TW201817826A - Conductive pattern printing composition and method for producing substrate with conductive pattern - Google Patents

Abstract

This invention provides a conductive pattern printing composition coping with absorption of solvent of the conductive pattern printing composition into blanket, improving transferability from blanket to substrate, and excellent in transferring even in the case that different line sizes of different sizes coexist in one substrate. A conductive pattern printing composition of this invention contains at least a conductive powder, a binder resin, and a mixed solvent, which contains a solvent (H) having an SP value of 9.4 or more and 12.1 or less in an amount of 2% by mass or more and 60% by mass or less, with respect to the whole mixing solvent, wherein the mixed solvent contains a solvent (A) with an SP value smaller than that of at least one of the solvent (H) at least by 0.3.

Description

 Conductive pattern printing composition and method of manufacturing substrate having conductive pattern  

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 having a specific SP value, and A method of producing a substrate having a conductive pattern of the composition.

An etching method, a printing method, and the like are known as a method of forming a conductive pattern such as a wiring, an electrode, or a conductive circuit of an electronic component/electrical component such as a touch panel, an electronic paper, a solar power generation panel, or a multilayer ceramic capacitor.

When a conductive pattern is formed by an etching method, a photoresist is applied onto a substrate on which a metal film is deposited, pattern exposure and development processing are performed, and a resist pattern is formed, and a portion having the resist pattern is not present. The metal film is dissolved and removed, and finally the resist pattern is removed.

However, in the etching method described above, it is necessary to have a plurality of steps as described above, and the steps are extremely complicated, and there is a material loss due to dissolution and removal of the metal film, and as a result, the mass production is poor.

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, and further, conductivity can be easily imparted by drying or hardening the printed composition. A conductive pattern is obtained.

The printing method used in the printing method described above conforms to the line width, pattern linearity, thickness, line width accuracy, relative positional accuracy, absolute positional accuracy, surface smoothness (surface unevenness reduction) of the pattern to be formed, Production speed, etc., such as flexographic printing, inkjet printing, gravure printing, screen printing (Patent Document 1, etc.), gravure offset printing (Patent Documents 2 to 5, etc.), screen printing have been proposed. (screen offset printing) (patent document 6 or the like), pad printing (tampo priting) (patent document 7 and the like), plate printing (lithographic printing), letterpress printing, rotary screen printing, letterpress inversion Printing, dispenser printing, electrostatic discharge inkjet printing, and the like.

Among them, after temporarily transferring or printing on a blanket, the printing method is again transferred to the substrate, and the pattern can be thinned, the pattern shape can be stabilized, and a certain amount of the printing composition can be transferred. Point is being noticed.

In the gravure transfer, the printing composition is filled with a doctor blade or the like in a concave plate in which a concave portion is formed corresponding to a desired pattern, and then the printing composition is transferred to the rubber blanket, and The blanket is again transferred to the substrate to form a pattern on the substrate. This pattern is hardened or calcined by heat such as heat or UV to form a conductive pattern.

In screen printing, a printing composition is printed onto a blanket from a screen formed corresponding to a desired pattern, and a pattern is formed on the substrate by transferring from the blanket to the substrate. The light is hardened or calcined by heat such as heat or UV to form a conductive pattern.

In pad printing, a printing composition is filled in a gravure in which a concave portion is formed corresponding to a desired pattern, and then the printing composition is transferred to a soft hemispherical or ship-bottom shape called a tampo. Next, the pad (rubber) is pressed against the substrate, and a pattern is formed on the substrate by retransfering the printing composition on the pad (rubber) to the substrate. This pattern is hardened or calcined by heat such as heat or UV to form a conductive pattern.

However, in any of the above printing methods, the transferability of the known conductive pattern printing composition from the plate to the blanket, particularly from the blanket to the substrate, is insufficient, and it is difficult to call it printability. Excellent.

In recent years, from the viewpoint of miniaturization and high integration of the electronic component, for example, formation of a high-definition conductive pattern having a line width of 5 μm or less is required, and depending on the use or function It is also possible to coexist a pattern having a line width of several hundred μm in the same substrate, and to form the pattern.

Further, it is necessary to form the printing in one printing. However, there is still a problem (not sufficient) in the related art, and there is room for further improvement in the composition for conductive pattern printing.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-269976

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-159350

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-235780

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2014-034589

[Patent Document 5] Japanese Laid-Open Patent Publication No. 2015-172103

[Patent Document 6] International Publication No. 2014/050560

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2014-226859

The present invention has been made in view of the above-described background art, and an object of the present invention is to provide a conductive pattern printing composition which is improved in a printing method from a step of temporarily transferring to a blanket, and is improved from a thin line pattern to a glue. The transfer property of the blanket, the case where the solvent for the conductive pattern printing composition (hereinafter referred to as the "printing composition") is absorbed by the blanket, and the transfer property from the blanket to the substrate is improved. Further, a method of manufacturing a substrate having a conductive pattern using the same is also provided.

In the following, the subject of "transferability of the composition for printing from the blanket to the substrate" will be specifically described.

Compared with a printing method for directly transferring a printing composition from a plate to a substrate, a printing method in which a printing composition is temporarily transferred from a plate to a substrate by a blanket is capable of being thinned and transferable by a certain amount. The printing composition and the shape of the pattern can be stably formed.

However, the printing method in which the printing composition is temporarily transferred from the plate to the substrate by the blanket does not have a practical printing composition.

In the present invention, it has been found that the transfer of the composition for printing from the blanket to the substrate is extremely important to solve the following problems.

The present invention has been made in an effort to provide a printing composition which has improved printability (especially, the transfer property from a blanket to a substrate is improved). However, the present invention has also found the following problems.

That is, when the width of the printed pattern is narrow (for example, when the width is 20 to 30 μm), the amount of the printing composition transferred from the blanket to the substrate is greatly reduced.

In general, the amount of transfer using the intaglio printing depends on the depth of the groove of the intaglio. The depth of the groove of the pattern having a line width of 20 μm to 30 μm is inevitably lightened by the manufacturing method of the plate, so the amount of transfer is extremely limited.

On the other hand, in the transfer of the printing composition from the blanket to the substrate, if the printing composition on the blanket is not nearly full, the above-mentioned "printing method having the step of temporarily transferring the printing sheet to the blanket" The specialty can not be used.

However, the width of the printed pattern is narrowed, and correspondingly, when the amount of the printing composition on the blanket is reduced, "the solvent from the surface of the pattern is promoted because the surface area per unit volume is increased due to the miniaturization of the pattern. "Evaporation" and "The solvent transferred to the printing composition of the blanket is absorbed into the blanket", so that the solid content concentration of the printing composition rises to a dry state, and adhesion (hereinafter, also referred to as " The phenomenon of viscous "reduction" becomes important. That is, since the width of the pattern becomes narrow, the total amount of the printing composition on the blanket becomes small, and even if only a slight solvent evaporates and is absorbed into the blanket, the pattern of the printing composition on the blanket is adhered. The decrease in the properties is also negligible, and the decrease in the adhesion property deteriorates the transfer property of the printing composition from the blanket to the substrate.

This phenomenon occurs even when a solvent having a low vapor pressure (a solvent which is difficult to dry, a so-called "slow-drying solvent") is used.

In order to suppress such a decrease in adhesion, it is considered to use a solvent which is difficult to be absorbed into the blanket.

However, when a solvent which is hard to be absorbed into the rubber blanket is used, this time, 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 pattern of the composition for printing on the blanket to the adhesive blanket and the adhesion to the substrate become too high, and further, since the pattern on the blanket contains a large amount of solvent, the composition on the blanket When it is softened, the pattern is separated in the thickness direction of the printing composition on the blanket (the pattern is bulk-destroyed (tears)), and the so-called "tear phenomenon" which causes deterioration of the transfer property to the substrate occurs.

In the following, it is suppressed that the solvent in the composition for printing is absorbed to the blanket, and the adhesion of the pattern of the printing composition on the blanket is lowered, and the printing composition from the blanket to the substrate is transferred. The nature of the phenomenon of sexual deterioration is referred to as "stickiness maintenance".

Further, the above-mentioned "the solvent in the composition for printing is difficult to be absorbed into the blanket or the like, and the pattern of the printing composition on the blanket becomes a thickness containing a large amount of solvent, and the composition of the pattern on the blanket is printed. The property that the directions are separated and the transfer property to the substrate is deteriorated is simply referred to as "volume destruction inhibition property".

As a result of careful examination of the above-mentioned problems, the present inventors have found that the SP value of each solvent is set to a specific range and relationship by using two or more types of mixed solvents, and the specific solvent content is specified. In view of the above, the above problems are solved and the present invention has been completed.

In other words, the present invention provides a conductive pattern printing composition comprising at least a conductive powder, an adhesive resin, and a mixed solvent, wherein the total amount of the mixed solvent is 2% by mass or more and 60% by mass or less. The solvent (H) having an SP value of 9.4 or more and 12.1 or less is contained, and the mixed solvent contains a solvent (A) having an SP value of 0.3 or more and less than at least one solvent (H).

Furthermore, the present invention provides a composition for conductive pattern printing, wherein 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 total content of the solvent (L) and the solvent (H) is 70% by mass or more based on the total amount of the mixed solvent.

Further, the present invention provides a method for producing 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 transferred from a printing plate. The step of printing the blanket and the step of transferring from the blanket to the substrate.

According to the present invention, it is possible to provide a conductive pattern printing composition that solves the above problems and problems, and that achieves both "viscosity maintenance" and "volume destruction inhibition".

That is, there is provided a composition for conductive pattern printing which improves transferability from a plate of a fine line pattern to a blanket in a printing method having a step of temporarily transferring to a blanket, and copes with a solvent for a composition for printing In the case of being absorbed by the blanket, the transferability from the blanket to the substrate is improved, and a method of manufacturing a substrate having a conductive pattern using the same is provided.

Further, it is possible to provide a composition for conductive pattern printing which can maintain the above-mentioned "stickiness" even when a pattern having a small line width and a large pattern are mixed in one substrate. "The nature" and the above "volume damage inhibition" take into consideration.

In other words, the composition for conductive pattern printing according to the present invention is easy to be a problem of "stickiness maintenance" when the line width is a small pattern, and is easy when the line width is a large pattern (a pattern having a large area). The problem of "volume damage suppression" that is a problem can be considered.

A method for producing a substrate having a conductive pattern in the step of transferring a printing composition from a printing plate to a blanket and transferring the substrate to a substrate by using the printing composition of the present invention A method of manufacturing a substrate having a conductive pattern that satisfies both "a pattern having a size and a line width in one substrate" and a combination of "viscosity maintenance" and "volume damage suppression" can be realized.

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

The conductive pattern printing composition of the present invention contains at least a conductive powder, an adhesive resin, and a mixed solvent, and the SP value is 9.4 or more with respect to 2% by mass or more and 60% by mass or less based on the entire mixed solvent. 12.1 The following solvent (H), and the mixed solvent contains a solvent (A) having an SP value of 0.3 or more with respect to at least one solvent (H).

In the following, the "conducting pattern printing composition" is simply referred to as "printing composition".

<Electrically conductive powder>

The composition for printing of the present invention contains a conductive powder. The conductive powder contained in the printing composition of the present invention is not particularly limited, and specific examples thereof include nickel, copper, gold, silver, aluminum, zinc, tin, lead, chromium, and platinum. a powder of a metal such as palladium, tungsten, molybdenum, indium, chromium, niobium or tantalum; a powder of the alloy; a powder of the mixture; a powder having good electrical conductivity among the metal compounds; silver oxide, a powder of a metal oxide such as copper oxide, aluminum oxide, nickel oxide or tin oxide; a powder in which particles of an inorganic substance or an organic substance are covered with a metal film; an organic conductive powder such as carbon black, thiophene or aniline. Among them, powders of metals such as nickel, copper, gold, silver, aluminum, platinum, and palladium are preferred, and powders of such alloys have stable and high electrical conductivity, are difficult to oxidize, and have good heat conduction characteristics. It is also excellent in terms of cost.

The specific silver powder is not particularly limited, and the following products can also 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 & Mining Co., Ltd.; Silbest AGS manufactured by Deli Chemical Research Institute -050, Silbest TC905S ("Silbest" 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 small with respect to the width of the pattern to be printed, but the median diameter (D50) is preferably 0.01 to 6 μm, more preferably in terms of the average particle diameter. It is 0.03 to 5 μm, particularly preferably 0.1 to 4 μm. Further, a flake powder and a spherical powder may be used together. Since the flake powder can increase the contact area between the particles, it is expected to have high conductivity.

When the average particle diameter is too small, the modulation of the conductive powder becomes difficult, the conductivity is lowered, the dispersion becomes difficult, and the adjustment of the structural viscosity becomes difficult. On the other hand, when the average particle diameter is too large, dispersion becomes difficult and dispersible. The stability is deteriorated, and the shape of the pattern is deteriorated.

If the average particle diameter of this range is multiplied by a mixed solvent to be described later, the viscosity, fluidity, structural viscosity, and thixotropy (time change of structural viscosity) of the printing composition are good, and the gravure is in the gravure. In the printing method using a blanket (printing head) such as transfer printing, screen printing, pad printing, etc., even when printing continuously on a printing machine, it is difficult to cause trouble and a good conductive pattern can be easily and stably obtained. .

The content ratio of the above-mentioned conductive powder to the adhesive resin to be described later is not particularly limited, and the amount of the adhesive resin is preferably 0.3% by mass or more and 30% by mass or less, more preferably 1% by mass or more per 100 parts by mass of the conductive powder. The mass% or less is particularly preferably from 3 mass% to 15 mass%.

<Adhesive Resin>

The composition for printing of the present invention contains an adhesive resin. The adhesive resin forms a resin film on the substrate after printing to fix the conductive powder on the substrate. In the present invention, the "adhesive resin" also contains a curable compound (curable resin) which is cured into a resin, and a relatively low molecular weight curable property such as an epoxy resin or a polyfunctional acrylic monomer (oligomer). Compound (curable resin). In addition, such mixtures are also included.

The adhesive resin may be one which is hardened or crosslinked in the presence of a curable compound or a hardener, or may be hardened or crosslinked.

In the case of the adhesive resin, it is preferred that a good film can be formed on the substrate, a good film can be formed on the rubber blanket, and a film of the printing composition can be completely transferred from the blanket to the substrate.

Preferably, the adhesive resin is soluble in the mixed solvent of the present invention having a specific SP value, and when the mixed solvent is used (when dissolved in the mixed solvent), if the content of the adhesive resin is When the molecular weight or the like is appropriately adjusted, the above-mentioned "viscosity maintenance property" and "volume destruction inhibition property" are obtained.

The adhesive resin in the present invention is hardened by heat, light, electron beam or the like from the viewpoints of improving the hardness of the conductive pattern on the substrate, improving the adhesion to the substrate, and improving the heat resistance. A preferred resin (compound) is preferred.

When a curable resin or compound is used, in the molecular structure of the above-mentioned resin, a functional group having curability is preferable.

The adhesive resin is not particularly limited, and specific examples of the functional group not containing a curable resin include polyester, polycarbonate, polyvinyl chloride, vinyl chloride, and other monomers having an unsaturated double bond. Copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, homopolymer of (meth) acrylate, (meth) acrylate and other unsaturated double bonds Monomer copolymer, polystyrene, copolymer of styrene with other monomers containing unsaturated double bonds, ketone-formaldehyde condensate or its hydride, epoxy resin, phenoxy resin, polyvinyl acetal or Copolymers, polyurethanes, polyureas, polyamines, and the like. These may be used alone or in combination of two or more.

The specific resin name of the polyester and the vinyl chloride-vinyl acetate copolymer described above is not particularly limited, and the following products can be used as an example.

About polyester, it is VYLON 200 manufactured by Toyobo Co., Ltd., and elitel UE3200 manufactured by UNITIKA Co., Ltd.; chloropolymer-vinyl acetate copolymer, SOLBIN AL, SOLBIN TA5R, SOLBIN TA3 manufactured by Nissin Chemical Industry Co., Ltd. Kanevinyl T555 manufactured by KANEKA Co., Ltd.

Further, a resin (polymer) or the like having a curable functional group at a side chain or a terminal of the above resin (polymer) may be mentioned. These include those having a functional group and those having no functional group, and these may be used alone or in combination of two or more.

The curable compound (curable resin) conceptually contained in the adhesive resin is preferably a functional group. The functional group is particularly preferably a polyol having a hydroxyl group, an epoxy resin having an epoxy group (epoxypropyl group) (epoxypropyl compound), a polyvalent carboxylic acid having a carboxyl group, and having a (meth)acrylic group ( A methyl acrylate monomer or oligomer or the like.

The epoxy resin may be a generally used epoxy resin as long as it is a polyfunctional epoxy resin having two or more epoxy groups in one molecule, and specific examples thereof include bisphenol A type and AP type. B type, BP type, C type, E type, F type, S type and other epoxy resin (bisphenol type epoxy resin); phenolic type epoxy resin; biphenyl type epoxy resin; naphthalene type epoxy resin; , 4-butanediol diepoxypropyl ether, cyclohexane dimethanol diepoxypropyl ether, trimethylolpropane diepoxypropyl ether, 3',4'-epoxycyclohexylmethyl - a polyvalent epoxy propyl compound such as 3,4-epoxycyclohexanecarboxylate, trimethylolpropane triepoxypropyl ether or hydroxyphenyl)methane triepoxypropyl ether.

The phenoxy resin-based thermoplastic resin is excellent in film-forming property, and even if a large amount of conductive powder is contained in the composition, contact between the conductive particles is less likely to be deteriorated.

In the case of the phenoxy resin, the number average molecular weight (Mn) is preferably 3,000 or more, more preferably 10,000 or more, more preferably 40,000 or less, and still more preferably 20,000 or less. In this range, the film forming property and the above effects are excellent.

The specific epoxy resin and phenoxy resin are not particularly limited, and the following products can be used as an example.

Epoxy resin, EPICLON830, EPICLON840, EPICLON850 manufactured by DIC Co., Ltd.; Epotohto YD-127, Epotohto YD-128 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; jER828 manufactured by Mitsubishi Chemical Corporation; Printec Corporation EPOX-MKR710, EPOX-MKR1710 manufactured by the company.

The phenoxy resin is JER1256 manufactured by Mitsubishi Chemical Corporation; Epotohto YP-50S manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; PKHC and PKHB manufactured by InChem Corporation.

The polyfunctional alcohol may, for example, be a low molecular polyol compound, and specific examples thereof include a bifunctional alcohol such as polyethylene glycol, polypropylene glycol or butylene glycol; trimethylolpropane, glycerin, and new A trifunctional or higher alcohol such as pentaerythritol or sorbitol.

Further, for example, a polymer polyol compound such as a polyester polyol having a molecular weight of 800 or more, a polyether polyol, a polycarbonate polyol, or a polycaprolactone polyol may be mentioned.

In addition, the adhesive resin is preferably used in combination of two or more kinds of polyester, phenoxy resin, epoxy resin, vinyl chloride-vinyl acetate co-heavy resin, and the like.

In the composition for printing of the present invention, the content of the adhesive resin varies depending on the printing method. For example, the gravure transfer, the screen transfer, and the pad printing are preferably 2% by mass based on the entire printing composition. The amount is 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 content of the adhesive resin is within this range, the viscosity, fluidity, structural viscosity, and thixotropy (time change of structural viscosity) of the printing composition are good by the synergistic effect with the mixed solvent described later. Even when printing continuously on a printing machine, it is difficult to cause trouble and it is possible to easily and stably obtain a good conductive pattern.

<hardener>

In the printing composition of the present invention, it is also preferred to cure the adhesive resin and to use a curing agent in combination therewith.

Specific examples of such a curing agent include oxetan compounds, acid anhydrides, amines, imidazoles, and phenols (resins). Further, the curing agent also contains a latent curing agent (an amine adduct, a blocked isocyanate compound, etc.) and a curing accelerator (octanoate or the like). These may be used alone or in combination of two or more.

The latent curing agent or the curing accelerator is not particularly limited, and specifically, the following products can be used as an example.

The closed polyisocyanate compound is Coronate AP-M, Coronate 2503, Coronate 2507, Coronate 2513, Coronate 2015 manufactured by Japan Polyurethane Industry Co., Ltd.; Duranate 17B-60P, Duranate TPA-B80E, Duranate by Asahi Kasei ChemMICALS Co., Ltd. MF-K60B, Duranate E402-B80B; Takeen B-830, Takenate B-815N, Takenate B-846N, Takenate B-882N from Mitsui Chemicals Co., Ltd.

About AA Adduct, AJICURE PN-23, AJICURE PN-H, AJICURE PN-40, AJICURE PN-F, AJICURE MY-24, AJICURE MY-25 manufactured by FINE TECHNO Co., Ltd.; CUREDUCT P-0505 manufactured by Industrial Co., Ltd.

The octanoate and the like are U-CAT SA1, U-CAT SA102, U-CAT SA102-50, and U-CAT SA106 manufactured by SAN-APRO Co., Ltd.

From the viewpoint of the fixing property to the conductive pattern of the substrate and the heat resistance, the curing agent preferably has a purpose of hardening by generating a covalent bond in the calcination step of the pattern after printing, and is compatible with The functional group of the aforementioned adhesive resin reaction.

This hardener is integrated with the adhesive resin in the above reaction, and becomes solid at 50 ° C, thereby exhibiting the fixability and heat resistance of the conductive pattern.

When the curing agent is contained, it is not particularly limited, and 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 based on the total of the curable adhesive resin.

<solvent>

The composition for printing of the present invention contains at least a conductive powder, an adhesive resin, and a mixed solvent, and the mixed solvent (1) contains an SP value of 2% by mass or more and 60% by mass or less based on the entire mixed solvent. 9.4 or more of the solvent (H) of 12.1 or less, and (2) the solvent (A) which has a SP value of 0.3 or less with respect to at least one solvent (H).

Here, the term "mixed solvent" means the entire mixture of all the solvents contained in the composition for printing. In addition, as described above, "the relatively low molecular weight curable compound which hardens into a resin" is conceptually contained in the adhesive resin even if it is liquid at normal temperature, and is not included in the (mixed) solvent.

Regardless of the SP value, any solvent can be used as the printing composition of the present invention as long as it is known as a printing ink. In particular, when the composition for printing of the present invention is a gravure transfer, a known solvent for gravure printing or gravure printing can be used; and if the printing composition of the present invention is a screen transfer user, A well-known solvent for screen printing can be used. If the printing composition of the present invention is a pad printing user, a known solvent for pad printing can be used.

Among these solvents, those which satisfy the specific SP value or the SP value which will be described later may be used in combination of two or more kinds.

The solvent is not limited, and specific examples thereof include the following.

Ethylene glycol condensate such as diethylene glycol or triethylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene Ethylene glycol monoalkyl ether such as alcohol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether or ethylene glycol monophenyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl Ethylene glycol dialkyl ether such as ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol dipentyl ether, ethylene glycol dihexyl ether, ethylene glycol diphenyl ether or Ethylene glycol diphenyl ether; the above "ethylene glycol" is replaced by a solvent such as "diethylene glycol" or "triethylene glycol".

In addition, the above-mentioned ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether or triethylene glycol monoalkyl ether monoacetate; ethylene glycol, diethylene glycol or triethylene glycol Alcohol diacetate and the like.

Further, the above-mentioned "ethylene glycol" may be substituted with a solvent of "propylene glycol".

Further, 3,5,5-trimethylhexanol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 3-methoxy-3- Alcohols such as methyl-1-butanol, polyester polyols, and aliphatic polyhydric alcohols; such carboxylic acid esters; cyclic esters such as γ-butyrolactone; propylene carbonate, butylene carbonate, ethylene carbonate, etc. Carbonate; N-methylpyrrolidone and the like.

Further, acetic acid; tetrahydrofuran; hydrocarbons such as benzene, toluene, cyclohexane, pentylbenzene, and xylene; esters of methyl acetate, ethyl acetate, dioctyl phthalate, ethyl formate, and aromatic ester; Ketones such as ketone, methyl ethyl ketone, cyclohexanone, acetone; chlorinated solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, dichloroethane, tetrachloroethane; octanediol, B Alcohol or mercaptan such as mercaptan, acetol or isopropanol; carbon disulfide; nitrogen-containing solvent such as propionitrile pyridine, nitroethane or acetonitrile; Alkane; ε-caprolactone and the like. Further, the solvents described in Tables 1 and 2 are repeated.

Two or more kinds of SP or SP values satisfying the specific SP to be described later can be mixed (combined) from these solvents, and used as the (mixed) solvent of the present invention.

The solvent having an SP value of 7.8 to 12.1 may, for example, be diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, or B. Diol 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, dipropylene 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 single Butyl ether, 3,5,5-trimethylhexanol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 3-methoxy-3- Methyl-1-butanol, γ-butyrolactone, benzene, ethyl acetate, tetrahydrofuran, pentylbenzene, xylene, methyl ethyl ketone, dioctyl phthalate, methyl acetate, two Alkane, cyclohexane, acetophenone, cyclohexanone, acetone, isopropanol, carbon tetrachloride, aromatic ester, benzene, chloroform, trichloroethylene, dichloromethane, dichloroethane, carbon disulfide, tetrachloro Ethane, propionitrile pyridine, nitroethane, acetonitrile, ε-caprolactone, octanediol, ethyl formate, ethanethiol, acetol, and the like. Further, the solvent described in Tables 1 and 2 is a solvent having a SP value of 7.8 to 12.1.

<<SP value of solvent>>

The "SP value" is a Solubility Parameter, which is a value defined by the normal solution theory introduced by Hildebrand, and is used as a measure indicating the polarity of the intermolecular force and physical properties.

The evaporation heat per 1 m of the liquid is set to ΔH [cal], and when the molar volume is set to V [cm ³ ], by [SP value] = (ΔH/V) ^1/2 [(cal/cm) ³ ) ^1/2 ] to define.

It is known empirically that the smaller the SP value difference between the two components, the greater the affinity and solubility.

The present inventors conducted a careful review of the influence of the (mixed) solvent on the silicone rubber on the surface of the blanket for the composition for conductive pattern printing, and found that by making the SP value within a predetermined range or having a predetermined relationship ( By mixing the solvent, it is possible to obtain a printing composition which achieves both the above-mentioned "viscosity maintenance property" and "volume destruction inhibition property", and it is also possible to cope with the printing of a pattern in which fine wires of different widths are mixed.

In the present invention, 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 based on the total of the "mixing solvent of the entire solvent of the composition for printing". Hereinafter, the solvent (H) having an SP value of 9.4 or more and 12.1 or less is simply referred to as "solvent (H)".

The content of the solvent (H) is required to be 2% by mass or more and 60% by mass or less, preferably 3% by mass or more and 57% by mass or less, and preferably 4% by mass or more and 55% by mass or less, based on the total amount of the mixed solvent. It is 5 mass% or more and 53 mass% or less. When two or more solvents (H) are contained, the above value is defined as the total content of all the solvents (H).

When it is more than the above lower limit value, the viscosity maintenance property is improved, and the effect on the silicone rubber on the surface of the blanket is reduced. In addition, when it is at most the above upper limit value, the volume breakage inhibition property is improved.

Further, when it is in the above range, the effects of the present invention described above can be preferably exhibited, and in particular, a printing composition which achieves both viscosity retention and volume breakage inhibition can be obtained, and even if the width or area is different The patterns are mixed together and any pattern printing can be done properly at the same time.

The content of the solvent (H) depends on the type of the adhesive resin and the concentration of the component other than the (mixed) solvent, but the concentration of the component other than the (mixed) solvent is high, and the solid content concentration is high. In this case, it is preferred that the content of the above solvent (H) is large.

In addition, the mixed solvent in the present invention contains a solvent (A) having an SP value of 0.3 or more and less than at least one solvent (H).

When two or more solvents (H) are contained, the solvent (A) having a SP value of 0.3 or more with respect to the solvent (H) having a high SP value may be contained.

Further, a solvent having a SP value of less than 0.3 with respect to at least one solvent (H) may be contained.

In addition, the "SP value is a solvent (A) which is 0.3 or less smaller than the solvent (H) of at least one type", and may be another solvent (H). That is, the present invention also includes a case where two solvents (H) having an SP value of 0.3 or more are included.

In the following, the "solvent (A) having a SP value of at least one solvent (H) of at least 0.3" is simply referred to as "solvent (A)".

The solvent (A) is a solvent having a SP value of 0.3 or more with respect to at least one solvent (H), more preferably a solvent having a SP value of 0.5 or more, and particularly preferably a solvent having a small 0.7 or more.

When the difference between the SP values of the solvent (A) and the solvent (H) is the above, that is, when at least two solvents having different SP values are contained, viscosity maintenance and volume destruction can be suppressed. In addition, even if patterns of different widths or areas are mixed together, printing of any pattern can be suitably performed at the same time.

When the solvent (H) having a SP value of 0.3 or more in the solvent (A) of the solvent (H) is present in the mixed solvent, the total content of the solvent (H) is preferably contained in the entire mixed solvent. 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. When it is too small, the aforementioned effect containing the solvent (H) is 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 total amount of the mixed solvent. It is more preferably 95% by mass or more, still more preferably 98% by mass or more, and particularly preferably 100% by mass.

When the solvent having an SP value of less than 7.8 is too large, the viscosity maintainability is deteriorated, and when the solvent having an SP value of more than 12.1 is too large, the volume damage suppressing property is deteriorated.

Further, in place of the "solvent having an SP value of 7.8 or more and 12.1 or less", it is more preferably "a solvent having an SP value of 8.0 or more and 11.0 or less", and particularly preferably a "solvent having an SP value of 8.3 or more and 9.6 or less". Further, the content of the solvent in the SP value range at this time is more preferably in the above range.

When the amount of the solvent whose SP value is too small is too large, the viscosity maintainability is deteriorated, and when the solvent having an excessive SP value is too large, the volume damage suppressing property is deteriorated.

The mixed solvent contained in the composition for printing of the present invention 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, and the solvent is used for the entire mixed solvent. The total content of the solvent (L) and the solvent (H) is preferably 70% by mass or more.

In other words, the solvent (H) and the solvent (A) must have a SP value of 0.3 or more (preferably 0.5 or more, particularly preferably 0.7 or more), and the distance (the portion of the difference between the SP values) preferably includes The SP value is in the range of 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 is simply referred to as "solvent (L)".

By containing the solvent (L) and the solvent (H), that is, by allowing the SP value to be in the range of 9.1 or more and 9.4 or less, and containing at least two solvents in the range above and below, the viscosity can be more preferably maintained. The printing composition which balances both the property and the volume damage suppression, and the patterning of any pattern can be simultaneously suitable even if the patterns of different widths or areas are mixed.

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% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

By including the solvent (L) and the solvent (H) in the above range, it is possible to particularly obtain a printing composition which achieves both adhesion maintenance and volume destruction inhibition, and further, even if patterns having different widths or areas are mixed, Printing of any pattern can be done at the same time as appropriate.

Further, in the above case, a solvent which is not a solvent (L) or a solvent (H) may be contained in a range of SP value 9.1 or more and 9.4 or less.

Further, the solvent (A) may be a solvent (H), a solvent having a SP value of 9.1 or more and 9.4 or less, or a solvent (L), preferably a solvent (L). That is, by containing a solvent (L) (may also be a solvent (A)) and a solvent (H) (by a solvent having an SP value of 9.1 or less and a solvent having an SP value of 9.4 or more), viscosity maintenance can be achieved. Both of the volume damage suppression properties can be considered, and even patterns having different widths or areas can be printed at the same time.

In order to obtain a printing composition excellent in viscosity retention, the solvent (H) is preferably (more preferably, either), and the vapor pressure at 20 ° C is 0.05 hPa or less. It is particularly preferable that the vapor pressure at 20 ° C is 0.01 hPa or less.

The solvent (H) is preferably (more preferably, either), and the boiling point in the normal pressure (1013 hPa) is 240 ° C or higher, more preferably 250 ° C or higher, and even more preferably 260 ° C or higher. Very good for those above 270 °C.

Specific solvent names and vapor pressures and boiling points of the respective solvents may be 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 (0.01hPa, 230.6 ° C), ethylene glycol monophenyl ether (0.013hPa, 244.7 ° C), triethylene glycol monomethyl ether (0.08hPa, 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 (0.01 hPa not Full, 302 ° C), 1,3-butanediol diacetate (0.00026 hPa, 232 ° C), etc., but is not limited thereto.

For example, when the line width is changed to a finer thickness of about 20 μm to about 30 μm, the depth of the intaglio plate becomes about 10 μm, and further, although (screen printing and pad printing are uniform), the printing is transferred to the blanket. It is unavoidable to reduce the amount (volume) of the composition, but in the (mixed) solvent, it is preferable to have a property that it is difficult to be absorbed into the blanket, and it is difficult to evaporate in order to improve the viscosity maintenance. The nature of the person.

In order to improve the "pattern linearity (less bending line)" and "pattern width reproducibility (less coarsening)", it is preferable that the surface tension (static) is 20 mN at 20 ° C in the mixed solvent. The solvent of at least 40 mN/m or less is contained in an amount of 80% by mass or more based on the total amount of the mixed solvent.

The surface tension (static) of the mixed solvent is not particularly limited, and 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.

In addition, the "solvent having a surface tension (static) of 20 mN/m or more and 40 mN/m or less at 20 ° C) preferably contains 80% by mass or more, preferably 90% by mass or more, and particularly preferably 95% by mass or more.

Further, the surface tension in the present invention is a value measured by a Wilhelmy method (manufactured by Kyowa Interface Science Co., Ltd., type: CBVP-Z) at a measurement temperature of 20 °C.

When the surface tension is too large, the linearity of the pattern on the rubber blanket or on the substrate when the surface of the blanket or the surface of the substrate is viewed from the vertical direction is deteriorated, and a beaded necking phenomenon (bending line) is generated, so that "pattern linearity" is present. (There is less bending line)" The case of deterioration, the case where the shape of the pattern is deformed, and the like.

On the other hand, when the surface tension is too small, when the surface of the blanket or the surface of the substrate is viewed from the vertical direction, the line width of the pattern is changed to be thicker than the line width of the printing plate (thickness), so that "the pattern width is wide. The case where the reproducibility (less thickening is small) is deteriorated, and the volume damage suppressing property is deteriorated.

With respect to specific solvent names and surface tensions, for example, diethylene glycol dibutyl ether (23.6 mN/m), triethylene glycol monomethyl ether (25.1 mN/m), triethylene glycol monobutyl Ether (27.7mN/m), diethylene glycol monobutyl ether (26.2mN/m), dipropylene glycol monobutyl ether (26.2mN/m), diethylene glycol monobenzyl ether (36.3mN/m) And other "solvents and surface tensions" described in Table 2, etc., but are not limited to these.

In the composition for printing of the present invention, the content of the mixed solvent is different depending on the printing method. For example, in the gravure transfer, it is preferably 3% by mass or more and 50% by mass or less based on the entire printing composition. It is preferably 5% by mass or more and 40% by mass or less, and particularly preferably 7% by mass or more and 35% by mass or less.

<Other ingredients>

Preferably, the printing composition of the present invention further contains "other components" as needed.

In the case of the "other components", in the case of gravure transfer, a known component of the gravure printing ink or the gravure printing ink may be mentioned, and in the case of the screen printing, a known screen printing ink may be mentioned. As the component, in the case of pad printing, a component of a known ink for pad printing can be cited.

Specific examples thereof include a fluidity-imparting agent, a fluidity-adjusting fine particle, a dispersion (stabilization) agent, an antifoaming agent, a release agent, a leveling agent, a plasticizer, a slip agent, a structural adhesive agent, and a touch. A denaturation agent, a stabilizer for suppressing a thermosetting reaction, and the like.

The fluidity-adjusting fine particles adjust the fluidity of the composition by the oil absorption amount and the specific surface area, and the printability is good. The number average particle diameter is preferably 1 μm or less, and particularly preferably 0.5 μm or less.

When the fluidity-adjusting fine particles are contained, the "flowability" of the composition for printing is improved.

The fluidity-adjusting fine particles are preferably, for example, a flame method (fumed) cerium oxide, colloidal cerium oxide, aluminum oxide, titanium oxide or the like. It is preferred to apply a treatment such as hydrophobic treatment.

The fluidity-adjusting fine particles are not particularly limited, and specifically, the following products can be used as an example.

SYLYSIA 310, SYLYSIA 320, SYLYSIA 350 manufactured by Fuji Silicea Chemical Co., Ltd.; AEROSIL 200 and AEROSIL 380 manufactured by AEROSIL Co., Ltd., Japan.

<Substrate>

The substrate on which the printing composition of the present invention is printed is not limited, and specific examples thereof include plastic (film), ceramic (film), tantalum wafer, glass, metal (plate), paper, cloth, rubber, wood, and the like. .

In the composition for printing of the present invention, both the viscosity-maintaining property and the volume-damage inhibiting property are obtained, and in particular, when the pattern having a line width of 50 μm or more is improved, the volume-damage inhibiting property is likely to be deteriorated, and when the pattern having a line width of 20 μm or less is improved, the film is easily deteriorated. Stickiness maintenance.

Therefore, in the substrate on which the composition for printing of the present invention is printed, a pattern having a pattern of a line width of 20 μm or less and a pattern having a line width of 50 μm or more is present on the same substrate, and the effect of the composition for printing of the present invention can be remarkably exhibited. It is better from the point of view.

In the case of the substrate, the printing composition of the present invention exhibits "viscosity maintenance" which is likely to be a problem when the thickness is thin, and the substrate is thicker than the thicker line. In addition, when it is thicker, it is easy to be a problem.

The composition for printing of the present invention is preferably used for a substrate printer having a pattern having a line width of 20 μm or less and a pattern having a line width of 50 μm or more, and more preferably a pattern having a line width of 20 μm or less and a line width of 100 μm. The substrate printer of the above-described pattern is particularly preferably used for a substrate printer having a pattern of a line width of 20 μm or less and a pattern having a line width of 150 μm or more. For the above reasons, it is more preferably used for a coexistence line width of 20 μm or less. A substrate printer with a pattern and a pattern having a line width of 300 μm or more.

Further, the above line width is defined as the line width on the substrate. There is a case where a pattern of a thin line width in a printing plate is combined, and a pattern of a thick line width is formed on a blanket or a substrate. Or consciously fit the pattern of the thinner line width in the plate to a pattern of thicker line width on the blanket or on the substrate.

In the present invention, the "viscosity maintenance property" and the "volume damage inhibition property" are characteristics at the time of transfer from the blanket to the substrate printing composition. Therefore, the line width is not specified as a plate. The line width is defined as the line width in the blanket and/or substrate. That is, it is not defined as the "width of the linear concave portion" of the intaglio plate in the gravure transfer or pad printing, nor is it defined as the "thickness of the portion lacking the linear portion" of the screen in the screen transfer.

<Use>

The printing target of the printing composition of the present invention is not particularly limited, but in order to remarkably exert the effect of the printing composition of the present invention, electronic components such as a touch panel, an electronic paper, a solar power generation panel, and a multilayer ceramic capacitor are preferable. Conductive patterns such as wiring, electrodes, and conductive circuits.

A particularly good object of the printed conductive pattern is a conductive pattern for a touch panel. That is, the substrate having the printed conductive pattern is particularly preferably a substrate having a conductive pattern for a touch panel.

<Printing method and manufacturing method of conductive pattern>

The printing composition of the present invention can be printed on a substrate by any printing method using a blanket to form a conductive pattern.

Since the printing composition of the present invention is improved in transferability from a blanket to a substrate, it is preferably used in a printing method using a blanket.

Another aspect of the present invention provides a method for producing a substrate having a conductive pattern, wherein a pattern is printed on a substrate by using the conductive pattern printing composition of the present invention, and a method for manufacturing the substrate having the conductive pattern has The step of transferring the conductive pattern printing composition from the printing plate to the blanket and the step of transferring the substrate to the substrate.

Examples of the printing method of the conductive pattern described above include gravure transfer, screen transfer, and pad printing.

Among them, in order to exert the above-described effects of the present invention particularly effectively, gravure transfer is preferred. That is, in the method for producing a substrate having a conductive pattern according to the present invention, the printing method is a method of transferring via gravure, and the printing plate is preferably a gravure plate or a gravure.

Gravure transfer, also known as gravure printing, is described, for example, in Patent Documents 2 to 5.

In the gravure transfer, a gravure plate (gravure plate) in which a concave portion corresponding to the electroconductive pattern is formed, a doctor blade in which a printing composition is filled in a concave portion of a gravure plate (gravure plate), and a surface are, for example, a silicone rubber The rubber blanket that constitutes it. Further, the intaglio plate used for the gravure transfer may be in a form different from the usual intaglio plate used in the gravure printing for general use. Hereinafter, there is a case where the "gravure plate or intaglio plate" used in the gravure transfer is simply referred to as "gravure plate (gravure plate)".

The printing composition is temporarily transferred from the concave portion of the gravure plate (gravure) to the blanket. The substrate is supplied in a manner opposite to the blanket, and the two are pressed, and the pattern on the blanket is transferred to the substrate again, thereby forming a printed pattern.

This printed pattern is heated and calcined to form a conductive pattern having conductivity.

According to this printing method, the shape of the printing pattern can be freely set by the shape of the concave portion, and the film transfer rate from the blanket to the substrate can be almost the same according to the printing composition of the present invention. Since it is 100%, it can be formed with high precision from a printing pattern corresponding to a fine wiring pattern to a pattern of a large area.

A gravure plate (gravure) can be used by a known person.

The gravure plate (gravure plate), the rubber blanket, and the substrate may each be a flat plate (sheet) or a cylindrical member. The blanket can also be crimped onto the substrate, and the pattern on the blanket can be continuously transferred to the substrate.

Further, when printing on a plurality of substrates using one blanket, it is preferable to include a step of drying the blanket absorbing the solvent after printing. This drying step can be carried out in one printing cycle or at intervals of 5 to 20 printing cycles.

The rubber blanket is preferably made of a silicone rubber. Preferably, a sheet having a silicone rubber layer on the surface is used. It is preferably used in a state called a rubber body which is wound into a rigid cylinder.

For example, a polyoxygenated rubber 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 into a rubber blanket.

Screen printing is described, for example, in Patent Document 6 and the like.

In the screen transfer, the printing composition is temporarily screen printed onto the blanket using a screen printing plate formed with a through hole corresponding to the conductive pattern. The substrate is supplied in such a manner as to face the blanket, and the two are pressed together to transfer the pattern on the blanket to the substrate again, thereby forming a printed pattern. The rubber blanket is preferably made of a silicone rubber.

This printed pattern is heated and calcined to form a conductive pattern having conductivity.

Pad printing, also known as staple printing, pad printing, is described, for example, in Patent Document 7.

In the pad printing, the printing composition on the intaglio plate is temporarily transferred to a soft hemispherical or ship-bottom rubber blanket (also referred to as a "printing head"), and then pressed on the substrate. A blanket (printing head) is used to transfer the printing composition on the blanket (printing head) to the substrate.

When a gravure is used, a doctor blade or the like is used in order to fill the concave portion with the printing composition, and is the same as the gravure transfer. The blanket (printing head) is preferably made of a silicone rubber.

For a specific pad printing blanket, for example, silicone pad R-12 manufactured by MINO GROUP can be used. 70 × 61 mm (bottom × height), hardness of 40 degrees.

In the method of manufacturing a substrate having a conductive pattern, a substrate belonging to a printing target (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 is coexisted on the same substrate, and the printing of the present invention is performed. It is preferable that the composition exhibits the advantages of both "viscosity maintenance" which is a problem of a thin line width and "volume destruction inhibition" which is a problem of a thick line width.

More preferably, a substrate having a pattern of a line width of 20 μm or less and a pattern having a line width of 100 μm or more is preferably a substrate having a pattern of a line width of 20 μm or less and a pattern having a line width of 150 μm or more, particularly preferably a pattern having a coexistence of a line width of 20 μm or less. A substrate having a pattern having a line width of 300 μm or more. In addition, in the actual substrate, most of them are those with a thinner line width and a thicker line width.

Further, there is a case where a pattern of a thin line width in a printing plate is used as a pattern of a thick line width on a blanket or a substrate, but the line width is defined as a line width on a substrate.

The "viscosity maintenance property" and the "volume destruction inhibition property" in the present invention are properties at the time of transfer from a blanket to a substrate printing composition. The above line width is not defined as the line width in the printing plate, but is defined as the line width in the blanket and/or the substrate.

 [Examples]  

In the following, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the examples as long as it does not exceed the gist of the invention. Here, "%" and "parts" are "% by mass" and "parts by mass" without particular restrictions.

Modulation example 1

<Modulation of Composition 1 for Conductive Pattern Printing>

In the composition described below, "Conductive Pattern Printing Composition 1" for gravure transfer is prepared.

In the case of the conductive powder, the average particle diameter is 0.5 μm of silver powder (SPQ03R manufactured by Mitsui Mining Co., Ltd.) in the median diameter (D50); the adhesive resin is a bisphenol epoxy resin. 1.5 parts of EPICLON 840 (made by DIC Co., Ltd.) and 5.0 parts of phenoxy resin (Epotohto YP-50S manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); hardener, amine compound (AjICURE made by Ajinomoto FINE TECHNO Co., Ltd.) MY-24) 0.8 parts; the fluidity-adjusting fine particles are 0.2 parts of a fire oxidized cerium oxide (SYLYSIA 320 manufactured by Fuji Silicea Chemical Co., Ltd.); and 30 parts of the above-mentioned "mixed solvent containing a solvent contained in Table 2" are used. Composition. In addition, the "mixed solvent" is the total amount of the solvent contained in the composition for printing, and "30 parts" is the total amount of all the solvents.

Modulation example 2

<Preparation of Composition 2 for Conductive Pattern Printing>

In the preparation of the following "Conductive Pattern Printing Composition 1" in Preparation Example 1, except that 30 parts of the mixed solvent was substituted, the mixed solvent amount was reduced to 25 parts (the mixed solvent amount was decreased, and the solid content concentration was increased). In the same manner as in Example 1, the "conductive pattern printing composition 2" for gravure transfer was prepared.

The content ratio of each solvent in the mixed solvent is the same as that of the "conductive pattern printing composition 1".

In the "conductivity pattern printing composition 1", the pattern of any line width is evaluated only for the case where the volume destruction inhibitory property is "x".

In the case of the "conducting pattern printing composition 2", the density of the solid portion is increased as compared with the "conducting pattern printing composition 1". The filling of the concave portion is insufficient, and the conductive pattern printed on the substrate is liable to cause defects such as "broken line" or "pinhole". Therefore, when the "conductivity pattern printing composition 1" is used, the volume damage suppression property is "x" in the pattern of any line width, and even if the "conductivity pattern printing composition 2" is evaluated, the latter will be comprehensively described. The best evaluation is only "△".

Evaluation Example 1

<Method of gravure transfer>

A pattern in which lines of 20 μm in width, 50 μm in width, and 150 μm in width were mixed was printed by gravure transfer. The gravure plate (gravure) used was 10 μm deep.

In the table, a pattern having a width of 20 μm is simply referred to as "a line width is small", a pattern having a width of 50 μm is simply referred to as "a line width", and a pattern having a width of 150 μm is simply referred to as a "line width".

A silicone rubber sheet having a thickness of 0.85 mm (composed of a silicone rubber/polyester film layer, a rubber hardness (JIS A) of 45 degrees, a surface average roughness Ra: 0.1 μm, and a surface tension of 21 mN/m) was used. The gravure transfer device of the blanket roll was printed on a substrate made of PET using the composition for printing obtained above. The evaluation and judgment are performed based on the evaluation examples described below.

Evaluation Example 2

<Evaluation method of viscosity maintenance>

For each printed piece, for the printed blanket and the substrate, the pattern remaining on the blanket and the pattern transferred onto the substrate were observed by optical microscopy and visual inspection. The judgment was made on the basis of the following criteria.

<Criteria for determination of viscosity maintenance>

○: In 10 sheets of printing, the pattern on the blanket was transferred to all 10 substrates without problems.

△: In 10 sheets of printing, "the pattern on the blanket was transferred from the first sheet to the substrate, but there was a pattern that was not transferred to the substrate in the middle of the film" or "the first sheet was not transferred." The pattern printed on the substrate, but the pattern is transferred to the substrate at the beginning.

×: In 10 sheets of printing, there were patterns that were not transferred onto all of the ten substrates.

Evaluation Example 3

<Evaluation method of volume damage inhibition>

For each printed piece, for the printed blanket and the substrate, the pattern remaining on the blanket and the pattern transferred onto the substrate were observed by optical microscopy and visual inspection. The determination was made on the basis of the following criteria.

<Criteria for determination of volume damage inhibition>

○: In 10 sheets of printing, all of the 10 sheets did not have a printing composition remaining on the blanket without problems.

△: In the ten-piece printing, "there is no printing composition remaining on the blanket from the first sheet, but there is a residue on the blanket in the middle of the film" or "the first sheet is left on the blanket." The composition, but there is no residue on the rubber blanket in the middle of the journey."

×: In 10 sheets of printing, all of the 10 sheets of the composition for printing remained on the blanket.

Evaluation Example 4

<Evaluation method of pattern straightness (less bending line)>

Using a "50 μm line and space 1:1 pattern" in a printing plate, an optical microscope (reflected light) was used to observe and photograph at a magnification of 100 times, and the pattern line width on the substrate was measured. The value of the formula (1) is judged as "pattern linearity (less bending line)". Further, the unit of the value of the following formula (1) has a numerator and a denominator of [μm].

100×[pattern line width (maximum value) - pattern line width (minimum value)]/50...(1)

<Determination of pattern linearity (less bending line)>

○: The value of the formula (1) is 0% or more and 20% or less.

△: the value of the formula (1) is more than 20% and less than 50%

×: The value of the formula (1) is greater than 50%

Evaluation Example 5

<Evaluation method of pattern wide reproducibility (less coarser)>

Using a "50 μm line and space 1:1 pattern" in a printing plate, an optical microscope (reflected light) was used to observe and photograph at a magnification of 100 times, and the pattern line width on the substrate was measured. The value of the formula (2) is judged as "the pattern width reproducibility (less coarser)". Further, the unit of the value of the following formula (2) has a numerator and a denominator of [μm].

100×[pattern line width on the substrate -50]/50...(2)

<Determination of pattern width reproducibility (less coarser)>

○: The value of the formula (2) is 20% or less (the negative % is also included)

△: the value of the formula (2) is more than 20% and less than 50%

×: The value of the formula (2) is greater than 50%

Evaluation Example 6

<Method of comprehensive evaluation>

The adhesion maintenance, volume damage inhibition, pattern linearity (less bending line), and pattern width reproducibility (less coarsening) were comprehensively evaluated.

In addition, the line composition width of the printing composition 1 is evaluated as the printing composition 2 in which the solid content concentration is increased by reducing the amount of the mixed solvent.

<Judging criteria for comprehensive evaluation>

○: Among the viscosity-maintaining property and the volume-damage inhibiting property of the composition for printing 1, there are no × and Δ is two or less, and the pattern linearity (less bending line) and pattern width reproducibility (less coarsening) are It is ○.

△: In the viscosity retaining property and the volume breakage inhibiting property of the composition for printing 1, there are no × and Δ is three or more, or the evaluation result of the printing composition 2 is not ×, or the pattern is linear ( The bending line is less), and the pattern width reproducibility (less of which is thicker) is Δ.

X: The composition for printing 1 and the composition for printing 2 have a "x" in both the viscosity retention property and the volume destruction inhibitory property.

As shown in Table 2, in the composition for conductive pattern printing (No. 11 to 31) using a mixed solvent, the mixed solvent is a solvent (H) having an SP value of 9.4 or more and 12.1 or less with respect to the entire mixed solvent. It is contained in an amount of 2% by mass or more and 60% by mass or less, and the solvent (A) having an SP value of 0.3 or more with respect to at least one solvent (H) is "○" or "△". It is judged to be good.

On the other hand, in the conductive pattern printing compositions (No. 32 to 42) which did not satisfy the requirements of the present invention, the comprehensive evaluations were all "x", and it was judged to be defective.

Among the conductive pattern printing compositions No. 11 to 31 which were judged to be good, the composition of the conductive pattern printing having a SP value of 7.8 or more and 12.1 or less was less than 90% by mass with respect to the entire mixed solvent. (No. 24), even if the above requirements are met, the overall evaluation is "△".

Further, among the conductive pattern printing compositions No. 11 to 31 which are judged to be good, the solvent (L) having an SP value of 7.8 or more and 9.1 or less and the SP value are 9.4 or more and 12.1 or less with respect to the entire mixed solvent. The composition for conductive pattern printing (No. 16, 17, 23, 25) in which the total content of the solvent (H) is less than 70% by mass, and the comprehensive evaluation is "△" even if the above requirements are satisfied.

Further, among the conductive pattern printing compositions No. 11 to 31 which are judged to be good, in the solvent (H), there is a conductive pattern printing composition having a vapor pressure at 20 ° C of more than 0.05 hPa ( No. 28, 30), even if the above requirements are met, the comprehensive evaluations are all "△".

In addition, among the components for conductive pattern printing No. 11 to 31 which were judged to be good, the solvent having a surface tension of 20 mN/m or more and 40 mN/m or less in the mixed solvent at 20 ° C was mixed with respect to the entire mixed solvent. Only the conductive pattern printing compositions (No. 29, 30) having a total amount of less than 80% by mass were contained, and even if the above requirements were satisfied, the comprehensive evaluations were all "△".

 [Industrial availability]  

In the conductive pattern printing composition of the present invention, it is estimated that it is excellent in transferability, and it is estimated that it can be widely used when forming conductive patterns such as wirings, electrodes, and conductive circuits of various electric parts/electronic parts.

Claims (13)

 A conductive pattern printing composition containing at least a conductive powder, an adhesive resin, and a mixed solvent, and 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 solvent (H), and the mixed solvent contains a solvent (A) having an SP value of 0.3 or more with respect to at least one solvent (H).    The conductive pattern printing composition according to the first aspect of the invention, wherein the solvent (A) is a solvent having a SP value of 0.5 or more with respect to the at least one solvent (H).    The conductive pattern printing composition according to the first or second aspect of the invention, wherein the solvent having a SP value of 7.8 or more and 12.1 or less is contained in an amount of 90% by mass or more based on the entire mixed solvent.    The composition for conductive pattern printing according to the first aspect of the invention, wherein the mixed solvent contains a solvent (L) having an SP value of 7.8 or more and 9.1 or less, and a solvent having an SP value of 9.4 or more and 12.1 or less ( H) The total content of the solvent (L) and the solvent (H) is 70% by mass or more based on the entire mixed solvent.    The conductive pattern printing composition according to the first or second aspect of the invention, wherein the solvent (H) has a vapor pressure of 0.05 hPa or less at 20 ° C.    The conductive pattern printing composition according to the first aspect of the invention, wherein the mixed solvent contains 80% by mass or more of the total surface tension of the mixed solvent at 20 ° C or more. It is a solvent of 20 mN/m or more and 40 mN/m or less.    The conductive pattern printing composition according to claim 1 or 2, wherein the conductive powder is a silver powder.    The conductive pattern printing composition according to claim 1 or 2, wherein the substrate is printed on a substrate, wherein the substrate has a pattern having a line width of 20 μm or less and a line width of 50 μm or more. Patterner.    The conductive pattern printing composition according to claim 1 or 2, wherein the printed conductive pattern is a conductive pattern for a touch panel.    The composition for conductive pattern printing according to claim 1 or 2, which is used for gravure offset printing.    A method for producing a substrate having a conductive pattern, which comprises using the composition for conductive pattern printing according to any one of claims 1 to 10, and printing a pattern on the substrate, which has the conductive The step of transferring the composition for pattern printing from the printing plate to the blanket, and the step of transferring the substrate to the substrate.    The method for producing a substrate having a conductive pattern according to claim 11, wherein the substrate has a pattern having a line width of 20 μm or less and a pattern having a line width of 50 μm or more.    The method for producing a substrate having a conductive pattern according to claim 11 or 12, wherein the printing method is a method of transferring by gravure, wherein the printing plate is a gravure plate. Or gravure.