WO2014142004A1

WO2014142004A1 - Resin composition for forming receiving layer, and receiving base, printed material, conductive pattern and electrical circuit which are obtained using same

Info

Publication number: WO2014142004A1
Application number: PCT/JP2014/055828
Authority: WO
Inventors: 公恵斉藤; 白髪　潤; 亘冨士川; 村川　昭
Original assignee: Dic株式会社
Priority date: 2013-03-13
Filing date: 2014-03-06
Publication date: 2014-09-18
Also published as: JP5594451B1; JPWO2014142004A1; TW201443151A

Abstract

The present invention provides a resin composition for forming a receiving layer, which is characterized by containing a urethane resin (C) that has a structure derived from a vinyl polymer (a1) in a side chain, said urethane resin (C) being obtained by reacting a polyol (A) that contains the vinyl polymer (a1), which has two hydroxy groups at one end, and a polyisocyanate (B). This resin composition for forming a receiving layer is able to form a receiving layer that is capable of holding a fluid such as an ink and exhibits excellent adhesion to various supporting bodies. This resin composition for forming a receiving layer is also able to form a receiving layer that is provided with excellent printability and does not cause bleeding of a fluid such as an ink.

Description

RECEPTION LAYER FORMING RESIN COMPOSITION AND RECEPTION SUBSTRATE, PRINTED MATERIAL, CONDUCTIVE PATTERN AND ELECTRIC CIRCUIT OBTAINED USING THE SAME

The present invention relates to a resin composition capable of forming a layer capable of receiving a fluid such as ink, a receiving substrate provided with a receiving layer, and a printed matter such as a conductive pattern.

In recent years, the ink-jet printing industry has been growing rapidly, and the performance of ink-jet printers and the functionality of inks have increased dramatically, making it easy for ordinary households to achieve high-definition and clear printability equivalent to silver halide photography. It is becoming possible to obtain images. For this reason, ink jet printers are starting to be used not only in homes but also in various fields including the production of large advertising signs.

On the other hand, the improvement in image quality of ink-jet prints is largely due to the improvement in printing ink as well as the higher performance of the printer. Specific improvements to printing inks include the selection of solvents in the ink and the selection of dyes or pigments. In recent years, pigment inks that are known to have high color development properties comparable to dye inks. Is attracting attention,

However, even when the pigment ink having the high color developability is used, depending on the composition of the ink receiving layer, a print image having high color density and excellent printability can be formed, such as causing ink bleeding. There were cases where it was difficult. Also, with the diversification of ink-jet prints, various materials are used as a support on which the ink receiving layer is provided. Conventional ink receiving layers are adhesive to plastic films such as polyethylene terephthalate. In this case, the receiving layer may be peeled with time.

By the way, it is being studied to use a conventionally known printing method such as the ink jet printing method or the screen printing method in the case of creating a conductive pattern such as an electronic circuit. This is because with recent demands for higher performance, smaller size, and thinner electronic devices, there is a strong demand for higher density and thinner electronic circuits and integrated circuits.

As a method for producing a conductive pattern such as the electronic circuit, specifically, a conductive ink containing a conductive substance such as silver is printed on the surface of the support by an ink jet printing method or a screen printing method, and then dried. And the method of heating and light irradiation as needed is mentioned.

However, even if the conductive ink is directly printed on the surface of various supports, the conductive ink is not easily adhered to the surface of the support, and thus easily peels off. In some cases, disconnection may occur. Especially, since the support made of polyimide resin, polyethylene terephthalate resin, etc. is rich in flexibility, it is expected to be used for the production of a foldable flexible device, but the surface of the support made of polyimide resin or the like is In particular, since ink and the like are difficult to adhere to each other, they are liable to be peeled off. In some cases, the finally obtained electronic circuit or the like is disconnected or the conductivity is lowered.

As a method for solving the above problem, for example, a method of producing a conductive pattern by drawing a pattern by a predetermined method using a conductive ink on an ink receiving substrate provided with a latex layer is known. It is known that an acrylic resin can be used as the latex layer (see Patent Document 1).

However, the ink receiving layer made of the latex layer constituting the conductive pattern may cause bleeding of the conductive ink, unevenness of the printing thickness, etc. In some cases, it is difficult to form a conducting wire composed of a thin wire having a width of approximately 0.01 μm to 200 μm, which is generally required.

Further, when the conductive pattern is formed, a printed matter printed with the conductive ink is generally used for the purpose of bringing the conductive substances contained in the conductive ink into contact with each other to impart conductivity. In many cases, it is heated and baked at a temperature of ℃ or higher.

However, since the ink receiving layer such as the latex layer described in the literature 1 is easily deteriorated due to the influence of heat received in the baking process, the adhesion of the interface between the ink receiving layer and the support is particularly high. It is easy to cause a drop, and even if a very slight force is applied, it may be easily peeled off.
Further, when the baking process is performed, excessive swelling and deformation of the latex layer, which is an ink-receiving layer, are likely to be caused. In addition, since the latex layer often does not have sufficient adhesion to the support before heating in the baking step, the support and the ink receiving layer are not subjected to the baking step. And may cause partial peeling.

By the way, when forming the conductive pattern, copper is formed on the surface of the conductive pattern from the viewpoint of forming a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time. In many cases, the plating process is performed by using, for example.

However, the plating agent used for the plating treatment and the agent used in the cleaning step are usually strongly alkaline and strongly acidic, and thus easily cause peeling from the support such as the receiving layer. In some cases, the conductive pattern may be disconnected.

Therefore, the conductive pattern is required to have a level of durability that does not cause peeling of the conductive ink-receiving layer from the support even when it is repeatedly immersed in the drug or the like for a long time. ing.

JP 2009-49124 A

The problem to be solved by the present invention is that, among the receiving layers capable of carrying a fluid such as ink, a receiving layer having excellent adhesion to various supports can be formed, causing bleeding of the fluid such as ink. It is an object of the present invention to provide a resin composition for forming a receiving layer capable of forming a receiving layer having excellent printability without any problems.

In addition, the second problem to be solved by the present invention is that, among the receiving layers capable of supporting a fluid such as conductive ink, a receiving layer having excellent adhesion to the support can be formed. Even if it is possible to draw fine lines at a level that can be used to achieve higher density of electronic circuits etc. without causing blurring or repellency, and even if chemicals such as plating chemicals or various organic solvents adhere Provided is a resin composition for forming a receiving layer capable of forming a printed matter such as a conductive pattern having a level of durability capable of maintaining good electrical conductivity without causing peeling of the receiving layer from the support. That is.

As a result of studying the above problems, the present inventors have found that the problems of the present invention can be solved when a specific urethane resin and vinyl polymer are used in combination.

That is, the present invention provides a vinyl polymer in the side chain obtained by reacting a polyol (A) containing a vinyl polymer (a1) having two hydroxyl groups at one end and a polyisocyanate (B). The present invention relates to a resin composition for forming a receiving layer, comprising a urethane resin (C) having a structure derived from (a1).

The resin composition for forming a receiving layer of the present invention can form a receiving layer having excellent adhesion to various supports, and is capable of printing with high color without causing bleeding of a fluid such as pigment ink. Since it contributes to the formation of printed images with excellent properties, it can be used for recording media used for the production of advertisements, signboards, signs, etc. that can be installed indoors and outdoors.

In addition, the resin composition for forming a receiving layer of the present invention can form a receiving layer having excellent adhesion to a support, and can realize high density of electronic circuits and the like without causing bleeding of conductive ink. Since it is possible to provide a thin line of a level capable of drawing a thin line that can be provided, and a receiving layer excellent in durability can be formed, for example, an organic solar cell, an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, Generally used in new fields such as printed electronics, such as peripheral wiring for RFID such as contactless IC cards, formation of electronic circuits, wiring for electromagnetic shielding of plasma displays, integrated circuits, manufacturing of organic transistors, etc. be able to.

In addition, the receptor layer formed using the resin composition for forming a receptor layer of the present invention is printed on the receptor substrate of the present invention using a fluid such as conductive ink or plating nucleating agent, and then heated. By forming a cross-linked structure in the ink receiving layer, it is possible to obtain a printed matter (plating structure) having a higher level of durability. Specifically, it is possible to obtain a printed matter (plating structure) having a level of durability that can prevent the conductive material contained in the fluid from being lost from the surface of the receiving layer in the plating process. It becomes.

The resin composition for forming a receiving layer of the present invention is obtained by reacting a polyol (A) containing a vinyl polymer (a1) having two hydroxyl groups at one end and a polyisocyanate (B). The side chain contains a urethane resin (C) having a structure derived from the vinyl polymer (a1).
The receiving layer forming resin composition absorbs the solvent in the fluid when the fluid containing the conductive material or the pigment is brought into contact, and carries the conductive material or the pigment. Can be used to form

First, the urethane resin (C) used in the present invention will be described.
The urethane resin (C) used in the present invention is one in which the structure derived from the vinyl polymer (a1) is grafted to the side chain of the structure of the urethane resin as the main chain. Specifically, as the urethane resin (C), a polyol (A) containing a vinyl polymer (a1) having two hydroxyl groups at one end, a polyisocyanate (B), and optionally a chain. A product obtained by reacting an extender is used.

The urethane resin (C) is preferably one having a structure derived from the vinyl polymer (a1) in the range of 1% by mass to 70% by mass with respect to the total amount of the urethane resin (C). It is preferable to use a material having a mass% to 50 mass% in order to give even better printability and fine lineability.

Further, as the urethane resin (C), in addition to imparting better adhesion, printability and fine lineability, and further improving the durability, a weight average in the range of 10,000 to 150,000 Those having a molecular weight are preferably used, and those having a weight average molecular weight in the range of 10,000 to 50,000 are more preferably used.

The resin composition for forming a receiving layer of the present invention contains the urethane resin (C), but as the solvent, it is used in combination with a solvent such as an aqueous medium (D) or an organic solvent. It is preferable for improving the coating workability.
When the aqueous medium (D) is used as the solvent, the urethane resin (C) is preferably present in a dispersed state in the aqueous medium (D). Examples of the method for dispersing the urethane resin (C) in the aqueous medium (D) include a method using a surfactant and a method using a urethane resin (C) having a hydrophilic group.

As the hydrophilic group, for example, an anionic group, a cationic group, or a nonionic group can be used, and an anionic group is more preferably used.

As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used. Among them, a part or all of the carboxyl group or the sulfonic acid group depends on a basic compound or the like. It is preferable to use a neutralized carboxylate group or sulfonate group in order to impart good water dispersibility.

Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine; metal bases including sodium, potassium, lithium, calcium, and the like Compounds. When forming a conductive pattern or the like, it is preferable to use the organic amine or alkanolamine because the metal salt compound may inhibit the conductivity.

When the carboxylate group or sulfonate group is used as the anionic group, they are preferably present in the range of 5 mmol / kg to 4,000 mmol / kg with respect to the entire urethane resin (C), and 50 mmol / kg. It is more preferable to exist in the range of ˜2,000 mmol / kg in order to maintain good water dispersion stability of the urethane resin (C).

Moreover, as said cationic group, a tertiary amino group etc. can be used, for example.
Examples of the acid that can be used for neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid; organic acids such as sulfonic acid and methanesulfonic acid. Sulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid can be used alone or in combination of two or more. In the case of forming a conductive pattern or the like, it is preferable to use acetic acid, propionic acid, lactic acid, maleic acid, or the like because chlorine, sulfur, or the like may inhibit the conductivity.

The tertiary amino group as the cationic group may be partially or fully quaternized. As the quaternizing agent, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like can be used, and dimethyl sulfate is preferably used.

Examples of the nonionic group include polyoxyalkylene groups such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group. Can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

The urethane resin (C) has a structure derived from the vinyl polymer (a1) in the side chain, and in the main chain of the urethane resin (C), a polyether polyol, a polyester polyol, a polyester ether polyol, and It is preferable to use one having a structure derived from one or more kinds of polyols (a2) selected from the group consisting of polycarbonate polyols, in order to impart further excellent adhesion, printability, and fine lineability, and is derived from polyester polyols. It is more preferable to use one having the structure of
Specific examples of the structure derived from the polyol (a2) include a polyether structure, a polyester structure, a polyetherester structure, and a polycarbonate structure.

The structure derived from the polyol (a2) is preferably present in the range of 5% by mass to 80% by mass with respect to the total amount of the urethane resin (C).

The polyol (A) used in the production of the urethane resin (C) has two hydroxyl groups at one end for the purpose of introducing a vinyl polymer structure into the side chain of the urethane resin structure as the main chain. Vinyl polymer (a1) is used.

As the vinyl polymer (a1) having two hydroxyl groups at one end used for the production of the urethane resin (C), for example, various vinyl monomers are polymerized in the presence of a chain transfer agent having two hydroxyl groups. What is obtained by doing can be used. Specifically, the vinyl monomer (a1-2) is radically polymerized in the presence of a chain transfer agent (a1-1) having two hydroxyl groups, a mercapto group, and the like, and the vinyl ester is originated from the mercapto group. The thing which the monomer polymerized is mentioned.

In addition, as the vinyl polymer (a1) having two hydroxyl groups at one end, for example, radical polymerization of a vinyl monomer in the presence of a chain transfer agent having a carboxyl group and a mercapto group, As a starting point, a polymer obtained by reacting the vinyl monomer with a compound having a hydroxyl group and a glycidyl group can be used.

Since the obtained vinyl polymer (a1) has two hydroxyl groups derived from the chain transfer agent at one end, the two hydroxyl groups react with an isocyanate group of the polyisocyanate (B) described later. By this, a urethane bond can be formed.

The vinyl polymer (a1) having two hydroxyl groups at one end facilitates viscosity control when reacting with the polyisocyanate (B), and provides better adhesion, printability, and fineness. In view of this, it is preferable to use those having a number average molecular weight in the range of 500 to 10,000, and it is more preferable to use those having a number average molecular weight in the range of 1,000 to 5,000.

In addition, as the vinyl polymer (a1), by imparting a hydrophilic group to the obtained urethane resin (C), from the viewpoint of imparting excellent storage stability to the resin composition for forming a receiving layer of the present invention. A vinyl polymer having a hydrophilic group can also be used.

As the hydrophilic group, an anionic group, a cationic group, or a nonionic group can be used. As the hydrophilic group that may be present in the vinyl polymer (a1), any of an anionic group and a cationic group can be used. Either one or a combination of both is preferred.

As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used. Among them, a part or all of the carboxyl group and the sulfonic acid group are formed by a basic compound or the like. It is preferable to use a neutralized carboxylate group or sulfonate group in order to impart good water dispersion stability. As the cationic group, for example, a tertiary amino group can be used, and as the nonionic group, for example, a polyethylene oxide chain can be used.

In addition, the vinyl polymer (a1) has a vinyl polymer structure derived from the vinyl polymer (a1) other than the two hydroxyl groups at one end in introducing the side chain of the urethane resin (C). It is preferable that they have no other hydroxyl groups. Specifically, it is preferable not to use a vinyl monomer having a hydroxyl group as much as possible as the vinyl monomer (a1-2) that can be used in the production of the vinyl polymer (a1).

Examples of the chain transfer agent that can be used for the production of the vinyl polymer (a1) having two hydroxyl groups at one end include, for example, a chain transfer agent (a1-1) having two hydroxyl groups and a mercapto group, a carboxyl group, and the like. And a chain transfer agent having a mercapto group can be used. Among these, it is preferable to use a chain transfer agent (a1-1) having two hydroxyl groups and a mercapto group because the vinyl polymer (a1) can be easily produced.

Examples of the chain transfer agent (a1-1) having two hydroxyl groups and a mercapto group include 3-mercapto-1,2-propanediol (thioglycerin), 1-mercapto-1,1-methanediol, -Mercapto-1,1-ethanediol, 2-mercapto-1,3-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol 1-mercapto-2,3-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like can be used. . Of these, it is preferable to use 3-mercapto-1,2-propanediol because it has less odor, is excellent in terms of workability and safety, and is versatile.

Examples of the vinyl monomer (a1-2) used for the production of the vinyl polymer (a1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl. (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate , (Meth) acrylic acid alkyl esters such as stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate; (meth) acrylic acid, ( Meta) Acid groups such as β-carboxyethyl crylate, 2- (meth) acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride or the like Vinyl monomers having acid anhydride groups; (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) Acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide; 2-aziridinylethyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylamino Propyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [2- (meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2 -Vinylpyridine; N-methylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate; aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate , Butyl vinyl benzyl amino Vinyl monomers having nitrogen atoms such as vinylphenylamine and p-aminostyrene; nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile; 2,2,2-trifluoroethyl (meth) acrylate, 2,2 , 3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate and other fluorine-containing vinyl monomers; vinyl acetate, vinyl propionate, vinyl versatate, etc .; methyl vinyl ether, ethyl vinyl ether Vinyl ethers such as propyl vinyl ether and butyl vinyl ether; vinyl compounds having an aromatic ring such as styrene, α-methyl styrene and divinyl styrene; isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinyl chloride Den, N-vinylpyrrolidone; vinyl polymers having a polyoxyethylene group such as polyoxyethylene monomethyl ether (meth) acrylate and polyoxyethylene monoethyl ether (meth) acrylate can be used.

As the vinyl monomer (a1-2), it is possible to use one containing at least one selected from the group consisting of the (meth) acrylic acid and the (meth) acrylic acid alkyl ester. It is preferable because the reaction can be easily controlled and production efficiency can be improved.

The polymerization reaction between the chain transfer agent (a1-1) having two hydroxyl groups and a mercapto group and the vinyl monomer (a1-2) is, for example, toluene or methyl ethyl ketone adjusted to a temperature of about 50 ° C. to 100 ° C. It can proceed by radically polymerizing the chain transfer agent (a1-1) and the vinyl monomer (a1-2) collectively or sequentially in a solvent such as the above. As a result, radical polymerization of the vinyl monomer (a1-2) proceeds from the mercapto group or the like of the chain transfer agent (a1-1), and the vinyl polymer (a1) having two hydroxyl groups at one end Can be manufactured. When producing a vinyl polymer (a1) having two hydroxyl groups at one end by the above method, a conventionally known polymerization initiator may be used as necessary.

The vinyl polymer (a1) having two hydroxyl groups at one end obtained by the above method is in the range of 1% by mass to 70% by mass with respect to the total mass of raw materials used for the production of the urethane resin (C). It is preferable to use in the range of 5% by mass to 50% by mass in order to impart further excellent adhesion, printability, and fine lineability. The total mass of raw materials used for the production of the urethane resin (C) refers to the vinyl polymer (a1), and later-described polyol (a2) and other polyols (a3) that can be used as necessary. When the chain extender is used, the total of the polyol (A), the polyisocyanate (B), and the chain extender is used. Indicates mass. The same applies hereinafter.

Moreover, as a polyol (a2) which can be used for manufacture of the said urethane resin (C), 1 or more types chosen from the group which consists of a polyether polyol, a polyester polyol, a polyester ether polyol, and a polycarbonate polyol, for example can be used. . Among them, it is preferable to use a polyester polyol or a polycarbonate polyol in order to give even better adhesion, printability, and fine lineability.

As the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolethane, Trimethylolpropane and the like can be used.

Further, as the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or the like can be used.

Specifically, it is preferable to use polyoxytetramethylene glycol, polypropylene glycol, or polyethylene glycol as the polyether polyol in order to impart even better adhesion, printability, and fine lineability. Further, as the polyether polyol, it is more preferable to use a polyether polyol having a number average molecular weight in the range of 1,000 to 3,000 in order to impart even more excellent adhesion, printability, and fineness. .

Examples of the polyester polyol include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ε-caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyester obtained by the above, copolyesters thereof and the like can be used.

As the low molecular weight polyol, for example, ethylene glycol, propylene glycol and the like can be used.

As the polycarboxylic acid, for example, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or esterified products thereof can be used.

As the polyester ether polyol, for example, those obtained by reacting a polyether polyol obtained by adding the alkylene oxide to the initiator and a polycarboxylic acid can be used. As the initiator and the alkylene oxide, the same ones exemplified as those usable when the polyether polyol is produced can be used. Moreover, as said polycarboxylic acid, the thing similar to what was illustrated as what can be used when manufacturing the said polyester polyol can be used.

Examples of the polycarbonate polyol that can be used include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A or the like.

As the carbonate ester, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

Examples of the polyol that can react with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-pro Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone Relatively low molecular weight dihydroxy compounds such as resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene adipate, polyhexa Polyester polyols such as methylene succinate and polycaprolactone can be used.

As the polyol (a2), those having a number average molecular weight in the range of 500 to 10,000 are preferable in order to impart even better adhesion, printability, and fineness, and 1,000 to 3,000. It is more preferable to use one having a number average molecular weight in the range of

The polyol (a2) is preferably used in the range of 5% by mass to 80% by mass with respect to the total mass of raw materials used for the production of the urethane resin (C). Furthermore, it is preferable to use in the range of 15% by mass to 80% by mass in order to give even better adhesion, printability, and fine lineability.

In addition, the polyol (a2) is preferably used in combination with the vinyl polymer (a1) in a specific range in order to impart much more excellent adhesion, printability, and fine lineability. For example, [(a1 ) / (A2)] = 1/20 to 20/1, more preferably 1/10 to 10/1.

Moreover, as a polyol (A) used for manufacture of the said urethane resin (C), other polyol (a3) is used as needed besides the above-mentioned vinyl polymer (a1) and polyol (a2). be able to.

As the other polyol (a3), for example, a polyol (a3-1) having a hydrophilic group can be used. In particular, when the vinyl polymer (a1) having no hydrophilic group is used, the resulting urethane resin (C) is provided with water dispersibility, and is used for forming a receiving layer having excellent storage stability. In obtaining the resin composition, it is preferable to use the polyol (a3-1) having the hydrophilic group.

As the polyol (a3-1) having a hydrophilic group, those having a hydrophilic group can be used. For example, a polyol having an anionic group, a polyol having a cationic group, a polyol having a nonionic group Among them, it is preferable to use a polyol having an anionic group or a polyol having a cationic group.

As the polyol having an anionic group, for example, a polyol having a carboxyl group or a polyol having a sulfonic acid group can be used.

As the polyol having a carboxyl group, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like can be used. Preference is given to using methylolpropionic acid. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group react with various polycarboxylic acids can also be used.

Examples of the polyol having a sulfonic acid group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and salts thereof, and the low molecular weight. A polyester polyol obtained by reacting with a polyol can be used.

Further, as the polyol having a cationic group, for example, a polyol having a tertiary amino group can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies in the molecule and a secondary amine can be used. A polyol obtained by reacting with can be used.

Also, as the polyol having a nonionic group, polyalkylene glycol having a structural unit derived from ethylene oxide can be used.

The polyol (a3-1) having a hydrophilic group is preferably used in the range of 1% by mass to 45% by mass with respect to the total mass of raw materials used for the production of the urethane resin (C).

Examples of the polyisocyanate (B) used in the production of the urethane resin (C) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, Aromatic polyisocyanates such as tolylene diisocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate or alicyclic structures Having polyisocyanate It is possible to use the door. Among them, it is preferable to use an aliphatic polyisocyanate in order to prevent yellowing of the receiving layer, and in order to prevent peeling of the receiving layer in the plating step, a polyisocyanate having an aliphatic cyclic structure is used. It is preferable.

When producing the urethane resin (C) used in the present invention, a chain extender is used as necessary for the purpose of making the molecular weight relatively high and further improving durability and the like. be able to.

As the chain extender, polyamines, hydrazine compounds, other active hydrogen atom-containing compounds and the like can be used.

Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like can be used.

Examples of the hydrazine compound include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propion Acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane can be used.

Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose. Glycols such as methylene glycol, glycerin and sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, water Etc. can be used.

The chain extender is preferably used, for example, in such a range that the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio), and 0.3 to 1 (equivalent ratio) It is more preferable to use in the range.

The urethane resin (C) is, for example, in the absence of a solvent or in the presence of an organic solvent, the vinyl polymer (a1) having two hydroxyl groups at one end, the polyol (a2) as necessary, and the necessity. Depending on the polyol (A) containing the other polyol (a3) such as the polyol (a3-1) having the hydrophilic group, the polyisocyanate (B), and a chain extender described later if necessary. The urethane resin (C) can be produced by reacting.

The reaction of the polyol (A) with the polyisocyanate (B) or the like is preferably from 50 ° C. to 120 ° C., more preferably from 80 ° C. to 100 ° C. The reaction can be carried out by mixing the polyol (B) and the polyol (A) at a reaction temperature of 0 ° C. and reacting them for about 1 to 15 hours.

In the reaction of the polyol (A) and the polyisocyanate (B), for example, the equivalent ratio of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (A) is 0.8 to 2.5. Preferably, it is carried out in the range of 0.9 to 1.5.

Examples of the organic solvent that can be used in producing the urethane resin (C) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile. Amides such as dimethylformamide and N-methylpyrrolidone can be used alone or in combination of two or more.
For example, the urethane resin (C) produced by the above method can be made water-based by the following method.

[Method 1] After neutralizing or quaternizing some or all of the hydrophilic groups of the urethane resin (C) obtained by reacting the polyol (A) with the polyisocyanate (B), the aqueous medium (D ) To disperse the urethane resin (C) in water.

[Method 2] After neutralizing or quaternizing some or all of the hydrophilic groups of the urethane resin (C) obtained by reacting the polyol (A) with the polyisocyanate (B), the aqueous medium (D ) And if necessary, the urethane resin (C) is dispersed in water by chain extension using the chain extender.

[Method 3] A urethane resin obtained by reacting the polyol (A) and the polyisocyanate (B) and, if necessary, the same chain extender as described above are charged into the reaction vessel in a batch or divided. The urethane resin (C) is produced by chain extension reaction, and then a part or all of the hydrophilic groups in the obtained urethane resin (C) are neutralized or quaternized, and then the aqueous medium (D) is used. A method to disperse and disperse in water.

In the above [Method 1] to [Method 3], an emulsifier may be used as necessary. In addition, when water is dissolved or dispersed, a machine such as a homogenizer may be used as necessary.

Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc. Anionic emulsifiers; cationic amines such as alkylamine salts, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts It is below.

The urethane resin (C) obtained by the above method has a printed material excellent in adhesion and printability, a conductive pattern excellent in fine line property and durability, and the like. Those having a weight average molecular weight in the range are preferably used, and those having a weight average molecular weight in the range of 20,000 to 120,000 are more preferably used.
The urethane resin (C) is preferably contained in an amount of 10% to 65% by mass, more preferably 10% to 35% by mass, based on the entire resin composition for forming a receiving layer of the present invention. preferable.

The urethane resin (C) obtained by the above method may have various functional groups as necessary, and examples of the functional group include crosslinks such as alkoxysilyl groups, silanol groups, hydroxyl groups, and amino groups. Sex functional group. The crosslinkable functional group may be bonded to the main chain of the urethane resin (C), or may be bonded to the vinyl polymer (a1).

The alkoxysilyl group and silanol group can be introduced into the urethane resin (C) by using γ-aminopropyltriethoxysilane or the like when the urethane resin (C) is produced.

On the other hand, as the crosslinkable functional group, one that forms a crosslink structure by reacting with the crosslinkable functional groups or the crosslinker (G) described later by heating to approximately 100 ° C or higher, preferably 120 ° C or higher is used. be able to.

Specifically, when a urethane resin having a functional group capable of undergoing a crosslinking reaction by heating to approximately 100 ° C. or higher, preferably 120 ° C. or higher is used, the receptor layer-forming resin composition containing the same is used. The receiving layer constituting the receiving substrate obtained by applying to the substrate and drying or the like does not substantially form a crosslinked structure. After printing on the receiving substrate using the fluid, a crosslinking reaction can be formed by heating or the like to form a crosslinked structure. As a result, in the plating treatment step described later, even when exposed to a plating agent made of a strong alkali or strong acid substance, the remarkably excellent durability does not cause peeling of the receiving layer from the support. A conductive pattern or the like such as a printed matter provided with can be formed.

The functional group capable of undergoing a cross-linking reaction by heating to 100 ° C. or higher, preferably 120 ° C. or higher, depends on the selection of the cross-linking agent (G) used in combination. For example, a cross-linking agent such as a blocked isocyanate compound is used. In this case, a hydroxyl group or an amino group can be used.

The crosslinkable functional group is preferably contained in a total range of 0.005 equivalent / kg to 1.5 equivalent / kg with respect to the total amount of the urethane resin (C).

In the composition for forming a receiving layer of the present invention, as a constituent of the solid content, in addition to the urethane resin (C), a solvent such as an aqueous medium (D) or an organic solvent, a resin, a crosslink as necessary. It may contain other compounds such as an agent (G), a filler, a pH adjuster, a film forming aid, a leveling agent, a thickener, a water repellent, and an antifoaming agent.
Examples of the aqueous medium (D) usable for the solvent include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

The solvent such as the aqueous medium (D) is preferably contained in an amount of 30% by mass to 85% by mass and more preferably 60% by mass to 85% by mass with respect to the total amount of the resin composition for forming a receiving layer. preferable.

In addition, the resin that can be used for the other compounds is used to further improve the printability and fine lineability when using a fluid such as an aqueous pigment ink, a conductive ink, or a plating nucleating agent. It is preferable to do.

Examples of the resin include vinyl resins such as acrylic resins, urethane resins, urethane-vinyl composite resins, polyester resins, imide resins, epoxy resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyalkylene oxide, starch, methyl cellulose, and hydroxy cellulose. , Cellulose derivatives such as hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, polyethyleneimine, polyamide, water-soluble resins having various quaternary ammonium bases, modified products thereof, and the like can be used.

As the curing agent, a compound having a functional group capable of reacting with an isocyanate group generated by dissociation of the blocking agent by heating or the like can be used. For example, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol Relatively low molecular weight polyols such as hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol, metal chelate compounds, polyamine compounds, aziridine compounds, metal salt compounds, etc. Compounds that can react at low temperatures to form a crosslinked structure, such as melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, etc. The compound capable of forming may be used.

Examples of the crosslinking agent (G) include heat that can react at a relatively low temperature of about 25 ° C. to less than 100 ° C. to form a crosslinked structure, such as metal chelate compounds, polyamine compounds, aziridine compounds, metal salt compounds, and isocyanate compounds. A cross-linked structure reacts at a relatively high temperature of approximately 100 ° C. or higher, such as one or more selected from the group consisting of a cross-linking agent (g1-1), a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a blocked isocyanate compound. A thermal crosslinking agent (g1-2) that can be formed and various photocrosslinking agents can be used.

In the case of a resin composition for forming a receiving layer containing the thermal crosslinking agent (g1-1), for example, it is applied to the surface of a support, dried at a relatively low temperature, and then printed using the fluid. After that, by forming a cross-linked structure by heating to a temperature of less than 100 ° C., it has excellent durability with a level that can prevent loss of conductive materials and pigments regardless of the influence of heat and external force over a long period of time. Can be formed.

On the other hand, if it is a resin composition for forming a receiving layer containing the thermal crosslinking agent (g1-2), for example, it is applied to the support surface and dried at a low temperature of from room temperature (25 ° C.) to less than about 100 ° C. Then, after manufacturing an ink receiving substrate that does not form a cross-linked structure and then printing using ink or the like, the cross-linked structure is formed by heating at a temperature of, for example, 100 ° C. or higher, preferably 120 ° C. or higher. As a result, it is possible to obtain a conductive pattern such as a printed matter having exceptionally excellent durability at a level that does not cause peeling of the ink regardless of the influence of heat or external force over a long period of time.

When the crosslinking agent (G) is used, it is preferable to use the urethane resin (C) having a group capable of reacting with the crosslinkable functional group of the crosslinking agent (G). Specifically, when the (block) isocyanate compound, melamine compound, oxazoline compound, and carbodiimide compound are used as a crosslinking agent, the urethane resin (C) may have a hydroxyl group or a carboxyl group. preferable.

Although the crosslinking agent (G) varies depending on the type and the like, it is usually preferable to use in the range of 0.01% by mass to 60% by mass with respect to the total amount of the urethane resin (C), and 0.1% by mass It is more preferably used in the range of ˜10% by mass, and the use in the range of 0.1% by mass to 5% by mass forms a receiving layer capable of forming a printed image with further excellent printability. In addition, it is preferable. In addition, even when forming a conductive pattern using conductive ink or the like, the level that can be used to realize higher density of electronic circuits or the like without causing bleeding of printed portions such as fine lines is much better. It is preferable because it can provide fine lineability and can further improve the adhesion between the receptor layer and the support.

The cross-linking agent (G) is preferably added and used before coating or impregnating the support layer-forming resin composition of the present invention on the support surface.

In addition, examples of the other compound that can be used in combination with the resin composition for forming a receiving layer of the present invention include various fillers such as inorganic particles. However, in the composition for forming a receiving layer of the present invention, the amount of the filler used is preferably as small as possible, and is 5% by mass or less based on the total amount of the composition for forming a receiving layer of the present invention. More preferred.

The amount of the other compound used is preferably in the range of 0% by mass to 50% by mass, and in the range of 0% by mass to 30% by mass with respect to the solid content contained in the composition for forming the receiving layer. It is more preferable.

In the receiving layer that can be formed using the receiving layer forming composition, the urethane resin (C) constituting the receiving layer is appropriately dissolved by a solvent contained in a fluid such as ink and absorbs the solvent. Thus, since it is a swelling type capable of accurately fixing conductive materials such as metals and pigments contained in the fluid to the surface of the receiving layer, printed matter such as conductive patterns without bleeding can be obtained. Is possible. In addition, the composition for forming a receiving layer of the present invention can form a transparent receiving layer as compared with a conventionally known porous type receiving layer.

Next, the fluid receiving substrate of the present invention will be described.

The receiving substrate of the present invention has a receiving layer formed by using the receiving layer forming composition on a part or all of the surfaces of various supports and on one or both sides of the support.

The receptor layer is a layer that absorbs a solvent in the fluid when the fluid contacts the surface of the receptor layer and carries a conductive substance or pigment on the surface of the receptor layer. For example, if a pigment ink is used as the fluid, it is possible to form a highly clear printed matter without bleeding, and if a conductive ink is used as the fluid, a conductive pattern without bleeding. If a plating nucleating agent is used as the fluid, a laminated body in which the plating nuclei are uniformly supported on the surface of the receiving layer can be formed.

The receiving layer may be laminated on the support, but a part of the receiving layer may be impregnated in the support.

The receiving substrate of the present invention is a method in which the receiving layer-forming composition is applied to a part or all of one side or both sides of a support, and the aqueous medium (D) contained in the applied surface is volatilized or supported. When the body is a fiber substrate, it can be produced by a method of impregnating the support layer-forming composition into the support and volatilizing the aqueous medium (D).

Examples of the support include fine paper, coated paper, polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), poly (meth) acrylate, and the like. Support made of acrylic resin, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, urethane resin, cellulose nanofiber, silicon, ceramics, glass, etc., porous support made of them, A support made of a metal such as a steel plate or copper can be used.

Also, as the support, for example, a base material made of synthetic fibers such as polyester fibers, polyamide fibers, and aramid fibers, natural fibers such as cotton and hemp can be used. The fibers may be processed in advance.

As a method of applying or impregnating the composition for forming a receiving layer on the support, known and conventional methods can be used, for example, gravure method, coating method, screen method, roller method, rotary method, spray method. Etc. can be applied.

In addition, the method for removing the solvent that may be contained in the composition after coating or impregnating the support layer-forming composition of the present invention on part or all of the surface of the support is not particularly limited. However, for example, a method of drying using a dryer is common. The drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support. When a bond is formed in the receiving layer after applying the fluid, it is preferable to dry at a temperature at which the blocking agent is dissociated and isocyanate groups are not generated.

The adhesion amount of the composition for forming a receiving layer on the support is 3 g / m ^{2 with} respect to the area of the support from the viewpoint of maintaining a very high level of color developability and maintaining good production efficiency. It is preferably in the range of ˜60 g / m ² , and 20 g / m ² to 40 g / m ² is particularly preferred in consideration of the absorbability of the solvent contained in the fluid and the production cost.

Further, by increasing the adhesion amount of the composition for forming a receiving layer on the support, it is possible to further improve the color developability of the obtained printed matter. However, since the texture of the printed matter tends to be slightly harder as the adhesion amount increases, it is preferable to adjust appropriately according to the use purpose of the printed matter.

Therefore, since the receiving substrate of the present invention can form a printed image having excellent printability and water resistance without causing bleeding or cracking, it can be used for indoor and outdoor advertisements such as signboards, body advertisements, and banners. It can be used.

The fluid that can be used for printing on the receiving substrate has a viscosity measured by a B-type viscometer at approximately 25 ° C. of 0.1 mPa · s to 500,000 mPa · s, preferably 0.5 mPa · s to 10, A liquid or viscous liquid having a viscosity of 000 mPa · s, in which a conductive substance, a pigment, or the like is dispersed in a solvent. When the fluid is printed by an inkjet printing method, it is preferable to use a fluid having a viscosity range of 0.5 mPa · s to 10000 mPa · s.

Specific examples of the fluid include printing inks such as conductive inks and pigment inks, and plating nucleating agents that may be used when plating is performed.

Examples of the fluid include an aqueous pigment ink in which a pigment is dispersed in an aqueous medium.

As the aqueous medium, only water or a mixed solution of water and a water-soluble solvent may be used. Examples of the water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone.

Examples of the pigment that can be dispersed or dissolved in the aqueous medium include quinacridone pigments, anthraquinone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, condensed azo pigments, Benzimidazolone pigments, monoazo pigments, insoluble azo pigments, naphthol pigments, flavanthrone pigments, anthrapyrimidine pigments, quinophthalone pigments, pyranthrone pigments, pyrazolone pigments, thioindigo pigments, anthanthrone pigments, Organic pigments such as dioxazine pigments, phthalocyanine pigments, and indanthrone; metal complexes such as nickel dioxin yellow and copper azomethine yellow; metal oxides such as titanium oxide, iron oxide, and zinc oxide, barium sulfate, calcium carbonate, etc. Metal salt, carbon black, clouds Inorganic pigments etc., fine metal powder such as aluminum, mica fine powder and the like can be used. The pigment is preferably used in an amount of 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total amount of the aqueous pigment ink.

Further, as the fluid, a solvent-based pigment ink in which a pigment or the like is dissolved or dispersed in a solvent composed of an organic solvent can also be used.

As the organic solvent, for example, alcohol, ether, ester, ketone and the like having a boiling point of 100 to 250 ° C., preferably having a boiling point of 120 to 220, are used from the viewpoint of preventing drying and clogging of the inkjet head. More preferred is one at ° C.

As the alcohol, for example, ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol and the like can be used.

Examples of ethers include ethylene glycol mono (methyl, ethyl, butyl, phenyl, benzyl, ethylhexyl) ether, ethylene glycol di (methyl, ethyl, butyl) ether, diethylene glycol mono (methyl, ethyl, butyl) ether, diethylene glycol di ( Methyl, ethyl, butyl) ether, tetraethylene glycol mono (methyl, ethyl, butyl) ether, tetraethylene glycol di (methyl, ethyl, butyl) ether, propylene glycol mono (methyl, ethyl, butyl) ether, dipropylene glycol mono (Methyl, ethyl) ether, tripropylene glycol monomethyl ether and the like can be used.

Examples of esters include ethylene glycol mono (methyl, ethyl, butyl) ether acetate, ethylene glycol di (methyl, ethyl, butyl) ether acetate, diethylene glycol mono (methyl, ethyl, butyl) ether acetate, diethylene glycol di (methyl, ethyl) , Butyl) ether acetate, propylene glycol mono (methyl, ethyl, butyl) ether acetate, dipropylene glycol mono (methyl, ethyl) ether acetate, tripropylene glycol monomethyl ether acetate, 2- (methoxy, ethoxy, butoxy) ethyl acetate, Examples include 2-ethylhexyl acetate, dimethyl phthalate, diethyl phthalate, and butyl lactate. Examples of ketones include cyclohexanone.

Of these, diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate are preferably used.

As the pigment used in the solvent-based pigment ink, the same pigments exemplified as those usable in the aqueous pigment ink can be used.

The receiving substrate of the present invention can be suitably used particularly when printing is performed using a solvent-based pigment ink among the pigment inks composed of the water-based pigment ink and the solvent-based pigment ink.

Various printing methods can be applied as a method for printing on the receiving substrate of the present invention using the pigment ink, but it is preferable to employ an inkjet printing method, a screen printing method, a letterpress reverse printing method, or a gravure offset printing method. .

Further, the receiving substrate of the present invention has excellent printability for conductive ink containing a conductive substance as the fluid, and is required when forming a conductive pattern such as an electronic circuit, for example. It is possible to print fine lines having a width of about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm without causing bleeding (thin lineability). Therefore, the receiving substrate of the present invention is formed of an electronic circuit using silver ink or the like, an organic solar cell, an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, an RFID or the like, and each layer or peripheral wiring. In addition, it can be suitably used in a new field generally referred to as a printed electronics field, such as manufacturing of an electromagnetic shielding wire for a plasma display.

The receiving substrate (conductive ink receiving substrate) of the present invention that can be used for forming the conductive pattern is similar to the above in that the receiving layer-forming composition is formed on part or all of the surface of various supports. It has a receiving layer formed using. The receptor layer may be laminated on a support, but a part of the receptor layer may be impregnated in the support. Moreover, the said receiving layer may be provided in either the single side | surface or both surfaces of a support body, and may be apply | coated to the one part or all part of the surface.

In the receiving substrate of the present invention, the composition for forming a receiving layer is applied to and impregnated part or all of one side or both sides of a support, and then contained in the composition for forming a conductive receiving layer. It can be manufactured by removing the medium (B).

Examples of the support suitable for laminating the receptor layer in producing the conductive pattern include polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene- Acrylic resins such as styrene (ABS) and poly (meth) methyl acrylate, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, urethane resin, cellulose nanofiber, silicon, ceramics, glass Etc., a porous support made of them, a support made of a metal such as a steel plate or copper, and the like can be used.

Among these, as the support, generally used as a support in forming a conductive pattern such as a circuit board, from polyimide resin, polyethylene terephthalate, polyethylene naphthalate, glass, cellulose nanofiber, etc. It is preferable to use a support.

In addition, among the above supports, substrates made of polyimide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), acrylic resin, glass, etc. are generally difficult to adhere, so resins, etc. Is often difficult to adhere.

In addition, when the support is used for applications that require flexibility, it is possible to use a material that is relatively flexible and capable of being bent. It is preferable for obtaining a final product. Specifically, it is preferable to use a film or sheet-like support formed by uniaxial stretching or the like.

Examples of the film or sheet-like support include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.

As a method of applying or impregnating the receiving layer forming composition to a part or all of the support surface, a known and commonly used method can be used, for example, gravure method, coating method, screen method, roller method. A rotary method, a spray method, an ink jet method, or the like can be applied.

The method for removing the aqueous medium (D) that can be contained in the composition after coating or impregnating the support layer-forming composition of the present invention on part or all of the surface of the support is particularly limited. For example, a method of drying using a dryer is common. The drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support.

The amount of the composition for forming the receiving layer on the surface of the support is determined based on the area of the support in consideration of the amount of the solvent contained in the fluid such as conductive ink and the thickness of the conductive pattern. On the other hand, the resin solid content is preferably in the range of 0.01 g / m ² to 20 g / m ² , taking into account the absorbability of the solvent in the fluid and the production cost, 0.01 g / m ² to 10 g / m. ² is particularly preferred.

Moreover, the fine-line property of a receiving base material can be improved further by increasing the adhesion amount of the said composition for receiving layer formation to the support body surface. However, when the adhesion amount increases, the texture of the receiving base material tends to be slightly hard. For example, when good flexibility such as a flexible printed board that can be bent is required, the texture is generally 0.02 g / m ^2. It is preferable to make it relatively thin, about ˜10 g / m ² . On the other hand, depending on the application, etc., it may be used in such a mode that it becomes a relatively thick film of about 10 g / m ² to 100 g / m ² .
→ The lower limit of film thickness has been changed.

The receiving substrate of the present invention obtained by the above method can be suitably used even when a conductive ink is used as the fluid. For example, in the printed electronics field described above, it is suitable only for the formation of a conductive pattern or the like. Can be used for More specifically, it can be suitably used for a circuit forming substrate used for an electronic circuit, an integrated circuit, or the like.

The receiving substrate and the circuit forming substrate can be printed using conductive ink as the fluid. Specifically, printing is carried out using a conductive ink on the receiving layer constituting the receiving substrate, and then a baking step is performed, for example, in the conductive ink on the receiving substrate. A conductive pattern made of a conductive material made of a metal such as silver can be formed.

As the conductive ink that can be used as the fluid, the viscosity measured by a B-type viscometer at about 25 ° C. is about 0.1 mPa · s to 500,000 mPa · s, preferably about 0. A liquid or viscous liquid having a viscosity of 5 mPa · s to 10,000 mPa · s, in which a conductive substance, a pigment or the like is dispersed in a solvent. When the fluid is printed by an inkjet printing method, it is preferable to use a fluid having a viscosity range of 0.5 mPa · s to 10000 mPa · s.

As the conductive ink, for example, an ink containing a conductive substance, a solvent, and, if necessary, an additive such as a dispersant can be used.

As the conductive substance, a transition metal or a compound thereof can be used. Among them, it is preferable to use an ionic transition metal, for example, it is preferable to use a transition metal such as copper, silver, gold, nickel, palladium, platinum, cobalt, and to use silver, gold, copper, or the like. It is more preferable because a conductive pattern having low electric resistance and strong against corrosion can be formed.

As the conductive material, it is preferable to use a particulate material having an average particle diameter of about 1 nm to 50 nm. In addition, the said average particle diameter means a center particle diameter (D50), and shows the value at the time of measuring with a laser diffraction scattering type particle size distribution measuring apparatus.

The conductive substance such as metal is preferably contained in the range of 10% by mass to 60% by mass with respect to the total amount of the conductive ink.

As the solvent used for the conductive ink, various organic solvents and an aqueous medium such as water can be used. The receiving substrate of the present invention can be suitably used when a solvent-based conductive ink is used.

In the present invention, a solvent-based conductive ink mainly containing an organic solvent as the solvent of the conductive ink, an aqueous conductive ink mainly containing water as the solvent, and a conductive material containing both the organic solvent and water. Ink can be appropriately selected and used.

Among these, from the viewpoint of improving the fineness and adhesion of the conductive pattern to be formed, the conductive ink containing both the organic solvent and water as the solvent of the conductive ink, and the main solvent as the solvent of the conductive ink. It is preferable to use a solvent-based conductive ink containing an organic solvent, and it is more preferable to use a solvent-based conductive ink mainly containing an organic solvent as a solvent for the conductive ink.

In particular, the receiving layer of the receiving substrate of the present invention can be used exclusively in combination with a conductive ink containing a polar solvent as the organic solvent, which can cause bleeding and reduced adhesion, etc., caused by the polar solvent. This is preferable because it can be sufficiently prevented and a level of fineness that can be used for realizing higher density of electronic circuits and the like can be realized.

Examples of the solvent used in the solvent-based conductive ink include methanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, and undecanol. , Dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol and other alcohol solvents, 2-ethyl 1,3-hexanediol, ethylene glycol, diethylene glycol, tri Ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanedio Glycol solvents such as 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol Rudibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, di Glycols such as propylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, dipropylene glycol dimethyl ether A polar solvent such as an ether ether solvent and glycerin can be used.

Among the polar solvents, use of a solvent having a hydroxyl group prevents bleeding and fine lineability of a conductive pattern and the like, and lack of a conductive substance contained in the conductive ink from the surface of the receiving layer. It is preferable for preventing the above.

Also, the solvent-based conductive ink can be used in combination with a ketone-based solvent such as acetone, cyclohexanone, methyl ethyl ketone, etc., for adjusting physical properties. In addition, ester solvents such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate, hydrocarbon solvents such as toluene, especially hydrocarbon solvents having 8 or more carbon atoms, For example, nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane can be used in combination as necessary. Furthermore, solvents such as mineral spirits and solvent naphtha, which are mixed solvents, can be used in combination.

However, since the receiving layer formed using the composition for forming a receiving layer of the present invention is preferably used in combination with a conductive ink containing a polar solvent, the nonpolar solvent is contained in the conductive ink. More preferably, it is 0% by mass to 40% by mass with respect to the total amount of the solvent contained in.

In addition, as an aqueous medium that can be used as the solvent of the conductive ink, for example, water alone may be used, or a mixed solution of water and a water-soluble solvent may be used. Examples of the water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, butyl cellosolve, and polar solvents such as N-methylpyrrolidone. It is preferable in terms of preventing the fine line property and the loss of the conductive substance contained in the conductive ink from the surface of the receiving layer.

The solvent contained in the conductive ink is preferably contained in the range of 40% by mass to 90% by mass with respect to the total amount of the conductive ink. The polar solvent is preferably contained in an amount of 40% by mass to 100% by mass with respect to the total amount of the solvent.

In addition to the metal and the solvent, various additives can be used as necessary for the conductive ink.

As the additive, for example, a dispersant can be used from the viewpoint of improving dispersibility of the metal in the solvent.

Examples of the dispersant include amine-based polymer dispersants such as polyethyleneimine and polyvinylpyrrolidone, hydrocarbon-based polymer dispersants having a carboxylic acid group in the molecule such as polyacrylic acid and carboxymethylcellulose, and polyvinyl alcohol. , A polymer dispersant having a polar group, such as a styrene-maleic acid copolymer, an olefin-maleic acid copolymer, or a copolymer having a polyethyleneimine moiety and a polyethylene oxide moiety in one molecule. Can do. The polyvinyl alcohol may be used as a dispersant even when a solvent-based conductive ink is used.

Examples of a method for printing on the receiving substrate using the conductive ink include, for example, an ink jet printing method, a screen printing method, a letterpress reverse printing method or a gravure offset printing method, an offset printing method, a spin coating method, and a spray coating method. , Bar coating method, die coating method, slit coating method, roll coating method, dip coating method and the like.

As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dimatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like.

The screen printing method is a method in which a conductive ink is applied to the surface of the receiving layer by using a mesh-shaped screen plate. Specifically, a conductive pattern having a predetermined pattern shape can be formed by printing a conductive pattern in a predetermined pattern shape using a metal screen plate generally called a metal mesh.

The letterpress reverse printing method is a method in which a conductive ink is applied on a blanket to form a conductive ink application surface and transferred to the receiving layer.

It is preferable to use a silicone blanket made of silicone as the blanket.

First, conductive ink is applied on the blanket to form a layer made of conductive ink. Next, the conductive ink contacting the relief plate is transferred from the blanket onto the relief plate surface by pressing a relief plate provided with a plate corresponding to a predetermined pattern shape as necessary to the layer made of the conductive ink. Is done.

Next, the conductive ink remaining on the blanket is transferred to the surface of the receiving layer by bringing the blanket into contact with the receiving layer. By such a method, a conductive pattern having a predetermined pattern can be formed.

Further, as the gravure offset printing method, for example, after supplying conductive ink to a groove portion of an intaglio printing plate having a predetermined pattern shape, the conductive ink is applied onto the blanket by pressing the blanket on the surface thereof. And then transferring the conductive ink on the blanket to the receiving layer.

As the intaglio printing plate, for example, a gravure plate, a glass intaglio plate formed by etching a glass plate, or the like can be used.

As the blanket, a blanket having a multilayer structure including a silicone rubber layer, a polyethylene terephthalate layer, a sponge-like layer, etc. can be used. Usually, a blanket wrapped around a rigid cylinder is used. To do.

Conductivity can be imparted to the printed matter that has been printed on the receiving substrate by the above-described method by closely contacting and joining the conductive substances contained in the conductive ink.

As a method of joining the conductive substances, a method of heating and baking and a method of irradiating light can be mentioned.

The firing is preferably performed in the range of approximately 80 ° C. to 300 ° C. for approximately 2 minutes to 200 minutes. The firing may be performed in the air, but from the viewpoint of preventing oxidation of the metal, part or all of the firing step may be performed in a reducing atmosphere.

Further, the firing step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, flash lamp irradiation, microwave, or the like.

The firing temperature is preferably in the range of approximately 80 ° C. to 300 ° C., more preferably 100 ° C. to 300 ° C., and particularly preferably 120 ° C. to 300 ° C. When the support is relatively weak against heat, the upper limit of the temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.

The conductive pattern is formed by the metal contained in the conductive ink on the surface of the printed matter obtained through the baking step. Such a conductive pattern can be used for circuit boards and integrated circuit boards for various electric products.

The conductive pattern was plated with a metal such as copper in order to form a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time. Things can be used. Specifically, as the conductive pattern, for example, a part of or the entire surface of the support has a receptor layer formed by using the receptor layer forming composition, and one surface of the receptor layer is formed. The plating nucleus is supported on a part or all by applying a plating nucleating agent, and after passing through a firing step or the like, if necessary, electrolytic plating treatment, electroless plating treatment, or further electrolysis after the electroless plating treatment What has a plating film formed by performing a plating process is mentioned.

As the plating nucleating agent, one corresponding to the conductive ink exemplified as the fluid can be used. For example, a plating nucleus, specifically, a conductive material dispersed in a solvent is used. Can do.

Examples of the conductive material used for the plating nucleating agent include metal particles such as those exemplified as the conductive material usable for the conductive ink, and oxides of the metal and those whose surface is coated with an organic substance. More than one type can be used.

The metal oxide is usually in an inactive (insulating) state, but it can be exposed to the metal and treated with a reducing agent such as dimethylaminoborane to impart activity (conductivity). It becomes.

Further, examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. These are usually in an inactive (insulating) state, but by removing the organic substance using, for example, a laser or the like, it becomes possible to expose the metal and impart activity (conductivity).

The conductive substance contained in the plating nucleating agent preferably has an average particle diameter in the range of about 10 nm to 1000 nm.

Further, as the solvent used for the plating nucleating agent, the same solvents as those exemplified as the solvent such as an aqueous medium and an organic solvent usable for the conductive ink can be used.

In the electroless plating treatment step, for example, a metal such as copper contained in the electroless plating solution by bringing the electroless plating solution into contact with the surface of a receiving substrate on which a plating nucleus such as palladium or silver is supported. In which an electroless plating film made of a metal film is formed.

As the electroless plating solution, for example, a material containing a conductive substance made of a metal such as copper, nickel, chromium, cobalt, or tin, a reducing agent, and a solvent such as an aqueous medium or an organic solvent may be used. it can.

As the reducing agent, for example, dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenols and the like can be used.

In addition, as the electroless plating solution, if necessary, monocarboxylic acids such as acetic acid and formic acid; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid; malic acid, lactic acid and glycolic acid Hydroxycarboxylic acids such as gluconic acid and citric acid; amino acids such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, and glutamic acid; aminopoly acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid It may contain complexing agents such as organic acids such as carboxylic acids, soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), amines such as ethylenediamine, diethylenetriamine, and triethylenetetramine. .

The temperature of the electroless plating solution when the electroless plating solution is brought into contact with the surface of the receiving substrate on which the plating nucleus in the plating nucleating agent is supported is generally in the range of 20 ° C. to 98 ° C. preferable.

In addition, the electrolytic plating treatment step may be performed by applying an electrolytic plating solution to the surface (x) of the receiving substrate on which the plating nucleus is supported or the surface (y) of the electroless plating film formed by the electroless treatment, for example. By energizing in the state of contact, a metal such as copper contained in the electrolytic plating solution can be used for the surface (x) of the receiving base placed on the negative electrode or the electroless plating film formed by the electroless treatment. It is a step of depositing on the surface (y) to form an electrolytic plating film (metal film).

As the electrolytic plating solution, a solution containing a conductive substance made of a metal such as copper, nickel, chromium, cobalt, tin, sulfuric acid, and an aqueous medium can be used.

The temperature of the electrolytic plating solution when the electrolytic plating solution is brought into contact with the surface of the receiving substrate on which the plating nucleus in the plating nucleating agent is supported is preferably in the range of about 20 ° C to 98 ° C.

In the electroless plating process and the electroplating process as described above, a strong acid or strong alkaline plating solution as described above is often used. Therefore, in a normal receiving substrate, the receiving layer is affected, It often causes peeling of the receiving layer from the support.

On the other hand, after printing on the receiving substrate of the present invention using a fluid such as a plating nucleating agent, the receptor layer is peeled off from the support in the plating treatment step for the cross-linked structure formed in the receiving layer. Will not cause. In particular, even if the support is made of a polyimide resin or the like, it does not cause peeling of the receiving layer, and therefore can be used very suitably for the production of the conductive pattern.

The conductive pattern as described above is, for example, the formation of an electronic circuit using silver ink or the like, the formation of a peripheral wiring constituting an organic solar cell, an electronic book terminal, an organic EL, an organic transistor, a flexible printed board, an RFID, etc. It can be suitably used for forming a conductive pattern, more specifically, a circuit board when manufacturing an electromagnetic wave shield for a plasma display.

In addition, among the conductive patterns obtained by the above method, after printing using a fluid such as conductive ink or plating nucleating agent, the conductive pattern obtained by forming a crosslinked structure in the receiving layer, Silver ink, etc., because it can provide excellent durability at a level that can maintain good electrical conductivity without causing peeling of the receptor layer from the support, etc., even after undergoing a plating process Formation of circuit forming substrates used in electronic circuits and integrated circuits, etc., organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, formation of peripheral wiring constituting RFID, plasma displays, etc. Among the wirings of the electromagnetic wave shield, etc., it can be suitably used for applications that require particularly durability. In particular, since the conductive pattern subjected to the plating treatment can form a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time, for example, a copper-clad laminate is generally used. (CCL: Copper Clad Laminate) and can be used for applications such as flexible printed circuit board (FPC), automatic tape bonding (TAB), chip-on-film (COF), and printed wiring board (PWB).

Hereinafter, the present invention will be described in detail by way of examples.

[Preparation Example 1] Preparation of vinyl polymer (a1-1) having two hydroxyl groups at one end In a four-necked flask equipped with a thermometer, stirrer, reflux condenser and nitrogen inlet tube, 700 parts by mass of methyl ethyl ketone Then, 291 parts by weight of methyl methacrylate, 8.7 parts by weight of 3-mercapto-1,2-propanediol, and 0.15 parts by weight of 2,2′-azobis (2-methylpropionitrile) are charged into the reaction vessel. To give a solvent solution of a vinyl polymer (a1-1) having two hydroxyl groups at one end having a number average molecular weight of 3,000.

[Preparation Example 2] Preparation of vinyl polymer (a1-2) having two hydroxyl groups at one end In a four-necked flask equipped with a thermometer, stirrer, reflux condenser and nitrogen inlet tube, 700 parts by mass of methyl ethyl ketone Then, 297 parts by mass of methyl methacrylate, 3 parts by mass of 3-mercapto-1,2-propanediol and 0.15 parts by mass of 2,2′-azobis (2-methylpropionitrile) are fed into the reaction vessel. Then, a solvent solution of a vinyl polymer (a1-2) having two hydroxyl groups at one end with a number average molecular weight of 12,000 was obtained.

[Comparative Preparation Example 3] Preparation of vinyl polymer (a1-3) having two hydroxyl groups in the main chain Methyl ethyl ketone 700 was added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube. Then, 261 parts by mass of methyl (meth) acrylate, 22 parts by mass of 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate), 17 parts by mass of 1-dodecanethiol, and 2,2′- Solvent of vinyl polymer (a1-3) having two hydroxyl groups in the molecular chain having a number average molecular weight of 3,000 by supplying 0.15 parts by mass of azobis (2-methylpropionitrile) and reacting them A solution was obtained.

[Example 1]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 286 parts by mass of the solvent solution of the vinyl polymer (a1-1) obtained in Preparation Example 1, neopentyl glycol and 1, 93 parts by mass of a polyester polyol (number average molecular weight 2,000) obtained by reacting 6-hexanediol with adipic acid, 35 parts by mass of 2,2-dimethylolpropionic acid and 86 parts by mass of dicyclohexylmethane diisocyanate were added to an organic solvent. As an organic solvent solution of urethane resin having a weight average molecular weight of 45,000, the reaction was carried out at 80 ° C. for 10 hours in the presence of 84 parts by mass of methyl ethyl ketone.

Next, 30 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and further, 685 parts by mass of water is added and the urethane is sufficiently stirred. An aqueous dispersion of resin was obtained.

Subsequently, the aqueous dispersion of the urethane resin was desolvated, and further adjusted by adding water so that the non-volatile content was 25% by mass, thereby obtaining the receiving layer forming resin composition of the present invention.

[Example 2]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 286 parts by mass of the solvent solution of the vinyl polymer (a1-2) obtained in Preparation Example 2, neopentyl glycol and 1, 96 parts by mass of a polyester polyol (number average molecular weight 2,000) obtained by reacting 6-hexanediol and adipic acid, 35 parts by mass of 2,2-dimethylolpropionic acid and 84 parts by mass of dicyclohexylmethane diisocyanate are mixed with an organic solvent. In the presence of 84 parts by mass of methyl ethyl ketone, the reaction was carried out at 80 ° C. for 10 hours to obtain an organic solvent solution of urethane resin having a weight average molecular weight of 46,000.

[Example 3]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 10 parts by mass of the solvent solution of the vinyl polymer (a1-1) obtained in Preparation Example 1, neopentyl glycol and 1, 172 parts by mass of polyester polyol (number average molecular weight 2,000) obtained by reacting 6-hexanediol and adipic acid, 35 parts by mass of 2,2-dimethylolpropionic acid and 91 parts by mass of dicyclohexylmethane diisocyanate Was reacted for 10 hours at 80 ° C. in the presence of 277 parts by mass of methyl ethyl ketone as an organic solvent solution of urethane resin having a weight average molecular weight of 46,000.

[Example 4]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 571 parts by mass of the solvent solution of the vinyl polymer (a1-1) obtained in Preparation Example 1, neopentyl glycol and 1, 11 parts by mass of a polyester polyol (number average molecular weight 2,000) obtained by reacting 6-hexanediol and adipic acid, 35 parts by mass of 2,2-dimethylolpropionic acid, and 82 parts by mass of dicyclohexylmethane diisocyanate were mixed at 80 ° C. Was reacted for 10 hours to obtain an organic solvent solution of urethane resin having a weight average molecular weight of 44,000.

[Example 5]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 286 parts by mass of the solvent solution of the vinyl polymer (a1-1) obtained in Preparation Example 1 and 1,6-hexanediol Methyl ethyl ketone 84 as an organic solvent was obtained by reacting 93 parts by weight of polycarbonate polyol (number average molecular weight 2,000), 35 parts by weight of 2,2-dimethylolpropionic acid and 86 parts by weight of dicyclohexylmethane diisocyanate. By reacting at 80 ° C. for 10 hours in the presence of part by mass, an organic solvent solution of urethane resin having a weight average molecular weight of 45,000 was obtained.

[Example 6]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 296 parts by mass of the solvent solution of the vinyl polymer (a1-1) obtained in Preparation Example 1, neopentyl glycol and 1, 156 parts by mass of a polyester polyol (number average molecular weight 2,000) obtained by reacting 6-hexanediol and adipic acid, 11 parts by mass of 2,2-dimethylolpropionic acid, and 49 parts by mass of dicyclohexylmethane diisocyanate are mixed with an organic solvent. As an organic solvent solution of urethane resin having a weight average molecular weight of 45,000, the reaction was carried out at 80 ° C. for 10 hours in the presence of 87 parts by mass of methyl ethyl ketone.

Next, 30 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and further 695 parts by mass of water is added and the urethane is sufficiently stirred. An aqueous dispersion of resin was obtained.

[Example 7]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 286 parts by mass of the solvent solution of the vinyl polymer (a1-1) obtained in Preparation Example 1, neopentyl glycol and 1, 93 parts by mass of a polyester polyol (number average molecular weight 2,000) obtained by reacting 6-hexanediol with adipic acid, 35 parts by mass of 2,2-dimethylolpropionic acid and 86 parts by mass of dicyclohexylmethane diisocyanate were added to an organic solvent. In the presence of 84 parts by mass of methyl ethyl ketone as an organic solvent solution of urethane resin having a weight average molecular weight of 100,000.

Next, the aqueous dispersion of the urethane resin was desolvated, and further adjusted by adding water so that the non-volatile content was 25% by mass, thereby obtaining the receiving layer forming resin composition of the present invention.
[Example 8]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 286 parts by mass of the solvent solution of the vinyl polymer (a1-1) obtained in Preparation Example 1 and polyoxytetramethylene glycol ( Number average molecular weight 2,000) 93 parts by mass, 2,2-dimethylolpropionic acid 35 parts by mass and isophorone diisocyanate 72 parts by mass in the presence of 84 parts by mass of methyl ethyl ketone as an organic solvent at 80 ° C. for 10 hours. Thus, an organic solvent solution of urethane resin having a weight average molecular weight of 45,000 was obtained.

[Comparative Example 1]
Polyester polyol (number average molecular weight 2,000) obtained by reacting neopentyl glycol, 1,6-hexanediol and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer ) 174 parts by mass, 35 parts by mass of 2,2-dimethylolpropionic acid and 91 parts by mass of dicyclohexylmethane diisocyanate were reacted at 80 ° C. for 10 hours in the presence of 284 parts by mass of methyl ethyl ketone as an organic solvent. Obtained an organic solvent solution of 46,000 urethane resin.

Subsequently, the aqueous dispersion of the urethane resin was desolvated, and water was added to adjust the non-volatile content to 25% by mass to obtain a resin composition for forming a receiving layer.

[Comparative Example 2]
The same as Example 1 except that 286 parts by mass of the solvent solution of the vinyl polymer (a1-3) obtained in Comparative Preparation Example 3 was used instead of the solvent solution of the vinyl polymer (a1-1). Thus, a resin composition for forming a receiving layer having a nonvolatile content of 25% by mass was obtained.

Abbreviations in Table 1 or 2 are described below.
“PES1”; polyester polyol obtained by reacting neopentyl glycol, 1,6-hexanediol and adipic acid (number average molecular weight 2,000)
“PTMG”: polyoxytetramethylene glycol (number average molecular weight 2,000)
“DMPA”; 2,2-dimethylolpropionic acid “HMDI”; dicyclohexylmethane diisocyanate “IPDI”; isophorone diisocyanate “PC”; polycarbonate polyol obtained by reacting 1,6-hexanediol and methyl carbonate (number average) Molecular weight 2,000)

[Production method of receiving substrate]
The resin composition for forming a receiving layer obtained in Example 1 was provided with a bar coater on the surfaces of three types of supports shown in the following (i) to (iii) so that the dry film thickness was 3 μm. Each was used for coating, and dried at 70 ° C. for 3 minutes using a hot air drier, thereby preparing three types of receiving substrates each having a receiving layer formed on each support.
Instead of the resin composition for forming a receiving layer obtained in Example 1, the resin composition for forming a receiving layer obtained in Examples 2 to 8 and Comparative Examples 1 and 2 was used. In the same manner as in [Preparation Method of Substrate], three types of receiving substrates with different supports were prepared per type of the resin composition for forming the receiving layer.

[Support]
(I) PET; polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness 50 μm)
(Ii) PI: Polyimide film (Kapton 200H manufactured by Toray DuPont Co., Ltd., thickness 50 μm)
(Iii) GL; glass: glass plate, JIS R3202, thickness 2 mm

[Method for evaluating adhesion between support and receiving layer]
A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the surface (on the receiving layer) of each receiving substrate before printing, and then the cellophane adhesive tape is attached to the receiving substrate. Peeling in the direction of 90 degrees with respect to the surface. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

The adhesive layer of the peeled cellophane adhesive tape was “A” in which no receptor layer was attached, and the receptor layer in a range of less than about 5% relative to the adhesive tape application area was peeled from the support, The adhesive layer attached to the adhesive tape is "B". The adhesive layer in the range of about 5% to less than 50% of the adhesive tape is peeled off from the support, and the adhesive layer attached to the adhesive tape is "C". About 50% or more of the receiving layer with respect to the affixing area was peeled off from the support and was attached to the adhesive tape as “D”.

[Method for evaluating printability]
An ink jet printer (SP-300V manufactured by Roland Co., Ltd.) was applied to the surface of the receiving substrate obtained by using “(i) PET; polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness 50 μm)” as a support. ), And the following nine colors of solvent-based pigment ink containing a glycol-based high-polarity solvent and a pigment as a fluid are printed in the order illustrated below to obtain a printed image with a solid image of 100% to 400%. Obtained.

[Description of 9 color inks]
・ C100% ink ・ Y100% ink ・ M100% ink ・ Bk100% ink ・ Total 200% ink composed of C100% and M100% ・ Total 200% ink composed of M100% and Y100% ・ Y100% and C100% 200% ink consisting of C100%, M100% and Y100% total 300% ink C100%, M100% Y100% and K100% total 400% ink

The printability of a print image obtained by printing using the solvent-based pigment ink was evaluated based on the following criteria.

A: A print image formed using the above “total 400% of ink” was free from uneven color, bleeding, cracks, etc., and formed a uniform print image.

B: The printed image formed using the “300% total ink” had no color unevenness, bleeding, cracks, etc., but was subsequently superimposed on the printed image, The printed image obtained by printing with “400% ink” showed slight blurring and color unevenness.

C: “200% total ink consisting of C100% and M100%”, “200% total ink consisting of M100% and Y100%”, and “200% total consisting of Y100% and C100%” The print image formed by printing using “ink” did not show any color unevenness, blurring, cracks, etc., but was subsequently superimposed on the print image, and the “total of 300% ink” was added. The printed image obtained by printing using the image had blurring and color unevenness.

D: Printed images formed using the “C100% ink”, “Y100% ink”, “M100% ink”, and “Bk100% ink” had no color unevenness, blurring, or cracks. However, the print image obtained by successively superimposing on the print image and printing using the “total of 200% of ink” showed blurring and color unevenness.

E: Bleeding, color unevenness, and generation of cracks in the obtained printed image when printing is performed using any of the inks “C100% ink”, “Y100% ink”, “M100% ink”, and “Bk100% ink” It was observed.

[Method for preparing conductive ink as fluid]

[Ink preparation method]
[Preparation of nano silver ink for inkjet printing]
Silver particles having an average particle diameter of 30 nm are dispersed in a mixed solvent composed of 65 parts by mass of diethylene glycol diethyl ether, 18 parts by mass of γ-butyrolactone, 15 parts by mass of tetraethylene glycol dimethyl ether, and 2 parts by mass of tetraethylene glycol monobutyl ether. Thus, a nano-silver ink for solvent-based inkjet printing was prepared.

[Preparation of silver paste for screen printing]
A silver paste (NPS manufactured by Harima Chemicals Co., Ltd.) was used.

[Printing by inkjet printing method]
The nano silver ink for inkjet printing was applied to the surface of three kinds of receiving substrates obtained using the supports (i), (ii) and (iii), respectively, and an inkjet printer (inkjet manufactured by Konica Minolta IJ Co., Ltd.). Using a test machine EB100, an evaluation printer head KM512L, and a discharge amount of 42 pl), a straight line having a line width of 100 μm and a film thickness of 0.5 μm is printed by about 1 cm, and then dried at 150 ° C. for 30 minutes, thereby producing a printed matter. (Conductive pattern) was obtained.

[Printing by screen printing]
The screen-printing silver paste was applied to the surfaces of three kinds of receiving substrates obtained using the supports (i), (ii) and (iii), respectively, using a screen plate of a metal mesh 250, A straight line having a width of 50 μm and a film thickness of 1 μm was printed by about 1 cm, and then dried at 150 ° C. for 30 minutes to obtain a printed matter (conductive pattern).

[Evaluation method for fine line properties]
The entire printed part (line part) formed on the surface of the printed matter (conductive pattern) obtained by the above-described method is observed using an optical microscope (Digital Microscope VHX-100 manufactured by Keyence Corporation), and the printed part The presence or absence of bleeding was confirmed.

Specifically, no blur is observed at the outer edge of the printed part (line part), the boundary between the printed part and the non-printed part is clear, and there is a difference in height between the outer edge part and the central part of the line part. “A”, which is not seen, is smooth as the entire line part, and although slight blurring is confirmed in a very small part of the outer edge of the printed part (line part), the printed part and the non-printed part as a whole “B” indicates that the boundary is clear and the entire line portion is smooth, and a slight blur can be confirmed within a range of about 1/3 of the outer edge portion of the print portion (line portion). Although the boundary between the non-printing portion and the non-printing portion is partially unclear, the entire line portion is smooth and usable level is “C”, which is about 1/3 of the outer edge portion of the printing portion (line portion). Bleeding can be confirmed in the range of about ½, and the boundary between the printed part and the non-printed part becomes partially unclear in that part, and the outer edge part and the middle part of the line part become unclear. “D” indicates that the portion was not smooth, and bleeding was confirmed in a range of about ½ or more of the outer edge portion of the printed portion (line portion), and the boundary between the printed portion and the non-printed portion was uniform in that portion. What was unclear in the part and was not smooth between the outer edge part and the center part of the line part was evaluated as “E”.

[Evaluation method of conductivity]
The nano silver ink for inkjet printing was applied to the surface of two types of receiving substrates obtained by using the supports (i) and (ii), respectively, and an inkjet printer (ink tester EB100 manufactured by Konica Minolta IJ Co., Ltd.) By using a printer head for evaluation KM512L and a discharge amount of 42 pl), a rectangular area (area) of 3 cm in length and 1 cm in width is printed with a film thickness of 0.5 μm, and then dried at 150 ° C. for 30 minutes. Each printed matter (conductive pattern) was obtained.

In addition, the screen printing silver paste, each of the two receiving substrate surfaces obtained using the support (i) and (ii), using a screen plate of a metal mesh 250, 3 cm in length, A 1 cm wide rectangular area (area) was printed at a film thickness of 1 μm, and then dried at 150 ° C. for 30 minutes to obtain a printed matter (conductive pattern).

The volume resistivity of the solid printed portion formed in the rectangular range of 3 cm in length and 1 cm in width formed on the surface of the printed matter (conductive pattern) obtained by the above-described method was measured using a Loresta pointer meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation). It measured using. What volume resistivity is less than 5 × ^{10 -6} Ω · cm "A", 5 × ^{10 -6} or 9 × ^{10 -6} Ω · less than cm "B what is sufficient available levels “C”, a level that is 9 × 10 ⁻⁶ or more and less than 5 × 10 ⁻⁵ Ω · cm and that can be used, and “C” that is 5 × 10 ⁻⁵ or more and less than 9 × 10 ⁻⁵ Ω · cm Was evaluated as “E” when it was “D”, 9 × 10 ⁻⁵ or more and difficult to use practically.

[Durability evaluation method after electroless plating]
Silver particles (plating nucleus) having an average particle diameter of 30 nm were mixed with a mixed solvent consisting of 65 parts by mass of diethylene glycol diethyl ether, 18 parts by mass of γ-butyrolactone, 15 parts by mass of tetraethylene glycol dimethyl ether and 2 parts by mass of tetraethylene glycol monobutyl ether. ) Was dispersed to prepare a solvent-based plating nucleating agent.

An ink jet printer (Konica Minolta IJ Co., Ltd. ink jet testing machine EB100, evaluation printer head KM512L, discharge amount 42 pl) is used on the surface of the receiving substrate obtained by using the support (ii). A solid range of 5 cm in length and 5 cm in width (area) was solid-printed with a film thickness of 0.5 μm, and then dried at 150 ° C. for 30 minutes to obtain printed materials.

An activator (A screen A220 manufactured by Okuno Pharmaceutical Co., Ltd.) is applied to the surface of the printed matter obtained above (the surface on which the plating nucleus is supported), and the plating nucleus is activated under the condition of 55 ° C. × 5 minutes. Processed.

Next, an electroless copper plating agent (OPC-750 manufactured by Okuno Pharmaceutical Co., Ltd.) was applied to the surface subjected to the activation treatment, and an electroless copper plating treatment was performed at 20 ° C. for 20 minutes.

Thereby, a conductive pattern X (plating structure X) in which a plating film made of copper was formed on the surface on which the plating nucleus was carried was obtained.

A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the plating film surface of the conductive pattern X (plating structure X) obtained above with a finger, and the cellophane adhesive tape is then electrically conductive. Peeling was performed in the direction of 90 degrees with respect to the surface of the pattern X (plating structure X). The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

“A” indicates that no adherent was observed on the adhesive surface of the peeled cellophane adhesive tape, and it is any of metal plating, silver, and receiving layer within a range of less than about 5% of the adhesive tape application area. Is peeled off from the support and adhered to the adhesive tape within a range of about 5% to less than 50% of the adhesive area of the “B” adhesive tape. "C" peels off the support and adheres to the adhesive tape, and the metal plating, silver, or receiving layer peels off from the support within a range of about 50% or more of the adhesive tape application area. The thing adhering to the tape was evaluated as "D".

[Durability evaluation method after electrolytic plating]
Silver particles (plating nucleus) having an average particle diameter of 30 nm were mixed with a mixed solvent consisting of 65 parts by mass of diethylene glycol diethyl ether, 18 parts by mass of γ-butyrolactone, 15 parts by mass of tetraethylene glycol dimethyl ether and 2 parts by mass of tetraethylene glycol monobutyl ether. ) Was dispersed to prepare a solvent-based plating nucleating agent.

Next, copper sulfate plating (Top Lucina 81SW manufactured by Okuno Seiyaku Kogyo Co., Ltd.) is applied to the surface subjected to the activation treatment, and an electroplating treatment is performed under the conditions of 25 ° C., 3 Amp, 90 minutes / dm 2, thereby conducting the conductive. A conductive pattern Y (plating structure Y) was obtained in which a plating film made of copper was laminated on the surface of the plating film made of copper of the conductive pattern X (plating structure X).

A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the plating film surface of the conductive pattern Y (plating structure Y) obtained above with a finger, and the cellophane adhesive tape is then electrically conductive. Peeling was performed in the direction of 90 degrees with respect to the surface of the pattern X (plating structure X). The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

“A” indicates that no adherent was observed on the adhesive surface of the peeled cellophane adhesive tape, and it is any of metal plating, silver, and receiving layer within a range of less than about 5% of the adhesive tape application area. Is peeled off from the support and adhered to the adhesive tape within a range of about 5% to less than 50% of the adhesive area of the “B” adhesive tape. "C" peels off the support and adheres to the adhesive tape, and the metal plating, silver, or receiving layer peels off from the support within a range of about 50% or more of the adhesive tape application area. The thing adhering to the tape was evaluated as "D". The case where the plating film was not peeled or the plating was not deposited during the plating treatment step was designated as “E”.

Claims

Structure derived from the vinyl polymer (a1) in the side chain, obtained by reacting the polyol (A) containing the vinyl polymer (a1) having two hydroxyl groups at one end and the polyisocyanate (B) A resin composition for forming a receiving layer, which comprises a urethane resin (C) having
2. The resin composition for forming a receiving layer according to claim 1, wherein the vinyl polymer (a1) having two hydroxyl groups at one end has a number average molecular weight of 500 to 10,000.
The vinyl polymer (a1) having two hydroxyl groups at one end is a chain transfer agent (a1-1) having two hydroxyl groups and one mercapto group, and a vinyl monomer (a1-2) The resin composition for forming a receiving layer according to claim 1, which is obtained by reacting.
2. The vinyl monomer (a1-2) contains one or more vinyl monomers selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid alkyl esters. Resin composition for forming a receiving layer.
The resin composition for forming a receiving layer according to claim 1, wherein the polyol (A) further contains one or more selected from the group consisting of polyether polyol, polyester polyol and polycarbonate polyol.
The urethane resin (C) is obtained by using the vinyl polymer (a1) in the range of 1% by mass to 70% by mass with respect to the total mass of raw materials used for the production of the urethane resin (C). The resin composition for forming a receiving layer according to claim 1, which is a product.
2. The resin composition for forming a receiving layer according to claim 1, wherein the resin composition for forming a receiving layer forms a layer for receiving a fluid containing a conductive substance or a pigment.
8. The receptor according to claim 7, wherein the fluid containing the conductive substance or the pigment is a conductive ink containing a conductive substance, a plating nucleating agent containing a conductive substance, or a pigment ink containing a pigment. Layer forming resin composition.
A receptor substrate comprising a receptor layer formed by using the resin composition for forming a receptor layer according to any one of claims 1 to 8 on a part or all of the surface of the support.
A printed matter printed on a receiving layer constituting the receiving substrate according to claim 9 by a fluid containing a conductive substance or a pigment.
Printing was performed on the receiving layer constituting the receiving substrate according to claim 9 by using a conductive ink containing a conductive substance or a fluid made of a plating nucleating agent containing a conductive substance. Conductive pattern.
The conductive pattern according to claim 11, wherein the conductive pattern is obtained by subjecting a surface of a printing part formed by printing the fluid to an electrolytic plating or an electroless plating treatment.
An electronic circuit comprising the conductive pattern according to claim 11 or 12.