with the large line width of the printing composition 1 and bulk fracture inhibitory property x, the printing composition 2 which reduced the amount of mixed solvents and raised solid content concentration was also evaluated.

<Criteria for comprehensive evaluation>
○: Tack maintainability and bulk breakage suppression property in printing composition 1, no x, Δ is 2 or less, pattern linearity (less undulation), pattern width reproducibility (less weight) Is also ○.
Δ: Tack maintaining property and bulk fracture suppressing property in the printing composition 1, there was no x, Δ was 3 or more, or there was no result x evaluated with the printing composition 2, or a pattern Either linearity (less undulation) or pattern width reproducibility (less weight) is Δ.
X: In both of the printing composition 1 and the printing composition 2, “x” is present in the tack maintenance property or the bulk fracture inhibition property.

As can be seen from Table 2, the solvent (H) having an SP value of 9.4 or more and 12.1 or less is contained in an amount of 2% by mass or more and 60% by mass or less with respect to the entire mixed solvent, and at least one kind In the conductive pattern printing composition (No. 11 to 31) using the mixed solvent containing the solvent (A) having an SP value of 0.3 or more smaller than that of the solvent (H), the overall evaluation is “Good”. "Or" △ "and judged to be good.
On the other hand, in the conductive pattern printing compositions (Nos. 32-42) that do not satisfy the requirements of the present invention, the overall evaluation was “x”, and it was judged as defective.

  Conductive pattern printing composition No. determined to be good. Among the above-mentioned requirements, the conductive pattern printing composition (No. 24) in which the solvent having an SP value of 7.8 or more and 12.1 or less is less than 90% by mass with respect to the whole mixed solvent among Nos. 11 to 31 is used. Even if the above is satisfied, the overall evaluation was “△”.

  Also, the conductive pattern printing composition no. 11 to 31, the total content of the solvent (L) having an SP value of 7.8 or more and 9.1 or less and the solvent (H) having an SP value of 9.4 or more and 12.1 or less is the mixture. In the conductive pattern printing composition (No. 16, 17, 23, 25) which is less than 70% by mass with respect to the whole solvent, the overall evaluation was “Δ” in all cases even if the above requirements were satisfied. .

Also, the conductive pattern printing composition no. Among the compositions 11 to 31, the conductive pattern printing composition (No. 28, 30) having a vapor pressure at 20 ° C. higher than 0.05 hPa in the solvent (H) satisfies the above requirements. In both cases, the overall evaluation was “Δ”.
Also, the conductive pattern printing composition no. Among the mixed solvents, among the mixed solvents, a conductive material whose surface tension is 20 mN / m or more and 40 mN / m or less at 20 ° C. is less than 80% by mass in total with respect to the entire mixed solvent. In the pattern printing compositions (Nos. 29 and 30), even when the above requirements were satisfied, the overall evaluation was “Δ”.

  Since the conductive pattern printing composition of the present invention is excellent in transferability, it is widely used when forming conductive patterns such as wirings, electrodes, and conductive circuits of various electric and electronic components. is there.

Claims (8)

At least a conductive resin, a binder resin that is one or more resins selected from the group consisting of epoxy resins and phenoxy resins, and a conductive pattern printing composition containing a mixed solvent,
A solvent (H) having an SP value of 9.4 or more and 12.1 or less is contained in an amount of 2% by mass or more and 60% by mass or less based on the entire mixed solvent,
The mixed solvent contains a solvent (A) having an SP value smaller than 0.7 by at least one kind of the solvent (H),
And this mixed solvent contains the solvent (L) whose SP value is 7.8 or more and 8.9 or less,
A conductive pattern printing composition for simultaneous printing of a pattern having a line width of 20 μm or less and a pattern having a line width of 50 μm or more.   2. The conductive pattern printing composition according to claim 1, wherein a total content of the solvent (H) and the solvent (L) is 70% by mass or more based on the entire mixed solvent.   The conductive pattern printing composition according to claim 1, wherein the conductive powder is a silver powder.   The conductive pattern printing composition according to claim 1, wherein the printed conductive pattern is a conductive pattern for a touch panel.   The mixed solvent contains at least one solvent selected from the group consisting of triethylene glycol monobutyl ether, diethylene glycol monobenzyl ether and 1,3-butylene glycol diacetate, and diethylene glycol monobutyl ether acetate. The composition for electroconductive pattern printing of any one of these.   6. The solvent according to claim 1, wherein a solvent having a surface tension of 20 mN / m or more and 40 mN / m or less at 20 ° C. in the mixed solvent is contained in a total amount of 80% by mass or more. 2. The conductive pattern printing composition according to item 1.   A substrate having a conductive pattern, wherein a pattern having a line width of 20 μm or less and a pattern having a line width of 50 μm or more are simultaneously subjected to gravure offset printing using the conductive pattern printing composition according to claim 1. A method for producing a substrate having a conductive pattern, comprising: a step of transferring the conductive pattern printing composition from a printing plate to a blanket; and a step of transferring the composition from the blanket to a substrate. Manufacturing method.   The method for manufacturing a substrate having a conductive pattern according to claim 7, wherein the blanket is a blanket having a flat surface.