JP6855201B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions.

As the coating layer that covers the surface of the target object, for example, a layer that suppresses damage or deterioration of the target object, a layer that improves the design of the target object, and various other coating layers are widely used in the industrial world depending on the purpose. Has been done. Such a coating layer is formed by, for example, coating a resin composition containing a resin as a constituent material on the surface of a target object.

For example, a color filter used in the field of electronic equipment includes a colored layer partitioned by a light-shielding layer on a transparent base material, and includes the colored layer and a coating layer covering the light-shielding layer.
As such a color filter, for example, at the time of its manufacture, a resin composition (resin composition for a protective film) for forming a coating layer (protective film) is applied to a coating layer forming surface, that is, a coating surface. At times, a part of the resin composition is repelled from the coated surface to cause pinhole-shaped coating omission, that is, the generation of so-called cissing can be suppressed (see Patent Document 1). Repellent is usually caused by the adhesion of foreign matter on the coated surface of the resin composition. Then, the coating layer on which the repelling is generated cannot sufficiently cover the target object and has defects. On the other hand, the above-mentioned resin composition suppresses the occurrence of cissing by containing a combination of a specific range of components.

On the other hand, a laminated body having a laminated structure similar to the above-mentioned color filter and used in the field of electronic equipment includes a laminated body in which a conductive layer is provided on a base material. For example, the laminate in which the conductive layer is patterned is used as a circuit board for communication equipment and the like. Further, the laminated body provided with the ultrafine wiring or the ultrathin wiring as the patterned conductive layer can further form a touch panel or an optical display by combining with a transparent base material. Further, even in such a laminated body, a coating layer covering the conductive layer is usually provided on the conductive layer, and the coating layer in this case is also required to have no defects due to the occurrence of cissing. Further, the base material is easily affected by the resin composition for forming the coating layer, but in the laminated body, it is also required that the base material is not deteriorated by the resin composition.

Japanese Patent No. 5178407

However, the coating layer disclosed in Patent Document 1 is formed on a base material provided with a colored layer and a light-shielding layer, and the surface of each of these layers (base material, colored layer, light-shielding layer) has a resin composition. It becomes the coated surface of the object. On the other hand, the coating layer in the laminate is formed on a base material provided with a conductive layer, and the surface of each of these layers (base material, conductive layer) is a coated surface of the resin composition. That is, the laminate provided with the conductive layer is completely different from the color filter disclosed in Patent Document 1 in the characteristics of the coating layer to be formed, in other words, the coated surface of the resin composition. Therefore, even if the resin composition disclosed in Patent Document 1 is used to form a coating layer during the production of the laminate provided with the conductive layer, it is not certain whether the generation of cissing can be suppressed. Further, it is not clear whether the deterioration of the base material in the laminated body can be suppressed.

The present invention has been made in view of the above circumstances, and is a resin composition that can be used for forming a coating layer in the production of a laminate in which a base material, a conductive layer, and a coating layer are laminated in this order. Therefore, it is an object of the present invention to provide a resin composition capable of suppressing the generation of repellent during the formation of a coating layer without deteriorating the base material.

In order to solve the above problems, the present invention provides a resin composition in which a polyurethane (meth) acrylate, an acrylic acid ester, and a solvent are blended and the solvent is a keto alcohol and an alcohol ether.
In the resin composition of the present invention, the SP value of the ketoalcohol is preferably 10.4 to 11.0, and the SP value of the alcohol ether is preferably 9.3 to 10.3.

According to the present invention, it is a resin composition that can be used for forming a coating layer at the time of manufacturing a laminate in which a base material, a conductive layer and a coating layer are laminated in this order, without deteriorating the base material. , A resin composition capable of suppressing the generation of repellent during the formation of a coating layer is provided.

It is sectional drawing which shows typically one Embodiment of the laminated body obtained by using the resin composition of this invention. It is sectional drawing which shows typically the other embodiment of the laminated body obtained by using the resin composition of this invention. It is sectional drawing for schematically explaining the manufacturing method of the laminated body shown in FIG. It is a graph which shows the relationship between the viscosity and the surface tension in the composition for a coating layer of an Example and a comparative example.

<< Resin composition >>
The resin composition of the present invention contains a polyurethane (meth) acrylate, an acrylic acid ester, and a solvent, and the solvent is ketoalcohol and alcohol ether.
The resin composition of the present invention has curability and is usually energy ray curable. The resin composition of the present invention can be used to form a coating layer on a target product, and the cured product of the resin composition is suitable as, for example, a protective film.

Examples of the energy rays include ultraviolet rays such as far ultraviolet rays, ultraviolet rays and near ultraviolet rays; infrared rays; electromagnetic radiations such as X-rays and γ-rays; particle radiations such as electron rays, proton rays and neutron rays.

In the resin composition, the polyurethane (meth) acrylate and the acrylic acid ester are resin components and are the main constituent components of the coating layer.
Further, in the resin composition, the ketoalcohol and the alcohol ether are solvents. Since the resin composition contains the keto alcohol and the alcohol ether, it is possible to suppress the generation of repellent of the resin composition when it is applied to the coated surface of the resin composition, that is, the surface on which the coating layer is formed. .. In addition, in this specification, "hajiki" means that a part of the coated resin composition is repelled from the coated surface and a part of the coated surface is not covered with the resin composition unless otherwise specified. , Means that a state of missing coating occurs. The shape of the coating missing is not particularly limited. Further, the resin composition does not deteriorate the base material when used for forming the coating layer in the production of a laminate in which the base material, the conductive layer and the coating layer are laminated in this order. For example, white turbidity does not occur due to erosion of the base material.

<Polyurethane (meth) acrylate>
In the resin composition, the polyurethane (meth) acrylate is not particularly limited, and is not particularly limited as long as it has a property of being cured by irradiation with energy rays, that is, an energy ray-curable one.

In addition, in this specification, "(meth) acrylate" is a concept including both "acrylate" and "methacrylate". The same applies to terms similar to "(meth) acrylate". For example, "(meth) acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid", and "(meth) acrylate" is used. ) "Acryloyl group" is a concept that includes both "acryloyl group" and "methacrylic acid group".

The weight average molecular weight of the polyurethane (meth) acrylate is not particularly limited, but is preferably 500 to 30,000, more preferably 800 to 20,000, and particularly preferably 1200 to 15,000.

In the resin composition, one type of polyurethane (meth) acrylate may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof are arbitrary. Can be selected.

<Acrylic acid ester>
In the resin composition, the acrylic acid ester (acrylate) is not particularly limited, and for example, acrylic acid alkyl ester (alkyl acrylate), acrylic acid aryl ester (aryl acrylate), acrylic acid aralkyl ester (aralkyl acrylate) and the like can be appropriately selected. You can choose.

In the resin composition, one type of acrylic acid ester may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof are arbitrarily selected. it can.

In the resin composition, the ratio of the total blending amount of the polyurethane (meth) acrylate and the acrylic acid ester (that is, the blending amount of the resin component) to the total blending component is preferably 14% by mass or more, preferably 15% by mass. The above is more preferable. When the ratio is at least the lower limit value, the effect of suppressing the generation of cissing of the resin composition without deteriorating the base material becomes higher.
Further, in the formed coating layer, bleeding is highly suppressed and the surface smoothness is further improved, so that the ratio is preferably 16.5% by mass or more, and is 17% by mass or more. Is more preferable, and 17.5% by mass or more is particularly preferable.

In the resin composition, the ratio of the total amount of the polyurethane (meth) acrylate and the acrylic acid ester to the total amount of the components is preferably 35% by mass or less, more preferably 30% by mass or less. It is more preferably 26% by mass or less, and particularly preferably 22% by mass or less. When the ratio is not more than the upper limit value, the handleability of the resin composition becomes better.

In the resin composition, the ratio of the total blending amount of the polyurethane (meth) acrylate and the acrylic acid ester to the total blending component is within a range set by arbitrarily combining any of the above lower limit values and upper limit values. Can be adjusted to be included in.

In the resin composition, the ratio of the blending amounts of polyurethane (meth) acrylate and acrylic acid ester is the mass ratio of [blending amount (mass) of polyurethane (meth) acrylate]: [blending amount (mass) of acrylic acid ester]. It is preferably 45:55 to 95: 5, more preferably 50:50 to 90:10, further preferably 55:45 to 85:15, and 60:40 to 80. : 20 is particularly preferable. When the ratio of the blending amounts is within such a range, the effect of suppressing the generation of cissing of the resin composition without deteriorating the base material becomes higher.

<Ket alcohol>
The ketoalcohol is not particularly limited as long as it is a compound having both a carbonyl group and a hydroxyl group in one molecule, having no ether bond, and being liquid at room temperature. That is, the ketoalcohol does not contain the alcohol ether.
In addition, in this specification, "room temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 30 ° C.

For example, the ketoalcohol may be linear, branched or cyclic, and when cyclic, it may be monocyclic or polycyclic.

The number of carbonyl groups and hydroxyl groups contained in one molecule of ketoalcohol may be one or two or more, and is not particularly limited.
The number of carbonyl groups and hydroxyl groups contained in one molecule of ketoalcohol may be the same or different from each other, but it is preferable that they are the same.
The number of carbonyl groups and hydroxyl groups contained in one molecule of ketoalcohol is preferably 2 or less, and more preferably 1 each.

The bonding positions of the carbonyl group and the hydroxyl group in the keto alcohol are not particularly limited. For example, when the ketoalcohol has a chain structure, the hydroxyl group may be present at the terminal portion of the main chain or at the non-terminal portion.
In the present specification, the "main chain" of a compound having a chain structure means "a site having the largest number of atoms constituting the chain skeleton".

The SP value of ketoalcohol is preferably 10.4 to 11.0, more preferably 10.6 to 11.0. When the SP value of the ketoalcohol is within such a range, the effect of suppressing the generation of repellent of the resin composition without deteriorating the base material becomes higher.

Preferred keto alcohols include, for example, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone, SP value 10.8) and the like.

In the resin composition, one type of ketoalcohol may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected. ..

<Alcohol ether>
The alcohol ether is not particularly limited as long as it is a compound which has both a hydroxyl group and an ether bond in one molecule, does not have a carbonyl group, and is liquid at room temperature. That is, the alcohol ether does not contain the keto alcohol.

For example, the alcohol ether may be linear, branched chain or cyclic, and when it is cyclic, it may be monocyclic or polycyclic.

The number of hydroxyl groups and ether bonds of one molecule of alcohol ether may be one or two or more, and is not particularly limited.
The number of hydroxyl groups and ether bonds of one molecule of alcohol ether may be the same or different from each other, but it is preferable that they are the same.
The number of hydroxyl groups and ether bonds of one molecule of alcohol ether is preferably 2 or less, and more preferably 1 of each.

The bonding position of the hydroxyl group and the ether bond in the alcohol ether is not particularly limited. For example, when the alcohol ether has a chain structure, the hydroxyl group may be present at the terminal portion of the main chain or at the non-terminal portion.

The SP value of the alcohol ether is preferably 9.3 to 10.3, more preferably 9.5 to 10.3. When the SP value of the alcohol ether is within such a range, the effect of suppressing the generation of cissing of the resin composition without deteriorating the base material becomes higher.

Preferred alcohol ethers include, for example, ethylene glycol monopropyl ether (SP value 10.2), 1-butoxy-2-propanol (propylene glycol 1-mono-n-butyl ether, SP value 9.7) and the like.

In the resin composition, one type of alcohol ether may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected. ..

In the resin composition, the SP value of keto alcohol and the SP value of alcohol ether are both preferably in the above-mentioned preferable numerical range.

In the resin composition, the difference between the SP value of keto alcohol and the SP value of alcohol ether ([SP value of keto alcohol]-[SP value of alcohol ether]) is preferably 0.4 or more. , 0.5 or more is more preferable. When the difference between the SP values is not more than the lower limit value, the effect of suppressing the generation of cissing of the resin composition without deteriorating the base material becomes higher.
On the other hand, the upper limit of the difference between the SP values is not particularly limited, but may be, for example, 1.3.
In the resin composition, the difference between the SP values can be adjusted so as to be included in a range set by arbitrarily combining any of the above lower limit values and upper limit values.

In the resin composition, the ratio of the total amount of ketoalcohol and alcohol ether to the total amount of the components is preferably 65 to 86% by mass, more preferably 70 to 85% by mass, and 74 to 74 to It is particularly preferably 84% by mass. When the ratio is in such a range, the effect of suppressing the generation of cissing of the resin composition without deteriorating the base material becomes higher.

In the resin composition, the ratio of the blending amounts of ketoalcohol and alcohol ether is expressed by the mass ratio of [blending amount of ketoalcohol (mass)]: [blending amount of alcohol ether (mass)], and is from 80:20. It is preferably 20:80, more preferably 76:24 to 24:76, and particularly preferably 72:28 to 28:72. When the ratio of the blending amounts is within such a range, the effect of suppressing the generation of cissing of the resin composition without deteriorating the base material becomes higher.

<Hardener>
The resin composition preferably contains a curing agent in addition to the polyurethane (meth) acrylate, acrylic acid ester, keto alcohol and alcohol ether.
The curing agent may be a known one, and may be appropriately selected depending on the intended purpose.
In the resin composition, one type of curing agent may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected. ..

In the resin composition, the ratio of the amount of the curing agent to the total amount of the polyurethane (meth) acrylate and the acrylic acid ester (that is, the amount of the resin component) is preferably 1 to 10% by mass, 2 It is more preferably about 8% by mass, and particularly preferably 3 to 7% by mass. When the ratio is at least the lower limit value, the effect of using the curing agent can be obtained more remarkably. Further, when the ratio is not more than the upper limit value, excessive use of the curing agent is suppressed.

<Additives>
The resin composition contains various known additives that do not fall under any of the polyurethane (meth) acrylate, acrylic acid ester, keto alcohol, alcohol ether and curing agent within a range that does not impair the effects of the present invention. It may be made of alcohol.
In the resin composition, one type of additive may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected. ..
The blending amount of the additive in the resin composition may be appropriately selected according to the type of the additive, and is not particularly limited.
Preferred additives include, for example, migration inhibitors, surfactants and the like.

[Migration inhibitor]
As will be described later, the resin composition is suitable for forming a coating layer in a laminate in which a base material, a conductive layer, and a coating layer are laminated in this order in the thickness direction thereof. Such a laminate will be described in detail later. Further, the resin composition used for forming such a coating layer may be particularly referred to as a "coating layer composition" in the present specification.
The migration inhibitor is a component for suppressing a change in the formation position of the conductive layer on the base material (migration of the conductive layer) in such a laminated body. Migration of the conductive layer is likely to occur between adjacent lines, for example, when the conductive layer is patterned in a line-and-space pattern.

Examples of the migration inhibitor include 1,2,3-benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [N, N-bis (2-ethylhexyl) amino. Methyl] methylbenzotriazole, 2,2'-[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol, 5-methylbenzotriazole, 1,2-bis [3- (4-hydroxy) -3,5-di-tert-butylphenyl) propionyl] hydrazine and the like.

In the resin composition, the ratio of the blending amount of the migration inhibitor to the total blending amount of the polyurethane (meth) acrylate and the acrylic acid ester (that is, the blending amount of the resin component) is preferably 1 to 10% by mass. It is more preferably 2 to 8% by mass, and particularly preferably 3 to 7% by mass. When the ratio is at least the lower limit value, the effect of using the migration inhibitor can be obtained more remarkably. Further, when the ratio is not more than the upper limit value, the effect of suppressing the generation of cissing of the resin composition without deteriorating the base material and the effect of using the migration inhibitor are more excellent. Obtained in balance.

[Surfactant]
The surfactant may be a known one, and may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant, and may be appropriately selected depending on the intended purpose.

Among them, the surfactant is preferably a nonionic surfactant.
The nonionic surfactant preferably has a fluorine atom, more preferably has a fluoroalkenyl group, and particularly preferably has a perfluoroalkenyl group.

In the resin composition, one type of surfactant may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof may be arbitrarily selected. it can.

When a surfactant is used, the ratio of the blending amount of the surfactant to the total amount of the blending components in the resin composition is preferably 0.05 to 1% by mass, preferably 0.05 to 0.5% by mass. More preferably. When the ratio is at least the lower limit value, the effect of using the surfactant can be obtained more remarkably. Further, when the ratio is not more than the upper limit value, excessive use of the surfactant is suppressed.

<Other solvents>
In addition to the ketoalcohol and alcohol ether, a solvent (may be abbreviated as "other solvent" in the present specification) is blended in the resin composition as long as the effect of the present invention is not impaired. You may. By blending another solvent, the characteristics of the resin composition may be adjusted.
The other solvent is not particularly limited and may be appropriately selected depending on the intended purpose.

Examples of the other solvent include aromatic hydrocarbons such as toluene, o-xylene, m-xylene and p-xylene; aliphatic hydrocarbons such as hexane, heptane and octane; ethanol, 1-propanol and 2-propanol. , 1-butanol, 2-butanol, 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-2-propanol (tert-butyl alcohol) and other monovalent alcohols; ethylene glycol (1,2-ethanediol) , Polyvalent alcohols including dihydric alcohols such as propylene glycol (1,2-propanediol), diethylene glycol (2,2'-oxydiethanol); 2-aminoethanol, 3-amino-1-propanol, 4- Amino alcohols such as amino-1-butanol (compounds having amino groups and hydroxyl groups); halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, monomethyl glutarate, dimethyl glutarate; diethyl ether, tetrahydrofuran (THF) , Ethers such as 1,2-dimethoxyethane (dimethylcellosolve); ketones such as acetone, methylethylketone (MEK), cyclohexanone, 2,6-dimethyl-4-heptanone, isophorone; nitriles such as acetonitrile; N, N-dimethylformamide Examples thereof include, but are not limited to, amides such as (DMF) and N, N-dimethylacetamide.

In the present invention, the ketone shall not contain ketoalcohol unless otherwise specified. That is, in the present invention, the ketone is one that does not contain a hydroxyl group (-OH), and the ketone is distinguished as being different from the keto alcohol.
Further, in the present invention, unless otherwise specified, the alcohol does not contain keto alcohol and alcohol ether. That is, in the present invention, the alcohol does not contain both a carbonyl group (-C (= O)-) and an ether bond (-O-), and the alcohol is distinguished from ketoalcohol and alcohol ether. ..

In the resin composition, one type of other solvent may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected. ..

The blending amount of the other solvent in the resin composition is not particularly limited, and may be appropriately adjusted according to the type of the other solvent.
For example, the SP values of other solvents are the preferred SP value of the keto alcohol (ie, SP value 10.4 to 11.0) and the preferred SP value of the alcohol ether (ie, SP value 9.3-10. When it is contained in any of 3), the ratio of the amount of the other solvent to the total amount of the ketoalcohol and the alcohol ether in the resin composition is 0 to 10% by mass and 0 to 5. It can be either% by mass and 0 to 2% by mass. However, this is just an example.
On the other hand, the SP values of the other solvents are the preferable SP value of the keto alcohol (that is, SP value 10.4 to 11.0) and the preferable SP value of the alcohol ether (that is, SP value 9.3 to 10. When it is not contained in any of 3), the ratio of the blending amount of the other solvent to the total blending amount of the keto alcohol and the alcohol ether in the resin composition is 0 to 3% by mass. Is preferable, and 0 to 1% by mass is more preferable.

<Other resins>
The resin composition is a resin other than the polyurethane (meth) acrylate and the acrylic acid ester (in this specification, it may be abbreviated as "other resin") within a range not impairing the effect of the present invention. It may be blended. By blending other resins, the characteristics of the resin composition may be adjusted.
The other resin is not particularly limited, and may be either an energy ray-curable resin or a thermosetting resin, and may be appropriately selected depending on the intended purpose.

In the resin composition, one type of other resin may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected. ..

The blending amount of the other resin in the resin composition is not particularly limited, and may be appropriately adjusted according to the type of the other resin.
Usually, in the resin composition, the ratio of the blending amount of the other resin to the total blending amount of the polyurethane (meth) acrylate and the acrylic acid ester is preferably 0 to 5% by mass, preferably 0 to 3% by mass. It is more preferably%, and particularly preferably 0 to 1% by mass.

The viscosity of the resin composition at 25 ° C., measured by the method described in Examples described later, is preferably 5 to 13.5 mPa · s, more preferably 6 to 13.5 mPa · s. , 7 to 13.5 mPa · s is more preferable, and 7.5 to 13.5 mPa · s is particularly preferable. When the viscosity is in such a range, the effect of suppressing the generation of cissing of the resin composition without deteriorating the base material becomes higher.
From the viewpoint of suppressing the generation of cissing of the resin composition, the viscosity may be, for example, 5.3 to 13.5 mPa · s.

The surface tension of the resin composition at 25 ° C., measured by the method described in Examples described later, is preferably 22.5 to 29.8 mN / m, preferably 22.7 to 29.7 mN / m. It is more preferably 22.9 to 29.6 mN / m, and particularly preferably 23.1 to 29.5 mN / m. When the surface tension is in such a range, the effect of suppressing the generation of cissing of the resin composition is further enhanced without deteriorating the base material.

In the resin composition, it is preferable that both the viscosity and the surface tension are in the above-mentioned preferable numerical range.

As described above, the resin composition is preferably used for forming a coating layer in the production of a laminate in which a base material, a conductive layer and a coating layer are laminated in this order. is there. However, the target of use of the resin composition is not limited to this, and it can be used on the entire coated surface where there is a concern that cissing may occur when using a normal resin composition.

<< Manufacturing method of resin composition >>
The resin composition can be obtained by blending the polyurethane (meth) acrylate, acrylic acid ester, keto alcohol, alcohol ether, and, if necessary, other components not corresponding to any of these. Here, examples of the "other component" include the curing agent, additives, other solvents, other resins, and the like.

At the time of producing the resin composition, after blending each component, the obtained one may be used as it is as the resin composition, or if necessary, the obtained one obtained by continuously performing a known purification operation is used as the resin composition. May be.

When blending each component, all the components may be added and then mixed, some components may be added sequentially and mixed, or all components may be added sequentially and mixed. Good.
The mixing method is not particularly limited, and a method of rotating and mixing a stirrer or a stirring blade or the like; a method of mixing using a mixer, a three-roll roll, a kneader or a bead mill or the like; a method of adding ultrasonic waves and the like, etc. It may be appropriately selected from known methods.

The temperature at the time of compounding is not particularly limited as long as each compounding component is not deteriorated, but is preferably 15 to 50 ° C. Then, the temperature at the time of blending may be appropriately adjusted according to the type and amount of the blending component so that the mixture obtained by blending has a viscosity that makes it easy to stir.
The blending time is also not particularly limited as long as each blending component is not deteriorated, but is preferably the time required for the blended components to be uniformly dissolved or dispersed, and is preferably 10 minutes to 12 hours, for example. ..

<< Second Resin Composition >>
Up to this point, a resin composition containing polyurethane (meth) acrylate, acrylic acid ester, keto alcohol and alcohol ether has been described. It was also explained that the SP value of ketoalcohol is preferably 10.4 to 11.0, and the SP value of alcohol ether is preferably 9.3 to 10.3.
On the other hand, a resin composition containing a polyurethane (meth) acrylate, an acrylic acid ester, a solvent having an SP value of 10.4 to 11.0, and a solvent having an SP value of 9.3 to 10.3 is also available. It has the same effect as the above-mentioned resin composition of the present invention. In the present specification, the former is referred to as a "second resin composition", and in order to distinguish it from the second resin composition, the latter resin composition described in detail above is referred to as a "first resin composition". Sometimes referred to. That is, the second resin composition can also be used for forming the coating layer during the production of the laminate, and can suppress the generation of cissing during the formation of the coating layer without deteriorating the base material.

In the second resin composition, the solvent having an SP value of 10.4 to 11.0 may be ketoalcohol or a solvent other than ketoalcohol as long as it is liquid at room temperature.
Further, in the second resin composition, the solvent having an SP value of 9.3 to 10.3 may be an alcohol ether or a solvent other than the alcohol ether as long as it is liquid at room temperature. ..

In the second resin composition, instead of containing keto alcohol, a solvent having an SP value of 10.4 to 11.0 is blended without being limited to keto alcohol, and alcohol ether is blended. Instead, it is the same as the first resin composition except that a solvent having an SP value of 9.3 to 10.3 is blended without being limited to alcohol ether.

<< Laminated body >>
The resin composition is suitable as a material for forming a coating layer in a laminate in which a base material, a conductive layer, and a coating layer are laminated in this order in the thickness direction thereof.
Hereinafter, the laminate that can be produced by using the resin composition will be described in detail.

FIG. 1 is a cross-sectional view schematically showing an embodiment of a laminate obtained by using the resin composition of the present invention. In addition, in the figure used in the following description, in order to make the explanation easier to understand, the main part may be enlarged and shown, and the dimensional ratio of each component is the same as the actual one. Is not always.

The laminate 1 shown here is formed by laminating the base material 11, the conductive layer 12, and the coating layer 13 in this order in the thickness direction thereof. In other words, the laminate 1 is configured by providing a coating layer 13 on the base material 11 and providing a conductive layer 12 between the base material 11 and the coating layer 13. The coating layer 13 is formed by using the resin composition of the present invention.

The base material 11 is preferably in the form of a film or a sheet.
The conductive layer 12 is linear and is provided in a part of one surface of the base material 11 (sometimes referred to as a “first surface” in the present specification) 11a. The line length direction (longitudinal direction) of the conductive layer 12 is a direction orthogonal to the cross section of the conductive layer 12 in FIG. The conductive layer 12 is laminated in direct contact with the first surface 11a of the base material 11.
The coating layer 13 covers the entire surface of the base material 11 on which the conductive layer 12 is formed, and is a region of the first surface 11a of the base material 11 where the conductive layer 12 is not provided and the surface 12a of the conductive layer 12. And are laminated in direct contact with. The coating layer 13 is preferably in the form of a film or a sheet. In FIG. 1, reference numeral 13a indicates the surface of the coating layer.

FIG. 2 is a cross-sectional view schematically showing another embodiment of the laminate obtained by using the resin composition of the present invention. In the drawings after FIG. 2, the same components as those shown in FIG. 1 are designated by the same reference numerals as in the case of FIG. 1, and detailed description thereof will be omitted.
In the laminated body 2 shown here, the conductive layer 22 is in the form of a film or a sheet, and is laminated by covering a part or all the regions of the first surface 11a of the base material 11, and the cross section of the coating layer 23 accordingly. It is the same as the laminated body 1 shown in FIG. 1 except that the shapes are different. In FIG. 2, reference numeral 22a indicates the surface of the conductive layer 22, and reference numeral 23a indicates the surface of the coating layer.

The laminate obtained by using the resin composition of the present invention is not limited to those shown in FIGS. 1 and 2, and can be, for example, those shown in FIGS. 1 and 2 within a range that does not impair the effects of the present invention. Other configurations may be added, or some configurations may be changed as appropriate.
For example, the shape of the conductive layer when the laminated body is viewed in a plan view so as to look down on the surface of the base material can be arbitrarily set according to the purpose, and the conductive layer is patterned into a shape other than linear. You may. The linearly patterned conductive layer is useful, for example, as wiring.

Further, the laminate may be, for example, one in which a layer other than the conductive layer and the coating layer is provided on the base material. Examples of the other layer include an intermediate layer provided between the base material and the conductive layer or between the conductive layer and the coating layer. Examples of the intermediate layer include an adhesion layer for improving the adhesion between adjacent layers, an adhesive layer for stably fixing adjacent layers, an adhesive layer, and the like, depending on the purpose. It may be selected as appropriate, and is not particularly limited.

However, it is preferable that the laminated body does not have the intermediate layer, the conductive layer is directly contacted with the base material and laminated, and the coating layer is directly contacted with the conductive layer and laminated. When the conductive layer is patterned, it is preferable that the coating layer is laminated in direct contact with the region where the conductive layer of the base material is not provided. In such a laminated body, the effect of the present invention can be obtained more remarkably. Further, such a laminated body has a simplified structure and can be manufactured by a simplified process. Further, in such a laminated body, by not providing the intermediate layer, it is possible to eliminate the possibility that the intermediate layer adversely affects the conductive layer and the coating layer in terms of quality.

Further, the laminate may be formed on, for example, on the other surface of the base material (the surface designated by reference numeral 11b in FIGS. 1 and 2, and may be referred to as a “second surface” in the present specification). The layers may be laminated. Here, examples of the material laminated on the second surface of the base material include those laminated on the first surface of the base material, such as a conductive layer, a coating layer, and an intermediate layer.

For example, the coating layer (on the second surface side) provided on the second surface of the base material may or may not be formed by using the resin composition of the present invention. (It may be formed by using a resin composition other than the resin composition of the present invention). When the coating layer on the second surface side of the base material is formed by using the resin composition of the present invention, this coating layer is provided on the first surface of the base material (first surface). The composition may be the same as or different from that of the coating layer (on the one side).

Similarly, other layers such as the conductive layer and the intermediate layer on the second surface side of the base material have the same composition as the other layers such as the conductive layer and the intermediate layer on the first surface side of the base material, respectively. It may be different.

The conductive layer, coating layer, intermediate layer, etc. on the second surface side of the base material have the same form (for example, shape, thickness, etc.) as the conductive layer, coating layer, intermediate layer, etc. on the first surface side of the base material, respectively. It may be, or it may be different.
Next, each configuration of the laminated body will be described in more detail.

<Base material>
The thickness of the base material is preferably 10 to 5000 μm, more preferably 10 to 3000 μm.

The material of the base material is not particularly limited, but preferred ones are, for example, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polymethylpentene (PMP), and poly. Acrylic resins such as cycloolefin, polystyrene (PS), polyvinyl acetate (PVAC), polymethylmethacrylate (PMMA), AS resin, ABS resin, polyamide (PA), polyimide, polyamideimide (PAI), polyacetal, polyethylene terephthalate. (PET), Polybutylene terephthalate (PBT), Polytrimethylene terephthalate (PTT), Polyethylene naphthalate (PEN), Polybutylene naphthalate (PBN), Polyphenylensulfide (PPS), Polysulfone (PSF), Polyethersulfonate PES), polyetherketone (PEK), polyetheretherketone (PEEK), polycarbonate (PC), polyurethane, polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyallylate, epoxy resin, melamine resin, phenol Examples thereof include synthetic resins such as resins and urea resins.
In addition to the above, examples of the material of the base material include ceramics such as glass and silicon, and paper.
Further, the base material may be a combination of two or more kinds of materials such as a glass epoxy resin and a polymer alloy.

The base material may be composed of a single layer or may be composed of a plurality of layers of two or more layers. When the base material is composed of a plurality of layers, the plurality of layers may be the same as or different from each other.
In the present specification, not only in the case of a base material, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers are different". It means that only some of the layers may be the same, and that "plurality of layers are different from each other" means that "at least one of the materials and thicknesses of each layer is different from each other". means.
When the base material is composed of a plurality of layers, the total thickness of each layer may be set to the above-mentioned preferable thickness of the base material.

However, regardless of whether the base material is a single layer or a plurality of layers, the base material with which the resin composition comes into direct contact is preferably made of polycarbonate or mainly composed of polycarbonate. By using such a base material, the effect of suppressing the generation of cissing of the resin composition is further enhanced without deteriorating the base material.
Here, the "base material containing polycarbonate as a main component" means "a base material containing polycarbonate and other components and having a polycarbonate content of 50% by mass or more". The content of polycarbonate in the base material containing polycarbonate as a main component is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. It is particularly preferably 90% by mass or more, and may be, for example, 95% by mass or more, 97% by mass or more, or 99% by mass or more.

<Conductive layer>
The material of the conductive layer is not particularly limited as long as it has conductivity, but from the viewpoint that a conductive layer having a low resistance value can be easily formed, a single metal such as silver or copper, or an alloy (hereinafter, these are summarized). (Sometimes abbreviated as "metal"), more preferably silver or copper.

The thickness of the conductive layer can be arbitrarily set depending on the intended purpose, but is preferably 3 nm to 40 μm, more preferably 4 nm to 30 μm. When the thickness of the conductive layer is at least the lower limit value, the conductivity can be further improved, and the structure of the conductive layer can be maintained more stably. Further, when the thickness of the conductive layer is not more than the upper limit value, the laminated body can be made thinner.

The conductive layer may be composed of a single layer or may be composed of a plurality of layers of two or more layers. When the conductive layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other.
When the conductive layer is composed of a plurality of layers, the total thickness of each layer may be set to be the above-mentioned preferable thickness of the conductive layer.

<Coating layer>
The coating layer is formed by using the resin composition of the present invention, and is made of a resin or contains a resin as a main component.
The coating layer is one or two or more selected from the group consisting of polyurethane (meth) acrylate and its cured product, and one or two selected from the group consisting of acrylic acid ester and its cured product as the resin. Contains more than seeds.
In the present specification, the "main component" means a component having a content of 30% by mass or more and less than 100% by mass in the target layer.
The coating layer preferably has light transmission, and preferably has high transparency.

In the coating layer, the content of the resin is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 85% by mass or more, and 90% by mass or more. Is particularly preferable, and for example, it may be any one of 92% by mass or more, 94% by mass or more, 96% by mass or more, and the like.
On the other hand, in the coating layer, the upper limit of the content of the resin is not particularly limited, and may be, for example, either 98% by mass or 99% by mass, and the content of the resin is 100% by mass. You may.

The thickness of the coating layer can be arbitrarily set depending on the intended purpose, but is preferably 200 nm to 50 μm, more preferably 500 nm to 40 μm, and particularly preferably 800 nm to 30 μm. When the thickness of the coating layer is at least the lower limit value, the coating effect of the conductive layer can be further improved, and the structure of the coating layer can be maintained more stably. Further, when the thickness of the coating layer is not more than the upper limit value, it is possible to prevent the coating layer from becoming excessively thick.

The coating layer may be composed of a single layer or may be composed of a plurality of layers of two or more layers. When the coating layer consists of a plurality of layers, the plurality of layers may be the same as or different from each other.
When the coating layer is composed of a plurality of layers, the total thickness of each layer may be set to be the above-mentioned preferable thickness of the coating layer.

<< Manufacturing method of laminated body >>
The laminate has, for example, a step of forming a conductive layer on a base material (hereinafter, may be abbreviated as "conductive layer forming step") and a step of forming a coating layer on the conductive layer (hereinafter, "" It can be manufactured by a manufacturing method having (sometimes abbreviated as "coating layer forming step").

FIG. 3 is a cross-sectional view for schematically explaining the manufacturing method of the laminated body 1 shown in FIG.
When the laminate 1 shown in FIG. 1 is manufactured, the base material 11 shown in FIG. 3 (a) is used. First, as shown in FIG. 3 (b), in the conductive layer forming step, the first base material 11 is used. The conductive layer 12 is formed on one surface 11a.
Next, as shown in FIG. 3C, in the coating layer forming step, the forming surface of the conductive layer 12 on the base material 11 is coated with the coating layer 13. As a result, the coating layer 13 is formed on the surface 12a of the conductive layer 12 and the region of the first surface 11a of the base material 11 that does not have the conductive layer 12.
From the above, the laminated body 1 is obtained.
Although the laminated body 1 shown in FIG. 1 has been cited and described here, the laminated body of the present invention other than the laminated body 1 can also be obtained by the same method as this method or by a method in which a part of this method is modified. Can be manufactured.
Hereinafter, each step will be described in more detail.

<Conductive layer forming process>
The conductive layer is formed by, for example, attaching a composition as a raw material for forming the conductive layer (hereinafter, may be abbreviated as "composition for a conductive layer") to a target portion on a base material. It can be formed by forming a layer and appropriately selecting a solidification treatment such as a drying treatment or a heating (firing) treatment on the composition layer (composition for a conductive layer). The heat treatment may also be performed as a drying treatment.
Further, in the conductive layer, the composition for the conductive layer is adhered to a predetermined region or the entire surface of the substrate surface to form a composition layer, and the composition layer (composition for the conductive layer) is formed by the same method as described above. It can also be formed by forming a conductive layer (conductive layer before patterning) and then patterning the conductive layer so as to have a desired shape by a known method such as etching.

When the material of the conductive layer is metal, a metal ink composition containing a metal or a metal-forming material may be used as the composition for the conductive layer.
The metal forming material in the metal ink composition may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be adjusted arbitrarily.

The metal (single metal or alloy) to be blended is preferably in the form of particles or fibers (tube-like, wire-like, etc.), more preferably nanoparticles or nanowires, and silver nanoparticles or silver nanos. Particularly preferred are wires, copper nanoparticles or copper nanowires.
In the present specification, the "nanoparticle" means a particle having a particle size of 1 nm or more and less than 1000 nm, preferably 1 to 100 nm, and the "nanowire" has a width of 1 nm or more and less than 1000 nm, preferably. It means a wire having a diameter of 1 to 100 nm.

The material for forming the metal to be blended may be any as long as it has a corresponding metal atom (element) and produces a metal by a structural change such as decomposition. For example, a metal salt, a metal complex, or an organic metal compound (metal-). Compounds having a carbon bond) and the like. The metal salt and the metal complex may be either a metal compound having an organic group or a metal compound having no organic group. Among them, the metal forming material is preferably a metal salt, more preferably a silver salt or a copper salt.
By using a metal forming material, a metal is generated from the material, and a conductive layer containing this metal is formed. In the conductive layer in this case, the ratio of the metal can be sufficiently high enough that the conductive layer can be regarded as apparently composed only of metal, and the ratio of the metal in the conductive layer is preferably 97% by mass or more. It is more preferably 98% by mass or more, and particularly preferably 99% by mass or more. The upper limit of the ratio of the metal in the conductive layer is, for example, 100% by mass, 99.9% by mass, 99.8% by mass, 99.7% by mass, 99.6% by mass, 99.5% by mass, 99. It can be any of 4% by mass, 99.3% by mass, 99.2% by mass and 99.1% by mass, but is not limited thereto.

The metal ink composition is preferably in a liquid state, and preferably in which the metal forming material is uniformly dispersed.

Hereinafter, a method for forming the conductive layer when a silver ink composition in which a material for forming metallic silver is blended is used as the metal ink composition will be described, but the same method will be used when the metal type is other than silver. Therefore, a conductive layer can be formed.
The material for forming metallic silver is decomposed by heating or the like to form metallic silver.

[Silver carboxylate]
Examples of the material for forming metallic silver include silver carboxylate having a group represented by the formula "-COOAg".
In the present invention, one type of silver carboxylate may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.
The silver carboxylate is not particularly limited as long as it has a group represented by the formula "-COOAg". For example, the number of groups represented by the formula "-COOAg" may be only one or two or more. Further, the position of the group represented by the formula "-COOAg" in silver carboxylate is not particularly limited.

The silver carboxylate is represented by silver β-ketocarboxylate represented by the following general formula (1) (hereinafter, may be abbreviated as “silver β-ketocarboxylate (1)”) and the following general formula (4). It is preferable that the amount is one or more selected from the group consisting of silver carboxylate (hereinafter, may be abbreviated as "silver carboxylate (4)").
In this specification, the description of "silver carboxylate" is not limited to "silver β-ketocarboxylate (1)" and "silver carboxylate (4)" unless otherwise specified. Inclusive, it shall mean "silver carboxylate having a group represented by the formula" -COOAg "".

（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１〜２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ^１−ＣＹ^１ _２−」、「ＣＹ^１ _３−」、「Ｒ^１−ＣＨＹ^１−」、「Ｒ^２Ｏ−」、「Ｒ^５Ｒ^４Ｎ−」、「（Ｒ^３Ｏ）_２ＣＹ^１−」若しくは「Ｒ^６−Ｃ（＝Ｏ）−ＣＹ^１ _２−」で表される基であり；
Ｙ^１はそれぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子であり；Ｒ^１は炭素数１〜１９の脂肪族炭化水素基又はフェニル基であり；Ｒ^２は炭素数１〜２０の脂肪族炭化水素基であり；Ｒ^３は炭素数１〜１６の脂肪族炭化水素基であり；Ｒ^４及びＲ^５はそれぞれ独立に炭素数１〜１８の脂肪族炭化水素基であり；Ｒ^６は炭素数１〜１９の脂肪族炭化水素基、水酸基又は式「ＡｇＯ−」で表される基であり；
Ｘ^１はそれぞれ独立に水素原子、炭素数１〜２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基、シアノ基、Ｎ−フタロイル−３−アミノプロピル基、２−エトキシビニル基、又は一般式「Ｒ^７Ｏ−」、「Ｒ^７Ｓ−」、「Ｒ^７−Ｃ（＝Ｏ）−」若しくは「Ｒ^７−Ｃ（＝Ｏ）−Ｏ−」で表される基であり；
Ｒ^７は、炭素数１〜１０の脂肪族炭化水素基、チエニル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基である。）

(In the formula, R is an aliphatic hydrocarbon group or phenyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a hydroxyl group, an amino group, or the general formula "R ^1- CY". ¹ ₂ − ”,“ CY ¹ ₃ − ”,“ R ¹ − CHY ¹ − ”,“ R ² O − ”,“ R ⁵ R ⁴ N − ”,“ (R ³ O) ₂ CY ¹ − ”or“ It is a group represented by "R ^6- C (= O) -CY ¹ _2-";
Y ¹ is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R ¹ is an aliphatic hydrocarbon group or a phenyl group having 1 to 19 carbon atoms; R ² is a fat having 1 to 20 carbon atoms. Group hydrocarbon groups; R ³ is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R ⁴ and R ⁵ are independently aliphatic hydrocarbon groups having 1 to 18 carbon atoms; R ⁶ is an aliphatic hydrocarbon group having 1 to 18 carbon atoms. An aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula "AgO-";
X ¹ is an independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and a phenyl group or a benzyl group, a cyano group, N in which one or more hydrogen atoms may be substituted with a substituent. -Phenyl-3-aminopropyl group, 2-ethoxyvinyl group, or general formula "R ⁷ O-", "R ⁷ S-", "R ^7- C (= O)-" or "R ^7- C ( = O) -O- "is a group represented by;
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or a diphenyl group in which one or more hydrogen atoms may be substituted with a substituent. )

（式中、Ｒ^８は炭素数１〜１９の脂肪族炭化水素基、カルボキシ基又は式「−Ｃ（＝Ｏ）−ＯＡｇ」で表される基であり、前記脂肪族炭化水素基がメチレン基を有する場合、１個以上の前記メチレン基はカルボニル基で置換されていてもよい。）

(In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group or a group represented by the formula "-C (= O) -OAg", and the aliphatic hydrocarbon group is a methylene group. If, one or more of the methylene groups may be substituted with a carbonyl group.)

(Silver β-ketocarboxylate (1))
The silver β-ketocarboxylate (1) is represented by the general formula (1).
In the formula, R is an aliphatic hydrocarbon group or phenyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a hydroxyl group, an amino group, or the general formula "R ^1- CY ^1". _2- "," CY ¹ _3- "," R ^1- CHY ^1- "," R ² O- "," R ⁵ R ⁴ N- "," (R ³ O) ₂ CY ^1- "or" R It is a group represented by ^6- C (= O) -CY ¹ _{2- ".}

The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may be linear, branched chain or cyclic (aliphatic cyclic group), and when cyclic, it may be monocyclic or polycyclic. .. Further, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Preferred aliphatic hydrocarbon groups in R include, for example, alkyl groups, alkenyl groups, alkynyl groups and the like.

Examples of the linear or branched alkyl group in R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-Pentyl group, Isopentyl group, Neopentyl group, tert-Pentyl group, 1-methylbutyl group, 2-Methylbutyl group, n-hexyl group, 1-Methylpentyl group, 2-Methylpentyl group, 3-Methylpentyl group, 4-Methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3- Ethylbutyl group, 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1, 1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group Group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propylbutyl group, n-octyl group, isooctyl group, 1-methylheptyl group, 2-Methylheptyl group, 3-Methylheptyl group, 4-Methylheptyl group, 5-Methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1 , 1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1-propylpentyl group, 2-propylpentyl group , Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group and the like.
Examples of the cyclic alkyl group in R include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group and a 1-adamantyl group. Examples thereof include a 2-adamantyl group and a tricyclodecyl group.

Examples of the alkenyl group in R include a vinyl group (ethenyl group, -CH = CH ₂ ), an allyl group (2-propenyl group, -CH ₂ -CH = CH ₂ ), and a 1-propenyl group (-CH = CH). -CH ₃ ), isopropenyl group (-C (CH ₃ ) = CH ₂ ), 1-butenyl group (-CH = CH-CH _{2 -CH 3} ), 2-butenyl group (-CH ₂ -CH = CH-) CH _3), 3- butenyl group _{(-CH 2 -CH 2 -CH = CH} 2), cyclohexenyl group, such as cyclopentenyl group, one single bond between carbon atoms of the alkyl group in R (C- Examples thereof include a group in which C) is replaced with a double bond (C = C).
Examples of the alkynyl group in R, for example, ethynyl (-C≡CH), such as propargyl _(-CH 2 -C≡CH), 1 single bond between carbon atoms of the alkyl group in R (C Examples thereof include a group in which −C) is replaced with a triple bond (C≡C).

The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may have one or more hydrogen atoms substituted with a substituent, and preferred examples of the substituent include a fluorine atom, a chlorine atom and a bromine atom. Can be mentioned. The number and position of the substituents are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other. That is, all the substituents may be the same, all the substituents may be different, or only some of the substituents may be different.

The phenyl group in R may have one or more hydrogen atoms substituted with a substituent, and the preferred substituent is, for example, a saturated or unsaturated monovalent aliphatic hydrocarbon having 1 to 16 carbon atoms. Hydrogen group, monovalent group formed by bonding the aliphatic hydrocarbon group to an oxygen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group (-OH), cyano group (-C≡N), phenoxy group (- OC ₆ H ₅ ) and the like can be mentioned, and the number and position of substituents are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.
Examples of the aliphatic hydrocarbon group as a substituent include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 16.

^{Y 1 in} R is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. Then, the general formula ^"R ₁ ^-CY 1 ₂ -", ^"CY _{1 3} -" and ^{"R 6 -C (= O) -CY} 1 2 - " In a plurality of ^{Y 1} are each, also identical to one another It may be different.

^{R 1} in R is an aliphatic hydrocarbon group or a phenyl group 1 to 19 carbon atoms _(C 6 _{H 5} -) a, The aliphatic hydrocarbon group for ^{R 1,} is a 1 to 19 carbon atoms Except for the point, the same as the above-mentioned aliphatic hydrocarbon group in R can be mentioned.
^{R 2} in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include the same group as the aliphatic hydrocarbon group in R.
^{R 3} in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and examples thereof include the same as the aliphatic hydrocarbon group in R except that the carbon number is 1 to 16.
^{R 4} and R ⁵ in R are aliphatic hydrocarbon groups having 1 to 18 carbon atoms independently. That is, R ⁴ and R ⁵ may be the same as or different from each other, and examples thereof include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1-18.
R ⁶ in R is an aliphatic hydrocarbon group of 1 to 19 carbon atoms, a group represented by a hydroxyl group or a formula "AgO-" The aliphatic hydrocarbon group for R ^6,. 1 to carbon atoms Except for the fact that it is 19, the same group as the aliphatic hydrocarbon group in R can be mentioned.

R is, among these, a linear or branched alkyl group, the general formula ^{"R 6 -C (= O) -CY} 1 2 - " group represented by be a hydroxyl group or a phenyl group preferable. R ⁶ is preferably a linear or branched alkyl group, a hydroxyl group, or a group represented by the formula “AgO−”.

In the general formula (1), X ¹ is an independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent. A benzyl group (C ₆ H _5- CH _2- ), a cyano group, an N-phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group (C ₂ H _5- O-CH = CH-), or the general formula "R". ^{It is a group represented by "7} O-", "R ⁷ S-", "R ^7- C (= O)-" or "R ^7- C (= O) -O-".
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in X ^{1 include the same group as the aliphatic hydrocarbon group in R.}

Examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Phenyl and benzyl groups in X ¹ may be one or more hydrogen atoms is substituted with a substituent, and preferred examples the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom ), Nitro group (-NO ₂ ) and the like, and the number and position of the substituent are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.

^{R 7} in X ¹ is an aliphatic having 1 to 10 carbon atoms hydrocarbon group, a thienyl group _{(C 4} H 3 S-), or one or more hydrogen atoms is a phenyl group or optionally substituted with a substituent diphenyl group (biphenyl _{group, C 6 H 5 -C 6 H} 4 -) is. Examples of the aliphatic hydrocarbon group in R ⁷ include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 10. Examples of the substituents of the phenyl group and the diphenyl group in R ⁷ include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), and the number and position of the substituents are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.
When R ⁷ is thienyl or diphenyl group, these adjacent group or atom in X ¹ (oxygen atom, a sulfur atom, a carbonyl group, carbonyloxy group) bonding position to is not particularly limited. For example, the thienyl group may be either a 2-thienyl group or a 3-thienyl group.

In the general formula (1), two X ^1s may be bonded to a carbon atom sandwiched between two carbonyl groups as one group via a double bond. For example, a group represented by the formula "= CH-C ₆ H _4- NO ₂ " can be mentioned.

X ^1, among the above, a hydrogen atom, a linear or branched alkyl group, a benzyl group, or formula "R ⁷ -C (= O) -" it is a group represented by preferably , It is preferable that at least one X ¹ is a hydrogen atom.

The silver β-ketocarboxylate (1) is silver 2-methylacetate acetate (CH _3- C (= O) -CH (CH ₃ ) -C (= O) -OAg), silver acetoacetate (CH _3- C (=)). O) -CH _2- C (= O) -OAg), 2-ethylacetate silver (CH _3- C (= O) -CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver propionyl acetate (CH ₃ CH _2- C (= O) -CH _2- C (= O) -OAg), silver isobutyryl acetate ((CH ₃ ) ₂ CH-C (= O) -CH _2- C (= O)- OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C-C (= O) -CH _2- C (= O) -OAg), silver caproyl acetate (CH ₃ (CH ₂ ) ₃ CH _2- C (= O) ) -CH _2- C (= O) -OAg), 2-n-silver acetate butylacetate (CH _3- C (= O) -CH (CH ₂ CH ₂ CH ₂ CH ₃ ) -C (= O) -OAg ), 2-benzylacetate silver acetate (CH _3- C (= O) -CH (CH ₂ C ₆ H ₅ ) -C (= O) -OAg), silver benzoyl acetate (C ₆ H _{5-C (= O))} ) -CH _2- C (= O) -OAg), silver pivaloyl acetoacetate ((CH ₃ ) ₃ C-C (= O) -CH _2- C (= O) -CH _2- C (= O) -OAg ), Silver Isobutyrylacetate Acetate ((CH ₃ ) ₂ CH-C (= O) -CH _2- C (= O) -CH _2- C (= O) -OAg), 2-Acetylpyvaloyl Acetate Silver ((CH ₃ ) ₃ C-C (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg), 2-acetylisobutyryl silver acetate ((CH ₃ )) ₂ CH-C (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg) or silver acetate dicarboxylate (AgO-C (= O) -CH _2- C ( = O) -CH _2- C (= O) -OAg) is preferable.

The silver β-ketocarboxylate (1) can further reduce the concentration of residual raw materials and impurities in the conductor (metal silver) formed by a solidification treatment such as a drying treatment or a heating (calcination) treatment. The smaller the amount of raw materials and impurities, for example, the better the contact between the formed metallic silver, the easier the conduction, and the lower the resistivity.

As will be described later, silver β-ketocarboxylate is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. without using a reducing agent or the like known in the art. It is possible to form metallic silver. Then, when used in combination with a reducing agent, it decomposes at a lower temperature to form metallic silver. The reducing agent will be described later.

In the present invention, one type of silver β-ketocarboxylate (1) may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.

(Silver carboxylate (4))
The silver carboxylate (4) is represented by the general formula (4).
In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group (-COOH) or a group represented by the formula "-C (= O) -OAg".
Examples of the aliphatic hydrocarbon group in R ⁸ include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 19. However, the aliphatic hydrocarbon group for ^{R 8} is preferably a carbon number of 1 to 15, and more preferably from 1 to 10.

When the aliphatic hydrocarbon group in R ⁸ _{has a methylene group (−CH 2-} ), one or more of the methylene groups may be substituted with a carbonyl group. The number and position of the methylene groups which may be substituted with a carbonyl group are not particularly limited, and all the methylene groups may be substituted with a carbonyl group. Here, the "methylene group", alone of formula _- not only a group represented by the formula "-CH 2" _- one alkylene in radicals group represented is continuous plurality in "-CH 2" It shall also include the group represented by the formula "-CH _{2-" of.}

The silver carboxylate (4) is silver pyruvate (CH _3- C (= O) -C (= O) -OAg), silver acetate (CH _3- C (= O) -OAg), silver butyrate (CH _3). -(CH ₂ ) _2- C (= O) -OAg), silver isobutyrate ((CH ₃ ) ₂ CH-C (= O) -OAg), silver 2-ethylhexanoate (CH _3- (CH ₂₎₎ ) _3- CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver neodecanoate (CH _3- (CH ₂ ) _5- C (CH ₃ ) _2- C (= O) -OAg), Shu It is preferably silver acid (AgO-C (= O) -C (= O) -OAg) or silver malonate (AgO-C (= O) -CH _2- C (= O) -OAg). Also, 2 of the silver oxalate (AgO-C (= O) -C (= O) -OAg) and malonic silver _{(AgO-C (= O)} -CH 2 -C (= O) -OAg) Of the groups represented by the formula "-COOAg", one of which is the group represented by the formula "-COOH" (HO-C (= O) -C (= O) -OAg, HO -C (= O) -CH _2- C (= O) -OAg) is also preferable.

Similar to silver β-ketocarboxylate (1), silver carboxylate (4) also contains residual raw materials and impurities in the conductor (metal silver) formed by solidification treatment such as drying treatment and heating (firing) treatment. The concentration can be further reduced. Then, when used in combination with a reducing agent, it decomposes at a lower temperature to form metallic silver.

In the present invention, one type of silver carboxylate (4) may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.

The silver carboxylate is silver 2-methylacetate acetate, silver acetoacetate, silver 2-ethylacetate acetate, silver propionyl acetate, silver isobutyryl acetate, silver pivaloyl acetate, silver caproyl acetate, silver 2-n-butylacetate acetate, 2-benzylacetate. Silver acetate, benzoyl silver acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate, silver acetone dicarboxylate, silver pyruvate, silver acetate, silver butyrate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, shu It is preferably one or more selected from the group consisting of silver acid acid and silver malonate.
Among these silver carboxylates, 2-methylacetoacetic acid silver and silver acetoacetic acid have excellent compatibility with nitrogen-containing compounds (among them, amine compounds) described later, and are particularly suitable for increasing the concentration of silver ink compositions. It can be mentioned as a compound.

In the silver ink composition, the content of silver derived from the metallic silver forming material is preferably 5% by mass or more, and more preferably 10% by mass or more. Within such a range, the formed conductor (metal silver) is superior in quality. The upper limit of the silver content is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 25% by mass in consideration of handleability and the like.
In the present specification, "silver derived from the metal silver forming material" is synonymous with silver in the metal silver forming material blended at the time of manufacturing the silver ink composition, unless otherwise specified. , Silver that still constitutes the metal silver forming material after compounding, silver in the decomposition product that was produced by the decomposition of the metal silver forming material after compounding, and silver that was produced by the decomposition of the metal silver forming material after compounding. It is a concept that includes all of itself (metal silver).

[Nitrogen-containing compound]
The silver ink composition is preferably one in which a nitrogen-containing compound is further blended in addition to the metal silver forming material, particularly when the metal silver forming material is the silver carboxylate.
The nitrogen-containing compound is an amine compound having 25 or less carbon atoms (hereinafter, may be abbreviated as "amine compound") and a quaternary ammonium salt having 25 or less carbon atoms (hereinafter, abbreviated as "quaternary ammonium salt"). ), Ammium, an ammonium salt formed by reacting an amine compound with 25 or less carbon atoms with an acid (hereinafter, may be abbreviated as "ammonium salt derived from an amine compound"), and ammonia reacting with an acid It is one or more selected from the group consisting of ammonium salts (hereinafter, may be abbreviated as "ammonium-derived ammonium salts"). That is, the nitrogen-containing compound to be blended may be only one kind, may be two or more kinds, and when two or more kinds are used in combination, the combination and the ratio thereof can be arbitrarily adjusted.

(Amine compound, quaternary ammonium salt)
The amine compound has 1 to 25 carbon atoms and may be any of a primary amine, a secondary amine and a tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either chain-like or cyclic. Further, the number of nitrogen atoms constituting the amine moiety or the ammonium salt moiety (for example, the nitrogen atom constituting the amino group (-NH ₂ ) of the primary amine) may be one or two or more.

Examples of the primary amine include monoalkylamines, monoarylamines, mono (heteroaryl) amines, diamines, etc., in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group constituting the monoalkylamine may be linear, branched or cyclic, and examples thereof include those similar to the alkyl group in R, which are linear or branched having 1 to 19 carbon atoms. It is preferably a chain alkyl group or a cyclic alkyl group having 3 to 7 carbon atoms.
Specific preferred monoalkylamines include, for example, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, isobutylamine, sec-butylamine, tert-butylamine, 3 -Aminopentane, 3-methylbutylamine, 2-heptylamine (2-aminoheptane), 2-aminooctane, 2-ethylhexylamine, 1,2-dimethyl-n-propylamine and the like can be mentioned.

Examples of the aryl group constituting the monoarylamine include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, and the number of carbon atoms is preferably 6 to 10.

The heteroaryl group constituting the mono (heteroaryl) amine has a hetero atom as an atom constituting the aromatic ring skeleton, and the hetero atom includes, for example, a nitrogen atom, a sulfur atom, an oxygen atom, and the like. Examples include a boron atom. Further, the number of the hetero atoms constituting the aromatic ring skeleton is not particularly limited, and may be one or two or more. When there are two or more, these heteroatoms may be the same or different from each other. That is, these heteroatoms may all be the same, all may be different, or only some may be different.
The heteroaryl group may be monocyclic or polycyclic, and the number of ring members (the number of atoms constituting the ring skeleton) is not particularly limited, but is preferably a 3 to 12 member ring.

Examples of the heteroaryl group having 1 to 4 nitrogen atoms as a monocyclic group include a pyrrolyl group, a pyrrolinyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a pyridadinyl group and a triazolyl group. Examples thereof include a tetrazolyl group, a pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a pyrazoridinyl group and a piperazinyl group, and a 3- to 8-membered ring is preferable, and a 5- to 6-membered ring is more preferable.
Examples of the heteroaryl group having a monocyclic structure having one oxygen atom include a furanyl group and the like, preferably having a 3- to 8-membered ring, and more preferably a 5- to 6-membered ring. ..
Examples of the heteroaryl group having a monocyclic structure having one sulfur atom include a thienyl group and the like, preferably having a 3- to 8-membered ring, and more preferably a 5- to 6-membered ring. ..
Examples of the heteroaryl group having a monocyclic structure having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms include an oxazolyl group, an isooxazolyl group, an oxadiazolyl group, a morpholinyl group and the like, and 3 to 8 thereof. It is preferably a membered ring, more preferably a 5-6 membered ring.
Examples of the heteroaryl group having a monocyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms include a thiazolyl group, a thiadiazolyl group, a thiazolidinyl group and the like, and have a 3 to 8 membered ring. It is preferably present, and more preferably a 5- to 6-membered ring.
Examples of the heteroaryl group having 1 to 5 nitrogen atoms as a polycyclic group include an indolyl group, an isoindryl group, an indridinyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, an indazolyl group, and a benzotriazolyl group. , Tetrazolopyridyl group, tetrazolopyridazinyl group, dihydrotriazolopyridazinyl group and the like, preferably a 7 to 12-membered ring, and more preferably a 9 to 10-membered ring.
Examples of the heteroaryl group having 1 to 3 sulfur atoms as a polycyclic group include a dithianaphthalenyl group and a benzothiophenyl group, and a 7 to 12-membered ring is preferable, and 9 It is more preferably a 10-membered ring.
Examples of the heteroaryl group having a polycyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms include a benzoxazolyl group, a benzoxaziazolyl group and the like, and 7 to 12 thereof. It is preferably a membered ring, more preferably 9 to 10 membered rings.
Examples of the heteroaryl group having a polycyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms include a benzothiazolyl group and a benzothiazolyl group, and have a 7 to 12-membered ring. It is preferably present, and more preferably 9 to 10-membered rings.

The diamine may have two amino groups, and the positional relationship between the two amino groups is not particularly limited. As the preferred diamine, for example, in the monoalkylamine, monoarylamine or mono (heteroaryl) amine, one hydrogen atom other than the hydrogen atom constituting the _{amino group (-NH 2) is replaced with an amino group.} Examples include those that have been used.
The diamine preferably has 1 to 10 carbon atoms, and more preferable diamines include, for example, ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane.

Examples of the secondary amine include dialkylamine, diarylamine, and di (heteroaryl) amine in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group constituting the dialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms or having 3 to 7 carbon atoms. It is preferably a cyclic alkyl group. Further, the two alkyl groups in one molecule of dialkylamine may be the same or different from each other.
Specific examples of the preferred dialkylamine include N-methyl-n-hexylamine, diisobutylamine, and di (2-ethylhexyl) amine.

The aryl group constituting the diarylamine is the same as the aryl group constituting the monoarylamine, and preferably has 6 to 10 carbon atoms. Further, the two aryl groups in one molecule of diallylamine may be the same as or different from each other.

The heteroaryl group constituting the di (heteroaryl) amine is the same as the heteroaryl group constituting the mono (heteroaryl) amine, and is preferably a 6 to 12-membered ring. Also, the two heteroaryl groups in a single molecule of di (heteroaryl) amine may be the same or different from each other.

Examples of the tertiary amine include trialkylamines and dialkylmonoarylamines in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group constituting the trialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 19 carbon atoms or a carbon number of 3 to 7 carbon atoms. It is preferably a cyclic alkyl group of. Further, the three alkyl groups in one molecule of trialkylamine may be the same or different from each other. That is, the three alkyl groups may be all the same, all may be different, or only some may be different.
Specific examples of the preferred trialkylamine include N, N-dimethyl-n-octadecylamine, N, N-dimethylcyclohexylamine and the like.

The alkyl group constituting the dialkyl monoarylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 6 carbon atoms or 3 to 6 carbon atoms. It is preferably a cyclic alkyl group of 7. Further, the two alkyl groups in one molecule of dialkyl monoarylamine may be the same or different from each other.
The aryl group constituting the dialkyl monoarylamine is the same as the aryl group constituting the monoarylamine, and preferably has 6 to 10 carbon atoms.

In the present invention, examples of the quaternary ammonium salt include tetraalkylammonium halide in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group constituting the halogenated tetraalkylammonium is the same as the alkyl group constituting the monoalkylamine, and preferably has 1 to 19 carbon atoms. Further, the four alkyl groups in one molecule of tetraalkylammonium halide may be the same or different from each other. That is, the four alkyl groups may be all the same, all may be different, or only some may be different.
Examples of the halogen constituting the halogenated tetraalkylammonium include fluorine, chlorine, bromine, iodine and the like.
Specific examples of the preferred tetraalkylammonium halide include dodecyltrimethylammonium bromide.

Up to this point, the chain amine compound and the quaternary organic ammonium salt have been mainly described, but the amine compound and the quaternary ammonium salt have a ring-skeleton structure in which the nitrogen atom constituting the amine moiety or the quaternary ammonium salt moiety is formed. It may be a heterocyclic compound which is a part of the heterocyclic skeleton structure). That is, the amine compound may be a cyclic amine, and the quaternary ammonium salt may be a cyclic ammonium salt. The ring (ring containing nitrogen atoms constituting the amine moiety or ammonium salt moiety) structure at this time may be either monocyclic or polycyclic, and the number of ring members (the number of atoms constituting the ring skeleton) is particularly limited. However, it may be either an aliphatic ring or an aromatic ring.
If it is a cyclic amine, preferred examples thereof include pyridine and the like.

In the primary amine, secondary amine, tertiary amine and quaternary ammonium salt, the "hydrogen atom which may be substituted with a substituent" is a nitrogen atom constituting an amine moiety or an ammonium salt moiety. It is a hydrogen atom other than the hydrogen atom bonded to. The number of substituents at this time is not particularly limited, and may be one, two or more, and all of the hydrogen atoms may be substituted with substituents. When the number of substituents is plural, these plurality of substituents may be the same or different from each other. That is, the plurality of substituents may all be the same, all may be different, or only some of them may be different. Further, the position of the substituent is not particularly limited.

Examples of the substituent in the amine compound and the quaternary ammonium salt include an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, and a trifluoromethyl group (-CF ₃ ). Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

When the alkyl group constituting the monoalkylamine has a substituent, the alkyl group is a linear or branched alkyl group having 1 to 9 carbon atoms or a substituent having an aryl group as the substituent. A cyclic alkyl group having 3 to 7 carbon atoms having an alkyl group having 1 to 5 carbon atoms is preferable, and as a monoalkylamine having such a substituent, specifically, for example, 2-. Examples thereof include phenylethylamine, benzylamine and 2,3-dimethylcyclohexylamine.
Further, the aryl group and the alkyl group, which are substituents, may further have one or more hydrogen atoms substituted with halogen atoms, and the monoalkylamine having a substituent substituted with such a halogen atom may be used. For example, 2-bromobenzylamine and the like can be mentioned. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

When the aryl group constituting the monoarylamine has a substituent, the aryl group is preferably an aryl group having a halogen atom as a substituent and having 6 to 10 carbon atoms, and a monoaryl having such a substituent. Specific examples of the amine include bromophenylamine and the like. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

When the alkyl group constituting the dialkylamine has a substituent, the alkyl group is preferably a linear or branched alkyl group having 1 to 9 carbon atoms and having a hydroxyl group or an aryl group as the substituent. Specific examples of the dialkylamine having such a substituent include diethanolamine and N-methylbenzylamine.

The amine compounds include n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, isobutylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-Methylbutylamine, 2-heptylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, Diisobutylamine, N-methylbenzylamine, di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine. Is preferable.
Among these amine compounds, 2-ethylhexylamine has excellent compatibility with the silver carboxylate, is particularly suitable for increasing the concentration of the silver ink composition, and further reduces the surface roughness of the conductive layer 13. It is mentioned as particularly suitable.

(Ammonium salt derived from amine compound)
In the present invention, the ammonium salt derived from the amine compound is an ammonium salt formed by reacting the amine compound with an acid, and the acid may be an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid. However, the type of acid is not particularly limited.
Examples of the ammonium salt derived from the amine compound include n-propylamine hydrochloride, N-methyl-n-hexylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride and the like. Not limited.

(Ammonia-derived ammonium salt)
In the present invention, the ammonium salt derived from ammonia is an ammonium salt formed by reacting ammonia with an acid, and examples of the acid include the same as in the case of the ammonium salt derived from the amine compound.
Examples of the ammonia-derived ammonium salt include, but are not limited to, ammonium chloride.

In the present invention, the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound, and the ammonium salt derived from ammonia may be used alone or in combination of two or more. Good. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.
Then, as the nitrogen-containing compound, one selected from the group consisting of the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from ammonia may be used alone. Two or more types may be used in combination. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.

In the present invention, for example, as the nitrogen-containing compound, a first nitrogen-containing compound having 8 or more carbon atoms and a second nitrogen-containing compound having 7 or less carbon atoms may be used in combination.
When the first nitrogen-containing compound and the second nitrogen-containing compound are used in combination, the ratio of the blending amount of the second nitrogen-containing compound to the blending amount of the first nitrogen-containing compound in the silver ink composition is larger than 0 mol%. It is preferably less than 18 mol%, more preferably 1 to 17 mol%. When the ratio is in such a range, for example, a fine linear silver layer can be formed more stably.

In the silver ink composition, the blending amount of the nitrogen-containing compound is preferably 0.3 to 15 mol, more preferably 0.3 to 5 mol, per 1 mol of the blended amount of the metallic silver-forming material. preferable. When the blending amount of the nitrogen-containing compound is in such a range, the stability of the silver ink composition is further improved, and the quality of the conductor (metal silver) is further improved. Further, the conductor can be formed more stably without heat treatment at a high temperature.

[Reducing agent]
The silver ink composition is preferably one in which a reducing agent is further blended in addition to the metal silver forming material. By blending the reducing agent, the silver ink composition can more easily form metallic silver, and for example, a conductor (metallic silver) having sufficient conductivity can be formed even by heat treatment at a low temperature.

The reducing agent is one or more reducing agents selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5) (hereinafter, may be abbreviated as "compound (5)"). It is preferably a compound (hereinafter, may be simply abbreviated as "reducing compound").
HC (= O) -R ²¹ ... (5)
(In the formula, R ²¹ is an alkyl group having 20 or less carbon atoms, an alkoxy group or an N, N-dialkylamino group, a hydroxyl group or an amino group.)

(Reducing compound)
The reducing compound, oxalic acid (HOOC-COOH), hydrazine _{(H 2} N-NH 2) and the compound represented by the general formula (5) (Compound (5)) one selected from the group consisting of That is all. That is, the reducing compound to be blended may be only one kind, may be two or more kinds, and when two or more kinds are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

The alkyl group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms and may be linear, branched or cyclic, and is the same as the alkyl group in R in the general formula (1). Things can be mentioned.

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and examples thereof include a monovalent group in which the alkyl group in ^{R 21 is bonded to an oxygen atom.}

The N, N-dialkylamino group having 20 or less carbon atoms in R ²¹ has 2 to 20 carbon atoms, and the two alkyl groups bonded to the nitrogen atom may be the same or different from each other. Each alkyl group has 1 to 19 carbon atoms. However, the total number of carbon atoms of these two alkyl groups is 2 to 20.
The alkyl group bonded to the nitrogen atom may be linear, branched or cyclic, respectively, and the alkyl in R of the general formula (1) except that the number of carbon atoms is 1 to 19. The same as the group can be mentioned.

As the reducing compound, hydrazine may be monohydrate (H ₂ N-NH ₂ · H ₂ O).

Preferred reducing compounds include, for example, formic acid (HC (= O) -OH); methyl formate (HC (= O) -OCH ₃ ), ethyl formate (HC (= O)). -OCH ₂ CH ₃ ), butyl formate (HC (= O) -O (CH ₂ ) ₃ CH ₃ ) and other formic acid esters; compound (HC (= O) -CH ₂ CH ₃ ), butanal Aldehydes such as (HC (= O)-(CH ₂ ) ₂ CH ₃ ), hexanal (HC (= O)-(CH ₂ ) ₄ CH ₃ ); formamide (HC (= O)- Formamides such as NH ₂ ), N, N-dimethylformamide (HC (= O) -N (CH ₃ ) ₂ ) (represented by the formula "HC (= O) -N (-)-" Compounds having a group); formic acid and the like.

In the silver ink composition, the blending amount of the reducing agent is preferably 0.04 to 3.5 mol, preferably 0.06 to 2.5 mol, per 1 mol of the blended amount of the metallic silver forming material. Is more preferable. When the blending amount of the reducing agent is in such a range, the silver ink composition can more easily and more stably form a conductor (metal silver).

[alcohol]
The silver ink composition may be further blended with alcohol in addition to the metal silver forming material.

The alcohol is preferably acetylene alcohols represented by the following general formula (2) (hereinafter, may be abbreviated as "acetylene alcohol (2)").

（式中、Ｒ’及びＲ’’は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基である。）

(In the formula, R'and R'' are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or phenyl groups in which one or more hydrogen atoms may be substituted with substituents, respectively.)

(Acetylene alcohol (2))
The acetylene alcohol (2) is represented by the general formula (2).
In the formula, R'and R'' are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or phenyl groups in which one or more hydrogen atoms may be substituted with substituents, respectively.
The alkyl group having 1 to 20 carbon atoms in R'and R'' may be linear, branched chain or cyclic, and when cyclic, it may be monocyclic or polycyclic. Examples of the alkyl group in R'and R'' include the same as the alkyl group in R.

Examples of the substituent in which the hydrogen atom of the phenyl group in R'and R'' may be substituted include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the fat. Examples include a monovalent group in which a group hydrocarbon group is bonded to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, etc., and the hydrogen atom of the phenyl group in R is substituted. It is the same as the above-mentioned substituent. The number and position of the substituents are not particularly limited, and when the number of substituents is plural, these plurality of substituents may be the same or different from each other.

R'and R'' are preferably hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and preferably hydrogen atoms or linear or branched alkyl groups having 1 to 10 carbon atoms. More preferred.

Preferred acetylene alcohols (2) include, for example, 3,5-dimethyl-1-hexin-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 2 -Propyne-1-ol, 4-ethyl-1-octyne-3-ol, 3-ethyl-1-heptin-3-ol and the like can be mentioned.

When acetylene alcohol (2) is used, the blending amount of acetylene alcohol (2) in the silver ink composition is preferably 0.01 to 0.7 mol per 1 mole of the metallic silver forming material. , 0.02 to 0.3 mol, more preferably. When the blending amount of the acetylene alcohol (2) is in such a range, the stability of the silver ink composition is further improved.

The alcohol may be used alone or in combination of two or more. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.

[Other ingredients]
The silver ink composition may be a mixture of other components other than the metallic silver forming material, nitrogen-containing compound, reducing agent and alcohol.
The other components in the silver ink composition can be arbitrarily selected depending on the intended purpose, and are not particularly limited, and preferred ones include, for example, a solvent other than alcohol, depending on the type and amount of the compounding components. It can be selected arbitrarily.
As the other components in the silver ink composition, one kind may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.

(solvent)
The solvent is not particularly limited as long as it is other than alcohol (those having no hydroxyl group).
However, the solvent is preferably liquid at room temperature.

Examples of the solvent include aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; pentane, hexane, cyclohexane, heptane, octane, cyclooctane, nonane, decane, undecane, dodecane, tridecane, and the like. Aliphatic hydrocarbons such as tetradecane, pentadecane and decahydronaphthalene; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, monomethyl glutarate, dimethylformamide; diethyl ether, tetrahydrofuran (THF), 1,2- Ethers such as dimethoxyethane (dimethylcellosolve); ketones such as acetone, methylethylketone (MEK), cyclohexanone; nitriles such as acetonitrile; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide and the like. ..

The blending amount of the other component in the silver ink composition may be appropriately selected according to the type of the other component.
For example, when the other component is a solvent other than alcohol, the blending amount of the solvent may be selected according to the purpose such as the viscosity of the silver ink composition. However, usually, in the silver ink composition, the ratio of the blending amount of the solvent to the total blending component is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. It is particularly preferable to have.
When the other component is a component other than the solvent, the ratio of the compounding amount of the other component to the total amount of the compounding component in the silver ink composition is preferably 10% by mass or less, preferably 5% by mass. More preferably, it is less than%.
The ratio of the blending amount of the other components to the total amount of the blending components is 0 mass, that is, even if the other components are not blended, the silver ink composition sufficiently exhibits its effect.

In the silver ink composition, all the compounding components may be dissolved, or some or all the components may be dispersed without being dissolved, but it is preferable that all the compounding components are dissolved. It is preferable that the undissolved components are uniformly dispersed.

[Manufacturing method of silver ink composition]
The silver ink composition is obtained by blending a component other than the metallic silver forming material and the metallic silver forming material. After blending each component, the obtained product may be used as it is as a silver ink composition, or if necessary, a product obtained by continuously performing a known purification operation may be used as a silver ink composition. In the present invention, particularly when silver β-ketocarboxylate (1) is used as the material for forming the metallic silver, impurities that inhibit conductivity are not generated when each of the above components is blended, or such Since the amount of impurities produced can be suppressed to an extremely small amount, a conductor (metal silver) having sufficient conductivity can be obtained even if a silver ink composition that has not been refined is used.

When blending each component, all the components may be added and then mixed, some components may be added sequentially and mixed, or all components may be added sequentially and mixed. Good. However, in the present invention, the reducing agent is preferably blended by dropping, and the surface roughness of metallic silver tends to be further reduced by suppressing fluctuations in the dropping rate.
The mixing method is not particularly limited, and a method of rotating and mixing a stirrer or a stirring blade or the like; a method of mixing using a mixer, a three-roll roll, a kneader or a bead mill or the like; a method of adding ultrasonic waves and the like, etc. It may be appropriately selected from known methods.
In the case of uniformly dispersing the undissolved components in the silver ink composition, for example, it is preferable to apply the method of dispersing using the above-mentioned three rolls, kneader, bead mill or the like.

The temperature at the time of compounding is not particularly limited as long as each compounding component is not deteriorated, but is preferably −5 to 60 ° C. Then, the temperature at the time of blending may be appropriately adjusted according to the type and amount of the blending component so that the mixture obtained by blending has a viscosity that makes it easy to stir.
The blending time is also not particularly limited as long as each blending component is not deteriorated, but is preferably 10 minutes to 36 hours.

Preferred silver ink compositions include, for example, those obtained by adding a material for forming metallic silver to a nitrogen-containing compound, then adding a reducing agent, and then adding alcohol. When each of the above components is added in such an order of addition, it is preferable to add the metallic silver forming material after adding the solvent to the nitrogen-containing compound.
By using the silver ink composition obtained in such an order of addition, a fine linear silver layer can be formed more stably.

[carbon dioxide]
The silver ink composition may be further supplied with carbon dioxide. Such a silver ink composition has a high viscosity, and for example, a printing method that requires thickening of ink, such as a flexo printing method, a screen printing method, a gravure printing method, a gravure offset printing method, and a pad printing method. Suitable for application.

Carbon dioxide may be supplied at any time during the production of the silver ink composition.
Then, in the present invention, for example, carbon dioxide is supplied to the first mixture formed by blending the metallic silver forming material and the nitrogen-containing compound to obtain a second mixture, and if necessary, the second mixture is subjected to. Further, it is preferable to blend the reducing agent to produce a silver ink composition. When the alcohol or other components are blended, they can be blended at the time of production of either one or both of the first mixture and the second mixture, and can be arbitrarily selected depending on the purpose.

The first mixture can be produced by the same method as the above-mentioned silver ink composition except that the compounding components are different.

In the first mixture, all the ingredients may be dissolved, or some of the ingredients may be dispersed without being dissolved, but it is preferable that all the ingredients are dissolved, and the first mixture is dissolved. It is preferable that the components that are not used are uniformly dispersed.

The compounding temperature at the time of producing the first mixture is not particularly limited as long as each compounding component is not deteriorated, but is preferably −5 to 30 ° C. The blending time may be appropriately adjusted according to the type of blending component and the temperature at the time of blending, but is preferably 0.5 to 12 hours, for example.

_{The carbon dioxide (CO 2} ) supplied to the first mixture may be either gaseous or solid (dry ice), or both gaseous and solid. It is presumed that when carbon dioxide is supplied, this carbon dioxide dissolves in the first mixture and acts on the components in the first mixture, thereby increasing the viscosity of the obtained second mixture.

The carbon dioxide gas may be supplied by various known methods of blowing the gas into the liquid, and a suitable supply method may be appropriately selected. For example, a method in which one end of the pipe is immersed in the first mixture, the other end is connected to a carbon dioxide gas supply source, and carbon dioxide gas is supplied to the first mixture through the pipe. At this time, carbon dioxide gas may be supplied directly from the end of the pipe, but for example, a large number of voids that can serve as gas flow paths such as porous ones are provided to diffuse the introduced gas. A gas diffusion member capable of being released as minute bubbles may be connected to the end of the pipe, and carbon dioxide gas may be supplied through the gas diffusion member. Further, carbon dioxide gas may be supplied while stirring the first mixture in the same manner as in the production of the first mixture. By doing so, carbon dioxide can be efficiently supplied.

The amount of carbon dioxide gas supplied may be appropriately adjusted according to the amount of the first mixture to be supplied and the viscosity of the target silver ink composition or the second mixture, and is not particularly limited. For example, in order to obtain about 100 to 1000 g of a silver ink composition having a viscosity at 20 to 25 ° C. of 5 Pa · s or more, it is preferable to supply 100 L or more of carbon dioxide gas, and more preferably 200 L or more. Although the viscosity of the silver ink composition at 20 to 25 ° C. has been described here, the temperature at which the silver ink composition is used is not limited to 20 to 25 ° C. and can be arbitrarily selected. Further, here, "viscosity" means what was measured using an ultrasonic vibration viscometer.

The flow rate of carbon dioxide gas may be appropriately adjusted in consideration of the required supply amount of carbon dioxide gas, but is preferably 0.5 mL / min or more per 1 g of the first mixture, and is preferably 1 mL / min or more. More preferably. The upper limit of the flow rate is not particularly limited, but it is preferably 40 mL / min per 1 g of the mixture in consideration of handleability and the like.
Then, the carbon dioxide gas supply time may be appropriately adjusted in consideration of the required carbon dioxide gas supply amount and the flow rate.

The temperature of the first mixture when supplying carbon dioxide gas is preferably 5 to 70 ° C, more preferably 7 to 60 ° C, and particularly preferably 10 to 50 ° C. When the temperature is at least the lower limit value, carbon dioxide can be supplied more efficiently, and when the temperature is at least the upper limit value, a better quality silver ink composition with less impurities can be obtained.

The flow rate and supply time of the carbon dioxide gas, and the temperature at the time of supplying the carbon dioxide gas may be adjusted within an appropriate range while mutually considering their respective values. For example, even if the temperature is set low, carbon dioxide gas flow rate is set high, carbon dioxide gas supply time is set long, or both are performed efficiently. Can supply carbon. Further, even if the flow rate of carbon dioxide gas is set to be small, carbon dioxide can be efficiently produced by raising the temperature, setting the supply time of carbon dioxide gas to be long, or both. Can be supplied. That is, by flexibly combining the values in the above numerical range exemplified as the flow rate of carbon dioxide gas and the temperature at the time of supplying carbon dioxide gas while considering the supply time of carbon dioxide gas, silver ink of good quality is obtained. The composition is efficiently obtained.

The carbon dioxide gas is preferably supplied while stirring the first mixture. By doing so, the supplied carbon dioxide gas can be more uniformly diffused into the first mixture, and carbon dioxide can be supplied more efficiently.
The stirring method at this time may be the same as the case of the mixing method at the time of producing the silver ink composition without using carbon dioxide.

The supply of dry ice (solid carbon dioxide) may be carried out by adding dry ice to the first mixture. The whole amount of dry ice may be added all at once, or may be divided and added stepwise (continuously with a time zone during which the addition is not performed).
The amount of dry ice used may be adjusted in consideration of the above-mentioned supply amount of carbon dioxide gas.
During and after the addition of dry ice, it is preferable to stir the first mixture, for example, it is preferable to stir in the same manner as in the production of the above silver ink composition without using carbon dioxide. By doing so, carbon dioxide can be efficiently supplied.
The temperature at the time of stirring may be the same as that at the time of supplying carbon dioxide gas. Further, the stirring time may be appropriately adjusted according to the stirring temperature.

The viscosity of the second mixture may be appropriately adjusted according to the purpose such as the silver ink composition or the handling method of the second mixture, and is not particularly limited. For example, when the silver ink composition is applied to a printing method using a high viscosity ink such as a screen printing method or a flexographic printing method, the viscosity of the second mixture at 20 to 25 ° C. is 3 Pa · s or more. Is preferable. Although the viscosity of the second mixture at 20 to 25 ° C. has been described here, the temperature at the time of using the second mixture is not limited to 20 to 25 ° C. and can be arbitrarily selected.

The second mixture can be further blended with one or more selected from the group consisting of the reducing agent, alcohol and other components, if necessary, to obtain a silver ink composition.
The silver ink composition at this time can be produced by the same method as the above-mentioned silver ink composition that does not use carbon dioxide, except that the compounding components are different. Then, in the obtained silver ink composition, all the compounding components may be dissolved, or some components may be dispersed without being dissolved, but all the compounding components are dissolved. It is preferable that the undissolved components are uniformly dispersed.

The temperature at the time of blending the reducing agent is not particularly limited as long as each blending component is not deteriorated, but is preferably −5 to 60 ° C. Then, the temperature at the time of blending may be appropriately adjusted according to the type and amount of the blending component so that the mixture obtained by blending has a viscosity that makes it easy to stir.
The blending time may be appropriately adjusted according to the type of blending component and the temperature at the time of blending, but is preferably 0.5 to 12 hours, for example.

As described above, the other components may be blended during the production of either the first mixture or the second mixture, or may be blended during the production of both. That is, in the process of producing the silver ink composition through the first mixture and the second mixture, the ratio of the amount of the other components to the total amount of the components other than carbon dioxide ([other components (mass)] / [ Metallic silver forming material, nitrogen-containing compound, reducing agent, alcohol, and other components (mass)] × 100) is preferably 10% by mass or less, more preferably 5% by mass or less, and 0 The silver ink composition fully exhibits its effect without blending by mass, that is, other components.

The silver ink composition to which carbon dioxide is supplied has a viscosity at 20 to 25 ° C., for example, when the silver ink composition is applied to a printing method using a high viscosity ink such as a screen printing method or a flexographic printing method. Is preferably 1 Pa · s or more.

For example, when the reducing agent is blended, the obtained blend (silver ink composition) tends to generate heat relatively easily. When the temperature at the time of blending the reducing agent is high, this blend is in the same state as during the heat treatment of the silver ink composition described later, and therefore, the reducing agent acts to promote the decomposition of the metallic silver forming material. It is presumed that the formation of metallic silver may be initiated in at least a part of the metallic silver forming material. Such a silver ink composition containing metallic silver may be able to form a conductor by performing post-treatment under milder conditions than the silver ink composition containing no metallic silver at the time of forming the conductor. Further, even when the blending amount of the reducing agent is sufficiently large, the conductor may be formed by performing the post-treatment under the same mild conditions. In this way, by adopting the conditions that promote the decomposition of the metallic silver forming material, the conductor can be post-treated by heat treatment at a lower temperature or by drying at room temperature without heat treatment. May be able to form. Further, such a silver ink composition containing metallic silver can be handled in the same manner as a silver ink composition containing no metallic silver, and the handleability is not particularly inferior.

The viscosity of the second mixture in the present invention is higher than usual due to the supply of carbon dioxide as described above. On the other hand, when the reducing agent is blended into the second mixture, depending on the type of the second mixture or the reducing agent, the formation of metallic silver is started in at least a part of the metallic silver forming material as described above, and the metallic silver is formed. May precipitate. Here, when the viscosity of the second mixture is high, the aggregation of the precipitated metallic silver is suppressed, and the dispersibility of the metallic silver in the obtained silver ink composition is improved. A conductor obtained by forming metallic silver by a method described later using such a silver ink composition is obtained by blending a reducing agent with a mixture having a low viscosity, that is, a mixture to which carbon dioxide is not supplied. It has higher conductivity (lower volume resistivity) and smaller surface roughness than the conductor when the silver ink composition is used, and has more preferable characteristics.

Further, in the present invention, it is also preferable to supply carbon dioxide to the mixture in which the metallic silver forming material, alcohol and nitrogen-containing compound are blended to produce a silver ink composition. In this case, the same method as described above can be adopted as the carbon dioxide supply method.

The silver ink composition can be adhered to the substrate by a known method such as a printing method, a coating method, or a dipping method.
Examples of the printing method include a screen printing method, a flexo printing method, an offset printing method, a dip printing method, an inkjet printing method, a dispenser printing method, a jet dispenser printing method, a gravure printing method, and a gravure offset printing method. Pad printing method and the like can be mentioned.
As the coating method, for example, various coaters such as a spin coater, an air knife coater, a curtain coater, a die coater, a blade coater, a roll coater, a gate roll coater, a bar coater, a rod coater, and a gravure coater, a wire bar, and the like are used. The method and the like can be mentioned.

In the conductive layer forming step, the thickness of the conductive layer can be adjusted by adjusting the amount of the silver ink composition adhered to the base material or the blending amount of the metallic silver forming material in the silver ink composition.

When the silver ink composition is dried, it may be carried out by a known method. For example, it may be carried out under normal pressure, reduced pressure or blowing conditions, and under any of atmospheric conditions and an inert gas atmosphere. You may do it. The drying temperature is not particularly limited, and either heat drying or room temperature drying may be used. A preferred drying method when heat treatment is not required includes, for example, a method of drying in the atmosphere at 18 to 30 ° C.

When the silver ink composition is heated (baked), the conditions may be appropriately adjusted according to the type of the compounding components of the silver ink composition. Usually, the heating temperature is preferably 60 to 370 ° C, more preferably 70 to 280 ° C. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 24 hours, more preferably 1 minute to 12 hours. Among the materials for forming metallic silver, the silver carboxylate, particularly silver β-ketocarboxylate (1), is different from the material for forming metallic silver such as silver oxide, and uses a reducing agent known in the art. Even without it, it decomposes at low temperatures. Then, reflecting such a decomposition temperature, the silver ink composition can form metallic silver at an extremely lower temperature than the conventional one, as described above.

As will be described later, when the silver ink composition is attached to a substrate having low heat resistance and heated (baked), the heating temperature is preferably less than 130 ° C, more preferably 125 ° C or lower. It is preferably 120 ° C. or lower, and particularly preferably 120 ° C. or lower.

The method of heat treatment of the silver ink composition is not particularly limited, and for example, heating by an electric furnace, heating by a heat-sensitive heat head, heating by far-infrared irradiation, heating by spraying high heat gas, or the like can be performed. Further, the heat treatment of the silver ink composition may be carried out in an atmosphere, an inert gas atmosphere, or a humidified condition. Then, it may be performed under normal pressure, reduced pressure, or pressurized.

In the present specification, "humidification" means artificially increasing the humidity unless otherwise specified, and preferably the relative humidity is 5% or more. It can be said that the relative humidity of 5% is clearly artificially increased because the humidity in the treatment environment becomes extremely low due to the high treatment temperature during the heat treatment.

When the heat treatment of the silver ink composition is performed under humidified conditions, the relative humidity is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, and 70%. The above is particularly preferable, and it may be 90% or more or 100%. Then, the heat treatment under the humidifying condition may be performed by spraying high-pressure steam heated to 100 ° C. or higher. By heat-treating under humidifying conditions in this way, higher-purity metallic silver can be formed in a short time.

The heat treatment of the silver ink composition may be performed in two steps. For example, in the first-step heat treatment, the silver ink composition is mainly dried instead of forming metallic silver, and in the second-step heat treatment, metallic silver is formed to the end.
In the first-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding component of the silver ink composition, but is preferably 60 to 120 ° C, and may be 70 to 110 ° C. .. The heating time may be adjusted according to the heating temperature, but is usually preferably 5 seconds to 12 hours, more preferably 30 seconds to 2 hours.
In the second step of heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding components of the silver ink composition so that metallic silver is formed well, but it may be 60 to 280 ° C. It is preferably 70 to 260 ° C., more preferably 70 to 260 ° C. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 12 hours, more preferably 1 minute to 10 hours.
As will be described later, when the silver ink composition is attached to a substrate having low heat resistance and heated (baked), the heating temperature in the first and second stages of heat treatment is less than 130 ° C. It is preferably 125 ° C. or lower, more preferably 120 ° C. or lower.

The heat treatment of the silver ink composition described so far is performed in the gas phase, but when the heat treatment of the silver ink composition is performed in two steps, the heat treatment of the second step is the gas phase. It may be done in the liquid phase instead of inside. The silver ink composition that has been completely or to some extent dried after the first-step heat treatment can be brought into contact with the heated liquid to perform the second-step heat treatment without damaging its shape. The heat treatment of the silver ink composition in the liquid phase of the second stage after the heat treatment of the first step is preferably performed by immersing the silver ink composition in the heated liquid. The heating temperature and heating time in the heat treatment in this liquid phase are the same as the heating temperature and heating time in the second stage heat treatment described above.
The heated liquid is preferably hot water (heated water), and the second-step heat treatment is performed by immersing the silver ink composition subjected to the first-step heat treatment in hot water, that is, by boiling water. It is preferable to do so.
When the second step heat treatment is performed in the liquid phase, the metallic silver formed by this heat treatment may be further dried.

When the second step heat treatment of the silver ink composition is carried out in the liquid phase, the first step heat treatment of the silver ink composition is preferably carried out under non-humidifying conditions.
In addition, in this specification, "non-humidifying" means that the above-mentioned "humidifying" is not performed, that is, the humidity is not artificially increased, and the relative humidity is preferably less than 5%. ..

When the heat treatment under humidified conditions is adopted, the heat treatment of the silver ink composition is performed in the first stage heat treatment under the non-humidified conditions, instead of forming metallic silver as described above. It is particularly preferable to carry out the drying by a two-step method in which the drying is mainly carried out, and in the second step of the heat treatment, the metallic silver is formed to the end as described above under humidifying conditions.

When the second stage heat treatment is performed under humidified conditions, the heating temperature during the first stage heat treatment under non-humidified conditions is preferably 60 to 120 ° C., even if it is 70 to 110 ° C. Good. The heating time is preferably 5 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and particularly preferably 30 seconds to 15 minutes.
The heating temperature during the heat treatment under the second stage humidifying condition, which is performed after the heat treatment under the first stage non-humidifying condition, is preferably 60 to 140 ° C., preferably 70 to 130 ° C. Is more preferable. The heating time is preferably 1 minute to 2 hours, more preferably 1 minute to 1 hour, and particularly preferably 1 minute to 30 minutes.
As will be described later, when the silver ink composition is attached to a substrate having low heat resistance and heated (baked), the first-stage heat treatment under non-humidifying conditions and the second-stage humidifying conditions The heating temperature in the heat treatment in the above is preferably less than 130 ° C., more preferably 125 ° C. or lower, and particularly preferably 120 ° C. or lower.

Up to this point, a method for forming a conductive layer has been described when a silver ink composition in which a material for forming metallic silver is blended is used as the metal ink composition. When the conductive layer is formed by using another composition for a conductive layer such as a metal ink composition when the metal type is other than silver, for example, in the production method when the above-mentioned silver ink composition is used. The conductive layer can be formed by applying a method in which a part of the composition is changed according to the type of the composition for the conductive layer.

<Coating layer forming process>
In the coating layer, the resin composition (hereinafter, may be referred to as “composition for coating layer” in this step) is adhered to a target portion on the base material on which the conductive layer is formed to be attached to the conductive layer. It can be formed by forming a composition layer to be coated with the above, and appropriately selecting and performing a solidification treatment such as a drying treatment or a heat treatment on the composition layer (composition for a coating layer). When the composition for the coating layer is a curable resin composition, the composition layer may be cured to form a coating layer. Then, the heat treatment may be performed in combination with a drying treatment and a curing treatment.

The coating layer composition can be attached to a target portion by a known method such as a printing method, a coating method, or a dipping method, as in the case of a silver ink composition, for example.

In the coating layer forming step, the thickness of the coating layer can be adjusted by adjusting the amount of the coating layer composition to be adhered to the target portion or the blending amount of the curable resin or the like in the coating layer composition. ..

The solidification treatment such as the drying treatment and the heat treatment of the coating layer composition can be performed by the same method as in the case of the silver ink composition.

In order to cure the composition for the coating layer, energy rays such as ultraviolet rays may be irradiated or heated depending on the type of the resin component to be blended.
For example, in case of curing by irradiation of energy rays, irradiation of energy rays is preferably 200~1200mJ / cm ^2, more preferably 300~1000mJ / cm ^2.

In the coating layer forming step, the coating layer composition (resin composition) of the present invention suppresses the generation of cissing when it is applied to the coated surface (that is, the surface of the base material and the conductive layer). .. Therefore, a highly uniform coating layer can be formed.

<Process of forming other layers>
In the case of producing a laminate of the present invention in which a layer other than the conductive layer and the coating layer is provided on the base material, the step of forming the other layer at a predetermined timing in the above production method. May be added as appropriate.

<< Electronic equipment, transparent conductive film >>
The laminate is suitable for forming various electronic devices, transparent conductive films, and the like.
For example, an electronic device can be configured to include the base material as a housing (exterior material) by using the laminated body, and at least a part of the housing (exterior material) is formed by the base material in the laminated body. Except for the points, the configuration can be the same as that of a known electronic device. For example, a flat or curved portion of an exterior material in a communication device such as a mobile phone is used as the base material, a thin wire made of the conductive layer is formed on the exterior material (base material), and the thin wire is used as a circuit. The laminate can be used as a circuit board. Then, for example, a mobile phone can be configured by combining a voice input unit, a voice output unit, an operation switch, a display unit, and the like in addition to the laminated body. Further, by using the patterned conductive layer as an antenna, the laminated body can be used as an antenna structure, and the configuration is the same as that of a known data receiving / transmitting body except that the antenna structure is used. As a result, it can be a new data receiver / transmitter. For example, in the laminated body, a non-contact data receiving / transmitting body can be configured by providing an IC chip electrically connected to a conductive layer on a base material to form an antenna portion.

Further, the transparent conductive film is known to be transparent except that the laminated body is used and the conductive layer is provided as ultrafine wiring or ultrathin wiring, and the conductive layer is provided as ultrafine wiring or ultrathin wiring. It can have the same configuration as the conductive film. In particular, the laminate is suitable for forming a touch panel, an optical display, or the like.
The line width of the ultrafine wiring is preferably 1 to 20 μm, more preferably 1.3 to 15 μm, and particularly preferably 1.5 to 13 μm.
Further, the cross-sectional shape of the ultrafine wiring is preferably a semi-elliptical shape in which almost half of the region in the minor axis direction of the ellipse is cut off.
On the other hand, the thickness of the ultrathin wiring is preferably 5 nm to 10 μm, more preferably 7 nm to 5 μm, and particularly preferably 10 nm to 1 μm.
The cross-sectional shape of the ultra-thin wiring is the same as the cross-sectional shape of the ultra-fine wiring.
In the transparent conductive film, it is preferable that the conductive layer satisfies at least one of such line width and thickness. If the conductive layer has such a line width or thickness, it is difficult to visually recognize its existence, and thus it is preferable as a transparent conductive film.

Further, in the laminated body, when the conductive layer is a silver layer, the silver layer can be formed at a low temperature, and a wide range of materials such as a base material can be selected, so that the degree of freedom in design is dramatically increased. It is also possible to improve and make electronic devices, transparent conductive films, etc. have more rational structures.
The above-mentioned electronic devices, transparent conductive films, and the like can maintain high performance for a long period of time.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.

The components used in the production of the coating layer composition are shown below.
[Resin component]
(A) -1: "UV-7610B" manufactured by Nippon Synthetic Chemical Co., Ltd., a mixture of ultraviolet curable resin, polyurethane acrylate 65-75% by mass and acrylic acid ester 25-35% by mass, molecular weight 11000, oligomer functional group number 9. It is recommended that this ultraviolet curable resin be cured by heating it at 80 ° C. for 10 minutes and then irradiating it with ultraviolet rays at an irradiation amount of ^{400 mJ / cm 2.}
(A') -1: A mixture of "TCG004" manufactured by Osaka Organic Chemical Industry Co., Ltd., an ultraviolet curable resin, a polyurethane acrylate of 25 to 55% by mass, and an acrylic acid ester of 30 to 55% by mass. It is recommended that this ultraviolet curable resin be cured by heating it at 120 ° C. for 30 minutes and then irradiating it with ultraviolet rays at an irradiation amount of ^{400 mJ / cm 2.}
(A') -2: "UA0262" manufactured by Ube Industries, Ltd., polyurethane acrylate (ultraviolet curable resin). It is recommended that this ultraviolet curable resin be cured by heating it at 80 ° C. for 10 minutes and then irradiating it with ultraviolet rays at an irradiation amount of ^{400 mJ / cm 2.}
(A') -3: "UA0282" manufactured by Ube Industries, Ltd., polyurethane acrylate (ultraviolet curable resin). It is recommended that this ultraviolet curable resin be cured by heating it at 80 ° C. for 10 minutes and then irradiating it with ultraviolet rays at an irradiation amount of ^{400 mJ / cm 2.}
[Curing agent]
(B) -1: "IRGACURE127" manufactured by Ciba Japan, photopolymerization initiator, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2 -Methyl-Propane-1-one [Migration Inhibitor]
(C) -1: 5-Methylbenzotriazole [surfactant]
(D) -1: Neos "Futergent 610FM", nonionic surfactant, fluorine-containing group (hydrophilic group / lipophilic group) -containing oligomer (d) -2: Neos "Futergent 602A", nonion Surfactant, fluorine-containing group (hydrophilic group / lipophilic group, ultraviolet reactive group) -containing oligomer [solvent]
DAA: Diacetone alcohol (4-hydroxy-4-methyl-2-pentanone)
EGMPE: Ethylene glycol monopropyl ether PGMBE: Propylene glycol 1-mono-n-butyl ether (1-butoxy-2-propanol)
DEGEME: Diethylene glycol ethyl methyl ether PGMMEA: Propylene glycol monomethyl ether acetate DPGDME: Dipropylene glycol dimethyl ether CHOHA: Cyclohexanol acetate (cyclohexyl acetate)
DEGDEE: Diethylene glycol diethyl ether EGMBEA: Ethylene glycol mono-n-butyl ether acetate (2-butoxyethyl acetate)
CHON: Cyclohexanone MBA: 3-Methoxybutyl acetate (3-methoxybutyl acetate)
DEGIPME: Diethylene glycol isopropyl methyl ether

[Example 1]
<Manufacturing of coating layer composition>
Under the condition of 25 ° C., the curing agent (b) -1 is added to a mixed solvent (DAA / EGMPE = 70/30 (mass ratio)) of diacetone alcohol (DAA) and ethylene glycol monopropyl ether (EGMPE). It was dissolved to give a solution. The amount of the curing agent (b) -1 added was set to be 5% by mass with respect to the amount of the resin component (a) -1 described later.
Next, the resin component (a) -1 and the migration inhibitor (c) -1 were added to this solution whose temperature was adjusted to 45 ° C. and stirred to obtain a coating layer composition. The amount of the resin component (a) -1 added at this time was such that the content of the resin component (a) -1 in the coating layer composition was 20.0% by mass. The amount of the migration inhibitor (c) -1 added was set to be 5% by mass with respect to the amount of the resin component (a) -1 added.
Table 2 shows the types and amounts of each compounding ingredient. In addition, in Table 2, the description of "-" in the column of the compounding component means that the component is not compounded.

The viscosity and surface tension of the coating layer composition obtained above were measured by the following methods. The results are shown in Table 8.
(Viscosity of composition for coating layer)
The viscosity of the coating layer composition placed at room temperature (25 ° C.) was measured using a vibrating viscometer (“VISCOMATE VM-10A” manufactured by SEKONIC Corporation).
(Surface tension of coating layer composition)
For the composition for the coating layer placed at room temperature (25 ° C.), a dynamic surface tension meter (“SITA science line t60” manufactured by Eiko Seiki Co., Ltd.) was used to determine the surface tension when the bubble generation cycle was 0.1 Hz. It was measured.

<Manufacturing of laminate (evaluation of composition for coating layer)>
(Manufacturing of silver ink composition)
2-Ethylhexylamine (1.45 times molar amount with respect to 2-methylacetate silver acetate described later) and n-hexane (1.63 times molar amount with respect to silver 2-methylacetate acetate described later) in a beaker. In this order, silver 2-methylacetate acetate was added to the beaker so that the liquid temperature became 50 ° C. or lower while rotating and stirring the mechanical stirrer.
After the addition of 2-methylacetate silver is completed, formic acid (0.5 times the molar amount of 2-methylacetate silver) is added dropwise in a beaker over 10 minutes while maintaining the same state. Then, after the dropping of formic acid was completed, the mixture was further stirred for 1.5 hours as it was.
Then, 3,5-dimethyl-1-hexin-3-ol (hereinafter, may be abbreviated as "DMHO") (0.032 times by molar amount with respect to silver 2-methylacetate acetate) and 4-ethyl-1. A mixture of −octyne-3-ol (hereinafter sometimes abbreviated as “EOO”) (0.004 times molar amount with respect to silver 2-methylacetate acetate) was added to the beaker, and after the addition was completed, the mixture was further added as it was. The silver ink composition was obtained by stirring in this state for 5 minutes.
As the DMHO, "Surfinol 61" manufactured by Air Products Japan Co., Ltd. was used, and as the EOO, the one manufactured by Tokyo Chemical Industry Co., Ltd. was used.

Table 1 shows the types and ratios of each compounding ingredient. In Table 1, the "nitrogen-containing compound (molar ratio)" refers to the amount of the nitrogen-containing compound (number of moles) per mole of the material for forming metallic silver ([number of moles of nitrogen-containing compound] / [metal]. Number of moles of silver forming material]). Similarly, the "reducing agent (molar ratio)" is also the amount of the reducing agent compounded per mole of the metal silver forming material (the number of moles) ([the number of moles of the reducing agent] / [the mole of the metal silver forming material]. Number]). Similarly, "acetylene alcohol (2) (molar ratio)" also contains the amount (molar number) of acetylene alcohol (2) per mole of the material for forming metallic silver ([the number of moles of acetylene alcohol (2)]]. / [Number of moles of metallic silver forming material]). Similarly, the "solvent (molar ratio)" is the amount of the solvent compounded per mole of the metallic silver forming material (the number of moles) ([the number of moles of the solvent] / [the number of moles of the metallic silver forming material]). Means.
In this embodiment, the "material for forming metallic silver" is "silver β-ketocarboxylate (1)".

(Formation of silver layer)
A printing pattern was formed by applying the silver ink composition obtained above on one surface of a polycarbonate base material (thickness 2 mm) by a gravure offset printing method. The printing pattern was a mesh pattern in which a large number of lines having the same width were arranged at predetermined intervals in two orthogonal directions.
Next, hot air at 65 ° C. was blown onto the base material on which the above-mentioned printing pattern was formed for 5 minutes, and then the base material was dried at 120 ° C. for 5 minutes and then at 100 ° C. for 10 minutes, and further, the relative humidity was further increased. By heating (baking) at 120 ° C. for 10 minutes under a humidifying condition of 70 to 100%, the line-and-space patterns of metallic silver having a width of 4 μm and a distance between adjacent lines in the same direction of 200 μm are orthogonal to each other. A metallic silver mesh pattern formed in two directions was formed. The thickness of the metallic silver (silver layer) forming this mesh pattern was 0.06 to 0.07 μm.

(Formation of coating layer, production of laminate)
The coating film composition obtained above was applied to the entire surface of the pattern-forming surface of the base material on which the metallic silver mesh pattern was formed by an inkjet printing method to form a coating film. At this time, "EB100" manufactured by Konica Minolta Co., Ltd. was used as the inkjet printing apparatus.
Next, the formed coating film was dried at 80 ° C. for 10 minutes, and then the dried coating film was irradiated with ultraviolet rays at an irradiation amount of ^{400 mJ / cm 2 to cure the resin component.} A coating layer that covers the entire surface of the pattern-forming surface of the material, that is, the surface of the metallic silver mesh pattern on the pattern-forming surface and the surface of the base material on which the metallic silver mesh pattern is not formed. Was formed. The maximum thickness of this coating layer was 5 μm.
As described above, a mesh-like silver layer is formed as a conductive layer on the base material, and a coating layer is formed on the silver layer and a region on the base material where the silver layer is not provided. I got a body.

The appearance of the laminate obtained above was visually observed and observed using an opto-digital microscope "DSX500" (manufactured by Olympus Corporation). Then, based on the results, the repelling of the coating layer composition, the white turbidity of the base material, and the bleeding / surface smoothness of the coating layer were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 8.

(Repellent composition for coating layer)
◯: No repelling of the coating layer composition occurred.
X: Repellent of the coating layer composition occurred.
(White turbidity of the base material)
◯: The base material did not become cloudy.
X: The base material became cloudy.
(Bleeding / surface smoothness of coating layer)
◯: The coating layer was not blurred, and the surface smoothness of the coating layer was high.
X: The coating layer was blurred, and the surface smoothness of the coating layer was low.

<Manufacturing of coating layer composition, manufacturing of laminate (evaluation of coating layer composition)>
[Examples 2 to 17, Comparative Examples 1 to 32]
The composition for the coating layer was prepared in the same manner as in Example 1 except that one or both of the types and amounts of the compounding components were set as shown in Tables 2 to 4 at the time of producing the composition for the coating layer. A product was produced, and a laminate was produced (the composition for the coating layer was evaluated).
The evaluation results are shown in Tables 8-9. In Tables 8 to 9, the description of "-" in the evaluation result column means that the item has not been evaluated.

As is clear from the above results, the coating layer compositions of Examples 1 to 17 contain both ketoalcohol and alcohol ether, so that the generation of repellent is suppressed at the time of coating. In addition, quality deterioration of the base material was also suppressed, such as suppressing white turbidity of the base material. Further, in the laminates of Examples 1 to 12 and 14 to 17, the coating layer was not blurred and the surface smoothness of the coating layer was high, and in these examples, a particularly preferable laminate was obtained. Only in the laminate of Example 13, the coating layer was blurred and the surface smoothness of the coating layer was low, but this was because the content of the resin component of the coating layer composition was lower than that of the other examples. It is presumed that this is due to the fact.

On the other hand, the coating layer compositions of Comparative Examples 1 to 32 did not contain ketoalcohol and alcohol ether in combination, and more specifically, because they did not contain alcohol ether, at least their coating was applied. Occasionally repelling occurred or the substrate became cloudy. Furthermore, in some comparative examples, the coating layer was blurred and the surface smoothness of the coating layer was low.

FIG. 4 shows a graph obtained by plotting the coating layer compositions of the above Examples and Comparative Examples with the viscosity on the horizontal axis and the surface tension on the vertical axis.
In this graph, not only the relationship between the viscosity and the surface tension of the coating layer composition is shown, but also the presence or absence of cissing of the coating layer composition is shown at the same time.
As is clear from FIG. 4, the coating layer composition in which the generation of cissing is suppressed has a viscosity in the range of approximately 5.5 to 13.5 mPa · s and a surface tension of 23.2 to 29.5 mN. It was within the range of / m. That is, it can be said that a coating layer composition having such a specific range of viscosity and surface tension is a preferable example in terms of suppressing cissing.

The present invention can be used in various electronic devices having a conductive layer and a coating layer on a base material, and is suitable for use in optical applications such as touch panels and optical displays, for example.

1, 2, ... Laminated body, 11 ... Base material, 11a ... One surface of the base material (first surface), 11b ... The other surface of the base material (second surface), 12, 22 ... Conductive layer, 12a, 22a ... Conductive layer surface, 13, 23 ... Coating layer, 13a, 23a ... Coating layer surface

Claims (1)

Polyurethane (meth) acrylate, acrylic acid ester, and solvent are blended together.
Wherein Ri solvent is keto alcohols and alcohol ethers der,
The keto alcohol is diacetone alcohol,
It said alcohol ether, Ru either or both der ethylene glycol monopropyl ether and 1-butoxy-2-propanol, the resin composition.

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