JP2016000847A - Copper film forming composition, copper film forming method, copper film, wiring substrate, and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper film forming composite for forming a copper film having an excellent contact in a low resistance with a substrate, a copper film forming method using that composite, and a copper film, a wiring substrate and a touch panel.SOLUTION: A copper film forming composite to be used for forming a copper film is prepared by containing (A) a copper salt, (B) a polymer having a glass-transition temperature (Tg) at or lower than 50°C, and (C) an amine compound. A coating film is formed on a substrate by using that copper film forming composite and is heated at 250°C or lower in a non-oxidation atmosphere so that a copper film to contact with said substrate is formed on the substrate, thereby to manufacture the wiring substrate. On the other hand, the copper film forming composite is used to form a coating film over a transparent substrate 22 having a first detection electrode 23, a second detection electrode 24 and the like, and the coating film is heated to form a lead-out wiring 31, thereby to manufacture a touch panel 21.

Description

  The present invention relates to a copper film forming composition, a copper film forming method, a copper film, a wiring board, and an electronic device.

  The wiring board is also referred to as a printed wiring board or the like, and has become a major component for fixing and wiring electronic components in the field of electronic equipment. In this wiring substrate, a patterned metal film is formed on the substrate, and constitutes a wiring, a plating power supply film, electrodes, terminals, and the like. In the field of electronic equipment, similar to a printed wiring board, a patterned metal film is formed on a board, and those used as wiring etc. are sensors, capacitors, arithmetic elements, touch panels, liquid crystal display elements. And organic EL elements.

  In manufacturing a wiring board, a touch panel, or the like, as a method for forming a pattern such as a wiring that is a metal film on the substrate, for example, a method using a photolithography technique is known. In this method, first, a uniform solid metal film is formed on a substrate. As a method for forming the metal film, a plating method is preferably used. Further, it is possible to use vapor deposition or sputtering. Then, a resist solution is applied on the formed metal film to form a resist layer. Next, the resist layer is patterned by irradiating the resist layer with ultraviolet rays using a photomask and then developing the resist layer. Next, the metal film not covered with the resist layer is removed by etching, and the remaining resist portion is peeled off to obtain a patterned metal film. The method using the photolithography technique can make the line width of the wiring pattern to be formed on the submicron order, and is an effective method for forming a metal film pattern.

In such a method using the photolithography technique, a plating method is preferably used for forming the metal film to be patterned as described above. In the plating method, formation of a seed layer by a sputtering method and a plating process are usually performed. Is required. Since the sputtering method needs to be performed in a vacuum, there are significant restrictions on the apparatus and operation. Also, the process takes a long time and the production efficiency is low. In the plating process, the waste liquid treatment of the plating solution is a big environmental problem.
Similarly, when vapor deposition or sputtering is used to form a metal film, it is necessary to form the metal film in a vacuum, so there are significant restrictions on the equipment and operation, and the processing takes a long time. Therefore, the metal film cannot be formed efficiently.

  Therefore, there is a demand for a metal film forming technique that can be easily formed in a short time with a low resistance metal film with few restrictions on the apparatus and the environment. The metal film formation technique is a technique capable of forming a uniform solid metal film on a substrate, and a technique capable of directly forming a patterned metal film. It is preferable.

  In recent years, a technique for directly drawing a patterned metal film using a dispersion obtained by dispersing metal fine particles in an organic solvent or the like has attracted attention. For example, a desired pattern is formed using a dispersion of metal fine particles by an ink jet printing method or a screen printing method. When the average particle diameter of the metal fine particles is about several nanometers to several tens of nanometers, the melting point is lower than that of the bulk metal, and the particles are fused by heating at a relatively low temperature of about 300 ° C. The above-described technology is a technology that utilizes such a phenomenon to obtain a patterned metal film by sintering metal fine particles at a relatively low temperature.

  As a dispersion composition for forming such a metal film, a composition containing silver nanoparticles, which are noble metal fine particles, in the metal fine particles is known.

  Further, a method of using a metal salt or the like as a metal raw material in place of the metal fine particles has attracted attention as a new metal film forming technique. For example, a method is known in which a composition is prepared by combining an easily available copper salt and a reducing agent, and a copper film is formed using the composition.

  Specifically, in the techniques disclosed in Patent Literature 1 and Patent Literature 2, copper formate as a raw material and an amine are combined to realize the production of fine particle size copper particles. Then, the manufactured fine particle size copper particles are dispersed to prepare an ink. Next, an ink containing the fine particle size copper particles is applied, and the coating film is baked at 300 ° C. in an argon atmosphere to form a line-shaped copper wiring.

  Moreover, in patent document 3, copper film formation is implement | achieved with the composition which combined the copper salt and the amine. In patent document 4, copper film formation is implement | achieved by the composition which combined the copper formate and the amine. In patent document 5, it implement | achieves with the composition which combined the copper formate and the alkanolamine.

  And in patent document 6 and patent document 7, copper film formation is implement | achieved by the composition containing a noble metal microparticle, copper salt, a reducing agent, and a monoamine.

JP 2008-13466 A JP 2008-31104 A JP 2004-162110 A Japanese Patent Laying-Open No. 2005-2471 JP 2010-242118 A JP 2011-34749 A JP 2011-34750 A

  As described above, for example, a metal film forming technique that can easily form a low-resistance metal film in a short time is required so as to be suitable for providing a wiring board, a touch panel, and the like. The metal film formation technique is a technique capable of forming a uniform metal film on one surface of a substrate, and a technique capable of directly forming a metal film patterned into a desired shape. It is preferable that Therefore, as described above, studies have been actively conducted on compositions containing metal fine particles and metal salts. However, each technology has problems to be solved.

  Specifically, in the case of a technique for forming a metal film using a composition containing metal fine particles, it has been difficult to completely fuse the metal fine particles by simple sintering at a relatively low temperature. For this reason, the metal film obtained after sintering has a problem in that it cannot realize electrical resistance characteristics when compared with bulk metal, that is, low resistance.

  In addition, in the case of the technique using the above-described dispersion composition containing silver nanoparticles or the like, there is a problem that silver tends to cause electromigration. Moreover, silver is a noble metal and becomes an expensive material compared with copper etc. which are easy to acquire. Therefore, there is a problem that the silver nanoparticles themselves are expensive and increase the cost of the metal film forming process. Electromigration is due to the influence of an electric field, and a metal component (for example, a metal such as silver used for wiring or electrodes) crosses over or inside a non-metallic medium (for example, an insulator, particularly a substrate). It is a phenomenon that moves.

  Therefore, in place of the metal fine particles, as described above, a technique for forming a metal film using a metal salt or the like as a raw material has attracted attention. In particular, a technique is expected that uses a copper compound such as a copper salt that is easily available and has little concern about electromigration as a raw material. However, it is difficult to form a low-resistance copper film by simple heating at a low temperature even in a method using such a readily available copper salt as a raw material.

  For example, Patent Document 1 and Patent Document 2 described above describe the formation of copper wiring using copper formate and amine, but how much resistance is reduced by the formed copper wiring. Not listed.

  Moreover, in patent document 3 mentioned above, although formation of the copper film by the composition which combined copper salt and amine is described, it is not described whether the formed copper film is low resistance. Similarly, in patent document 4, although formation of the copper film by the composition which combined copper formate and an amine is described, it is not described whether the formed copper film is low resistance.

  Further, in Patent Document 6 and Patent Document 7, a combination of noble metal fine particles and a copper salt is used to form a copper film with a composition containing a reducing agent and a monoamine, but expensive noble metal fine particles or noble metal compounds are essential. As a component, the cost of raw materials is increased, and a copper film cannot be easily formed with high productivity.

  As another problem, in the technique of the dispersion composition using the metal fine particles and the technique of the composition using the metal salt, the metal film is formed between the metal film and the substrate. In some cases, sufficient adhesion could not be obtained.

  For example, in the case of a touch panel, a metal film on a substrate is pressed by a user's touch operation, and the substrate may be deformed. Therefore, a metal film forming a pattern such as a wiring is required to have high adhesion to the substrate so that peeling does not occur due to such an external influence.

  In particular, the touch panel is a glass substrate and a transparent conductive material such as a polyethylene terephthalate (PET) film or a transparent conductive material such as an ITO (Indium Tin Oxide) film formed on the resin substrate. A pattern such as a wiring that is a metal film may be provided on the film. In that case, the metal film is required to have excellent adhesion between a glass substrate, a resin substrate such as a PET film, and a transparent conductive film such as an ITO film, so that a highly reliable touch panel can be provided.

  However, it is difficult to improve the adhesion with the substrate in the above-described metal film according to the prior art. For example, in the case of a copper film, it has been difficult to achieve excellent adhesion between a glass substrate, a resin substrate such as a PET film, and a transparent conductive film such as an ITO film. Therefore, when the touch panel has a patterned metal film as a wiring or the like, it is difficult to achieve both excellent detection capability for a user's touch operation and reliability for sustaining it.

  As described above, for example, a metal film formation technique using a composition is required to reduce the resistance of the metal film and improve the adhesion to the substrate so as to be suitable for providing a wiring board and a touch panel. ing. However, with the conventional technology, it has been difficult to realize both of them.

  Therefore, there is a need for a metal film forming technique that can form a metal film having low resistance and excellent adhesion to a substrate by heating at a lower temperature than in the past. That is, a copper film having low resistance and excellent adhesion to a substrate is required, and a copper film forming method capable of forming the copper film is required.

  And the composition for copper film formation suitable for the copper film formation method is calculated | required.

  The present invention has been made based on the above findings. That is, the objective of this invention is providing the composition for copper film formation which can form the copper film which was low resistance and excellent in adhesiveness with a board | substrate.

  Another object of the present invention is to provide a copper film forming method for forming a copper film having low resistance and excellent adhesion to a substrate.

  Another object of the present invention is to provide a copper film having low resistance and excellent adhesion to a substrate.

  Another object of the present invention is to provide a wiring board having a copper film having low resistance and excellent adhesion to the board.

  Furthermore, the objective of this invention is providing the electronic device which has a copper film which was low resistance and excellent in adhesiveness with a board | substrate.

  Other objects and advantages of the present invention will become apparent from the following description.

The first aspect of the present invention is:
(A) copper salt,
(B) It is related with the composition for copper film formation characterized by including the polymer whose glass transition temperature (Tg) is 50 degrees C or less, and (C) amine compound.

In the first aspect of the present invention,
(A) Copper salt is copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper pivalate, copper formate, copper hydroxyacetate, copper glyoxylate, copper oxalate Acetylacetonato copper, 1,1,1-trifluoroacetylacetonato copper, and 1,1,1,5,5,5-hexafluoroacetylacetonato copper preferable.

  1st aspect of this invention WHEREIN: It is preferable that Tg of (B) polymer exists in the range of -70 degreeC or more and 25 degrees C or less, ie, -70 degreeC-25 degreeC.

  In the first aspect of the present invention, the polymer (B) is at least one selected from the group consisting of a (meth) acrylic compound having a weight average molecular weight of 300,000 or less, an elastomer, and a hydrogenated product of the elastomer. preferable.

  In the first aspect of the present invention, the elastomer comprises natural rubber, styrene elastomer, olefin elastomer, urethane elastomer, polyester elastomer, acrylic elastomer, polyamide elastomer, silicone elastomer, chlorosulfonated polyethylene, fluororubber, and polysulfide elastomer. It is preferably at least one selected from the group. The elastomer hydrogenated product is preferably at least one selected from the group consisting of elastomeric hydrogenated products. Here, the hydrogenated product of the elastomer refers to a compound in which all or part of the conjugated double bond structure of the elastomer is hydrogenated and all or part of the conjugated double bond structure is converted to a single bond structure.

  In the first aspect of the present invention, the (C) amine compound is preferably represented by at least one of the following general formula (1), the following general formula (2), and the following general formula (3). .

(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having ³ to 18 carbon atoms. R ³ represents , A single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon having 3 to 18 carbon atoms. Group, amino group, dimethylamino group, or diethylamino group.)

(In General Formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. R ⁷ represents , A methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group, and R ⁸ represents an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. (However, when R ⁵ and R ⁶ are hydrogen atoms, R ⁸ represents a group other than a methyl group or an ethyl group.)

In (formula ^{(3), R 9, R} 10 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or,, ^{.R 11} of an alicyclic hydrocarbon group having 3 to 18 carbon atoms , A methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group, R ¹² and R ¹³ are each independently an alkyl group having 1 to 18 carbon atoms or an alicyclic ring having 3 to 18 carbon atoms. Represents a hydrocarbon group.)

  In the second aspect of the present invention, a coating film is formed using the composition for forming a copper film of the first aspect of the present invention, and the coating film is heated in the air at 250 ° C. or lower or in a non-oxidizing atmosphere. The present invention relates to a method for forming a copper film, characterized by comprising the step of:

  A third aspect of the present invention relates to a copper film formed using the composition for forming a copper film according to the first aspect of the present invention.

  According to a fourth aspect of the present invention, there is provided a wiring board comprising the copper film according to the third aspect of the present invention.

  According to a fifth aspect of the present invention, there is provided an electronic apparatus comprising the copper film according to the third aspect of the present invention.

  According to the 1st aspect of this invention, the composition for copper film formation which forms the copper film which was low resistance and excellent in adhesiveness with a board | substrate is provided.

  According to the second aspect of the present invention, there is provided a copper film forming method for forming a copper film having low resistance and excellent adhesion to a substrate.

  According to the third aspect of the present invention, a copper film having low resistance and excellent adhesion to a substrate is provided.

  According to the fourth aspect of the present invention, a wiring board having a copper film having low resistance and excellent adhesion to the board is provided.

  According to the fifth aspect of the present invention, an electronic apparatus having a copper film having low resistance and excellent adhesion to a substrate is provided.

It is a top view which shows the touchscreen of embodiment of this invention. It is sectional drawing which follows the B-B 'line of FIG.

  In the present invention, a copper salt of component (A) (hereinafter also referred to as (A) copper salt) is used as a raw material for the copper film, and the glass transition temperature (Tg) of component (B) is 50 ° C. or less. A composition for forming a copper film is prepared together with a coalescence (hereinafter also referred to as (B) polymer) and an amine compound (hereinafter also referred to as (C) amine compound) of component (C). In the present invention, the composition for forming a copper film is used, for example, applied onto a substrate to form a coating film. Subsequently, the coating film is heated at a temperature that is lower than that of the prior art to form a copper film having low resistance and excellent adhesion to the substrate.

  At this time, the heating of the coating film of the composition for forming a copper film of the present invention does not require the hydrogen gas that has been frequently used in the prior art, but in the atmosphere, or with nitrogen gas, argon gas, helium gas, or the like. A low resistance copper film having adhesion to the substrate can be formed by heating in the utilized non-oxidizing atmosphere. That is, the composition for forming a copper film of the present invention can form a low-resistance copper film by heating even in an oxidizing atmosphere such as the air. If the atmosphere environment excluding the oxidizing atmosphere such as the atmosphere is defined as a non-oxidizing atmosphere, the composition for forming a copper film of the present invention has a desired resistance characteristic by heating even in a non-oxidizing atmosphere. A copper film can be formed. Therefore, the composition for forming a copper film of the present invention does not dare to use hydrogen gas, which has an explosion risk in the heating process at the time of forming the copper film, and can form the copper film by a safe and simple heating process. it can.

  The composition for forming a copper film of the present invention is capable of forming a uniform solid copper film on a substrate, and becomes a wiring, electrode, terminal, etc. by combining with an appropriate coating method. It is also possible to form the formed copper film directly on the substrate. Therefore, in the present invention, the “copper film” is a concept including a patterned copper film together with a solid film made of copper. That is, patterns such as copper wirings and copper electrodes are also included in the “copper film” of the present invention. Similarly, the “film” may be used as a concept including a pattern.

  In the present invention, the “wiring board” is not limited to the wiring board known as a so-called printed wiring board. In the present invention, the “wiring substrate” includes all substrates in which a patterned metal film is formed on the substrate to form wirings, electrodes, terminals, and the like. For example, in the present invention, the “wiring board” includes a substrate for constituting a touch panel, a liquid crystal display element, an organic EL element and the like in addition to the above-described printed wiring board. That is, a substrate for constituting them, which includes a substrate in which a patterned metal film is formed on the substrate and constitutes wirings, electrodes, terminals, and the like.

  In the following description of the present invention, conductive electrically conductive members referred to as wiring, electrodes, terminals, and the like included in the wiring board are collectively referred to as wiring for convenience.

  Next, the composition for forming a copper film of the embodiment of the present invention will be described in more detail. Then, preparation of the composition for copper film formation of embodiment of this invention and the copper film formation method of embodiment of this invention using the composition for copper film formation of embodiment of this invention are demonstrated.

<Composition for forming copper film>
The composition for forming a copper film according to an embodiment of the present invention includes (A) a copper salt as a raw material for the copper film, and (B) a polymer having a glass transition temperature (Tg) of 50 ° C. or less, and (C ) A composition containing an amine compound and a reduction reaction type composition for forming a copper film.

  Moreover, the composition for copper film formation of embodiment of this invention can contain a solvent in addition to said each component. Furthermore, the composition for forming a copper film of this embodiment can contain other optional components in addition to the metal fine particles, in addition to the above components. The composition for forming a copper film of this embodiment can form a patterned coating film by various known coating methods, and the coating film can be heated to form a copper film. .

  At this time, the composition for forming a copper film according to the embodiment of the present invention has the above-described composition, so that it is applied onto an appropriate substrate to form a coating film, and then in the atmosphere or, for example, nitrogen gas or the like By heating in a non-oxidizing atmosphere, the copper film of the embodiment of the present invention can be formed on the substrate. The heating temperature can be 250 ° C. or lower, which is lower than that of the prior art, and can be 200 ° C. or lower.

  Therefore, in the composition for forming a copper film of the embodiment of the present invention, it is not particularly necessary to form a reducing atmosphere using a reducing gas such as hydrogen gas, and by heating at a relatively low temperature in a simple and safe state. A copper film having excellent resistance characteristics can be formed.

  Hereinafter, each component of the composition for copper film formation of this embodiment is demonstrated.

[(A) Copper salt]
The (A) copper salt contained in the composition for forming a copper film of the embodiment of the present invention is not particularly limited as long as it is a compound containing copper ions. Examples thereof include a copper salt composed of at least one of an anionic species and an organic anionic species.

  Among these, from the viewpoint of solubility, it is preferable to use one or more selected from the group consisting of a copper carboxylate and a complex salt of copper and an acetylacetone derivative.

  Examples of the copper carboxylate include, for example, copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper 2-ethylbutyrate, copper valerate, and copper isovalerate. , Copper salts with aliphatic carboxylic acids such as copper pivalate, copper hexanoate, copper heptanoate, copper octoate, copper 2-ethylhexanoate, copper nonanoate, copper malonate, copper succinate, copper maleate, etc. Copper salt with dicarboxylic acid, copper salt with aromatic carboxylic acid such as copper benzoate, copper salicylate, copper formate, copper hydroxyacetate, copper glyoxylate, copper lactate, copper oxalate, copper tartrate, copper malate, Suitable examples include copper salts with carboxylic acids having a reducing power such as copper citrate.

  Examples of the complex salt of copper and an acetylacetone derivative described above include acetylacetonato copper, 1,1,1-trimethylacetylacetonato copper, 1,1,1,5,5,5-hexamethylacetylacetonate. Suitable examples include copper, 1,1,1-trifluoroacetylacetonato copper, 1,1,1,5,5,5-hexafluoroacetylacetonato copper and the like.

  Among these, from the viewpoint of forming a soluble and low resistance copper film, copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper pivalate, copper formate, Copper hydroxyacetate, copper glyoxylate, copper oxalate, acetylacetonatocopper, 1,1,1-trifluoroacetylacetonatocopper and 1,1,1,5,5,5-hexafluoroacetylacetonatocopper preferable.

  In the composition for forming a copper film of the embodiment of the present invention, a copper salt other than the above may be used as the component (A), but it is difficult to obtain or expensive, so high production efficiency. May be disadvantageous from the viewpoint of realizing. Moreover, as (A) copper salt, it may be a commercially available one or synthesized by a known method, and further, a compound containing copper ions and at least one of an inorganic anion species and an organic anion species are mixed. By doing so, even those formed in the system can be used without any limitation, and are not particularly limited.

  In addition, when a copper salt with (A) a carboxylic acid having a reducing power is used as the copper salt, a carboxylic acid having a reducing power as a counter anion acts as a reducing agent, so that it is not necessary to add a reducing agent separately. There is no problem.

  In the composition for forming a copper film of the embodiment of the present invention, (A) the purity of the copper salt is not particularly limited, but when the copper film is formed to be too low in purity, the conductivity (resistance characteristics) is increased. May cause adverse effects. Therefore, the purity of (A) copper salt is preferably 90% or more, and more preferably 95% or more.

  As content of (A) copper salt in the composition for copper film formation of this embodiment, 1 mass%-70 with respect to 100 mass% of all the components which the composition for copper film formation of this embodiment contains. % By mass is preferable, and 5% by mass to 50% by mass is more preferable. (A) By making content of a copper salt into 1 mass%-70 mass%, the copper film which has the outstanding electroconductivity can be formed. By setting the content of the copper compound to 5 mass% to 50 mass%, a copper film having a lower resistance value can be formed.

[(B) Polymer whose glass transition temperature (Tg) is 50 ° C. or lower]
(B) As a polymer having a glass transition temperature (Tg) of 50 ° C. or less ((B) polymer), a (meth) acryl compound having a weight average molecular weight of 300,000 or less (hereinafter also referred to as “component (B1)”). And elastomers (hereinafter also referred to as component (B2)) and hydrogenated elastomers (hereinafter also referred to as component (B3)). That is, the polymer (B) is at least one selected from the group consisting of a (meth) acrylic compound (B1) having a weight average molecular weight of 300,000 or less, an elastomer (B2), and a hydrogenated elastomer (B3). Is preferred.

  In the present invention, the glass transition temperature (Tg) is a value obtained by measuring the temperature with a temperature gradient of 10 ° C./min using differential scanning calorimetry (DSC).

  The (meth) acrylic compound having a weight average molecular weight of 300,000 or less, which is the component (B1) described above, is (b1) an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid anhydride (hereinafter collectively referred to as “ Unsaturated carboxylic acid monomer (b1) ") and (b2) other ethylenically unsaturated compounds (hereinafter also simply referred to as" other monomer (b2) ") in a solvent. Thus, it can be produced by radical polymerization in the presence of a polymerization initiator.

  Examples of the unsaturated carboxylic acid monomer (b1) include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; Mention may be made of dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; anhydrides of the above dicarboxylic acids.

  Among these unsaturated carboxylic acid monomers (b1), acrylic acid, methacrylic acid, maleic anhydride, copolymerization reactivity, solubility of the resulting polymer in an alkaline aqueous solution and easy availability. 2-Methacryloyloxyethyl hexahydrophthalic acid and the like are preferable.

  In the production of the component (B1), the unsaturated carboxylic acid monomer (b1) can be used alone or in admixture of two or more.

  In the component (B1), the content of the repeating unit derived from the unsaturated carboxylic acid monomer (b1) is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight, More preferably, it is 15 to 30% by weight. In this case, when the content of the repeating unit derived from the unsaturated carboxylic acid monomer (b1) is in the above range, the polymer (B) has resistance characteristics and resistance to the substrate in the formed copper film. It becomes a more effective component for achieving both adhesion.

  Other monomers (b2) mentioned above include (meth) acrylic acid alkyl esters, (meth) acrylic acid alicyclic esters, (meth) acrylic acid aryl esters, dicarboxylic acid dialkyl esters, (meth) ) Acrylic acid epoxy alkyl esters; dicarbonylimide derivatives; conjugated diene compounds, vinyl aromatic compounds and the like.

Among these other monomers (b2), from the viewpoint of copolymerization reactivity and solubility of the resulting polymer in an aqueous alkali solution, 2-methylcyclohexyl acrylate, hydroxyethyl methacrylate, tricyclomethacrylate [5. 2.1.0 ^2,6 ] decan-8-yl, styrene, glycidyl methacrylate, 3- (methacryloyloxymethyl) -3-ethyloxetane, tetrahydrofurfuryl methacrylate, 1,3-butadiene, phenylmaleimide, cyclohexyl Maleimide and the like are preferred.

  In the production of the component (B1), the other monomer (b2) can be used alone or in admixture of two or more.

  In the component (B1), the content of the repeating unit derived from the other monomer (b2) is preferably 50% by weight to 95% by weight, more preferably 60% by weight to 90% by weight, and still more preferably. Is 70% to 85% by weight. In this case, when the content of the repeating unit derived from the other monomer (b2) is in the above range, the polymer (B) has a resistance characteristic and adhesion to the substrate in the formed copper film. It becomes a more effective ingredient for achieving both.

  Examples of the solvent used for the production of the component (B1) include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether. Propionate, aromatic hydrocarbon, ketone, ester and the like can be mentioned.

  Of the above-mentioned solvents, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable. Among them, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Particularly preferred are ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, and 3-methoxybutyl acetate.

  The said solvent can be used individually or in mixture of 2 or more types.

  The polymerization initiator used in the radical polymerization is not particularly limited, and examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvalero). Nitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobis (2-methylpro) Azo compounds such as pionate) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butyl) Peroxy) organic peroxides such as cyclohexane; hydrogen peroxide and the like. Moreover, when using a peroxide as a polymerization initiator, it is good also as a redox type initiator combining it and a reducing agent.

  These polymerization initiators can be used alone or in admixture of two or more.

  It is also possible to introduce a (meth) acryloyloxy group into the polymer by reacting a carboxyl group in the component (B1) with a (meth) acrylic acid ester having an epoxy group.

  In the reaction between a carboxyl group in the polymer and an unsaturated compound such as a (meth) acrylic acid ester having an epoxy group, a polymer containing a polymerization inhibitor, preferably in the presence of a suitable catalyst as necessary. An unsaturated compound having an epoxy group is added to the solution and stirred for a predetermined time under heating. Examples of the catalyst include tetrabutylammonium bromide. Examples of the polymerization inhibitor include p-methoxyphenol. And reaction temperature has preferable 70 to 100 degreeC. The reaction time is preferably 8 hours to 12 hours.

  In that case, the content of the structural unit having a (meth) acryloyloxy group is preferably 10 mol% to 70 mol%, and more preferably 20 mol% to 50 mol%, of all the components (B1).

  In the component (B1), when the content of the structural unit having a (meth) acryloyloxy group is in the above range, the polymer (B) has resistance characteristics and adhesion to the substrate in the formed copper film. It becomes a more effective ingredient for achieving both.

  Next, specific examples of the elastomer as the component (B2) include styrene elastomer, olefin elastomer, nitrile rubber (poly (acrylonitrile-co-butadiene)), ethylene-propylene rubber (poly (ethylene-co-propylene). )), Acrylic elastomer, epichlorohydrin rubber, silicone elastomer, fluorine rubber, urethane elastomer (urethane rubber), chlorosulfonated polyethylene, polyester elastomer and polyamide elastomer, natural rubber and polysulfide elastomer.

  Examples of the styrene elastomer include styrene / butadiene random copolymer, styrene / butadiene / styrene block copolymer, styrene / isoprene random copolymer, styrene / isoprene block copolymer, styrene / isoprene / styrene block copolymer, styrene / ethylene / butylene / styrene. These include block copolymers, styrene / ethylene / propylene / styrene block copolymers and styrene / butadiene / methacrylate block polymers. The styrene elastomer may contain monomer units of styrene derivatives such as α-methyl styrene, 3-methyl styrene, 4-propyl styrene, and 4-cyclohexyl styrene together with styrene or instead of styrene.

  Commercially available styrene elastomers include Tufrene (registered trademark), Solprene T, Asaprene (registered trademark) T, Tuftec (registered trademark) (above, manufactured by Asahi Kasei Kogyo Co., Ltd.), Elastomer AR (produced by Aron Kasei Co., Ltd.) Clayton (registered trademark) G, Califlex (registered trademark) (manufactured by Shell Japan), JSR-TR, TSR-SIS, Dynalon (registered trademark) (manufactured by JSR), Denka STR (manufactured by Denki Kagaku) ), QUINTAC (registered trademark) (manufactured by ZEON Corporation), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), LAVALON (registered trademark) (manufactured by Mitsubishi Chemical Corporation), Septon (registered trademark), HYBRAR (registered trademark) ( As mentioned above, Kuraray Co., Ltd., Sumiflex (registered trademark) (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer (registered trademark), Actima ) (Or more, there is a Rikenbinirukogyo Co., Ltd.) and Paraloid (R) EXL series (Rohm & Haas).

  The above-mentioned olefin elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. Specific examples of the olefin elastomer include ethylene-propylene copolymer (EPR) and ethylene / propylene / diene copolymer (EPDM). The olefin elastomer is a copolymer of a diene having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctanediene, methylene norbornene, ethylidene norbornene, butadiene and isoprene, and α-olefin, epoxidized polybutadiene. Alternatively, carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer may be used. Other examples of the olefin elastomer include ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, propylene-α-olefinine copolymer rubber, isoprene rubber (polyisoprene), and butadiene rubber. (Polybutadiene), chloroprene rubber (polychloroprene) and butyl rubber (poly (butylene-co-butadiene)).

  Commercially available olefin elastomers include Miralastomer (registered trademark) (manufactured by Mitsui Petrochemical Co., Ltd.), EXACT (registered trademark) (manufactured by Exxon Chemical Co., Ltd.), ENGAGE (registered trademark) (manufactured by Dow Chemical Company), Nipol ( Registered trademark) series (manufactured by ZEON Corporation), hydrogenated styrene-butadiene rubber DYNABONSHSBR (manufactured by JSR Corporation), butadiene-acrylonitrile copolymer NBR series (manufactured by JSR Corporation), both-end carboxyl group-modified butadiene-acrylonitrile having a crosslinking point XER series of copolymers (manufactured by JSR), BF-1000 of epoxidized polybudadiene partially epoxidized with polybutadiene (manufactured by Nippon Soda Co., Ltd.), and liquid butadiene-acrylonitrile copolymer HYCAR (registered trademark) series ( Made by Ube Industries) It is below.

  The above-mentioned acrylic elastomer includes acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate and ethoxyethyl acrylate, monomers having an epoxy group such as glycidyl methacrylate and allyl glycidyl ether, and / or vinyl such as acrylonitrile and ethylene. It is obtained by copolymerizing with a monomer. Acrylic elastomers include acrylic rubbers (poly (acrylic ester-co-chloroethyl vinyl ether) and poly (acrylic ester-co-acrylonitrile). More specifically, acrylonitrile-butyl acrylate copolymer, acrylonitrile / Examples include butyl acrylate / ethyl acrylate copolymers and acrylonitrile / butyl acrylate / glycidyl methacrylate copolymers.

  The above-mentioned silicone elastomer is an elastomer containing organopolysiloxane as a main component, and is classified into a polydimethylsiloxane system, a polymethylphenylsiloxane system, and a polydiphenylsiloxane system. A part of the organopolysiloxane may be modified with a vinyl group, an alkoxy group or the like. Specific examples of silicone elastomers include silicone rubber (poly (dimethylsiloxane) and poly (dimethylsiloxane-co-methylvinylsiloxane)).

  Commercially available silicone elastomers include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), the SE series, the CY series and the SH series (manufactured by Toray Dow Corning Silicone).

  The above-mentioned urethane elastomer has a hard segment generated from a low molecular (short chain) diol and a diisocyanate and a soft segment generated from a high molecular (long chain) diol and a diisocyanate. Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, and poly (1,6 -Hexylene carbonate) and poly (1,6-hexylene-neopentylene adipate). The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. Examples of the low molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48 to 500.

  Commercially available urethane elastomers include PANDEX (registered trademark) T-2185, T-2983N (manufactured by Dainippon Ink & Chemicals, Inc.), sylactolan E790, and Hitaroid (registered trademark) series (manufactured by Hitachi Chemical). There is.

  The above-mentioned polyester elastomer is an elastomer having a hard segment and a soft segment, and is obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and cyclohexanedicarboxylic acid. And alicyclic dicarboxylic acids such as acids. The hydrogen atom of the aromatic ring of the aromatic dicarboxylic acid may be substituted with a methyl group, an ethyl group, a phenyl group, or the like. These compounds can be used alone or in combination of two or more. Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. Or alicyclic diol, bisphenol A, bis- (4-hydroxyphenyl) -methane, bis- (4-hydroxy-3-methylphenyl) -propane, and resorcin. These compounds can be used alone or in combination of two or more. A multi-block copolymer having an aromatic polyester (eg, polybutylene terephthalate) portion as a hard segment and an aliphatic polyester (eg, polytetramethylene glycol) portion as a soft segment can be used.

  The above-mentioned polyester elastomers are available in various grades depending on the types and ratios of hard segments and soft segments, and the difference in molecular weight. Commercially available polyester elastomers include Hytrel (registered trademark) (manufactured by DuPont-Toray), Perprene (registered trademark) (manufactured by Toyobo) and Espel (registered trademark) (manufactured by Hitachi Chemical Co., Ltd.). .

  The polyamide elastomer described above has a hard segment made of polyamide and a soft segment made of polyether or polyester. Polyamide elastomers are roughly classified into two types: polyether block amide type and polyether ester block amide type. Examples of the polyamide include polyamide 6, polyamide 11, and polyamide 12. Polyethers include polyoxyethylene, polyoxypropylene and polytetramethylene glycol.

  Commercially available polyamide elastomers include UBE polyamide elastomer (manufactured by Ube Industries), Daiamide (registered trademark) (manufactured by Daicel Huls), PEBAX (registered trademark) (manufactured by Toray Industries, Inc.), and Grilon (registered trademark). There are ELY (manufactured by MMS Japan Co., Ltd.), Novamid (registered trademark) (manufactured by Mitsubishi Chemical Co., Ltd.) and GREL (registered trademark) (manufactured by Toyobo Co., Ltd.).

  In addition to the above elastomer, a rubber-modified epoxy resin can be used as the rubbery elastomer. The rubber-modified epoxy resin includes, for example, a part or all of epoxy groups such as bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin, or cresol novolac type epoxy resin, It can be obtained by modification with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends and a terminal amino-modified silicone rubber.

  The elastomer as the component (B2) may be a fine particle elastomer (hereinafter also referred to as “elastomer fine particles”). The elastomer fine particles are dispersed in a fine particle state in the composition for forming a copper film of the present embodiment. The elastomer fine particles may contain an elastomer that forms islands in a sea-island structure by phase separation in an incompatible system, or an elastomer that forms so-called microdomains.

  The elastomer fine particles are obtained by copolymerizing a crosslinkable monomer having two or more unsaturated polymerizable groups and one or more other monomers selected so that the Tg of the elastomer fine particles is 50 ° C. or less (so-called crosslinked fine particles). Is preferred. The other monomer may have a functional group other than the polymerizable group, for example, a functional group such as a carboxyl group, an epoxy group, an amino group, an isocyanato group, or a hydroxyl group.

  Examples of crosslinkable monomers include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol di (Meth) acrylate and polypropylene glycol di (meth) acrylate may be mentioned. Of these, divinylbenzene is preferred.

  In producing the elastomer fine particles, the crosslinkable monomer is used in an amount in the range of 1% by weight to 20% by weight, more preferably in the range of 2% by weight to 10% by weight, based on the total monomers used for copolymerization.

  Examples of other monomers include diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene and 1,3-pentadiene, (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α- Unsaturated nitrile compounds such as ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile and fumaric acid dinitrile, (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N, N '-Ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylami , N, N-bis (2-hydroxyethyl) (meth) acrylamide, unsaturated amides such as crotonic acid amide and cinnamic acid amide, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters such as propyl acid, butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate, styrene, α -Aromatic vinyl compounds such as methylstyrene, o-methoxystyrene, p-hydroxystyrene and p-isopropenylphenol, diglycidyl ether of bisphenol A, diglycidyl ether of glycol, etc. and (meth) acrylic acid and hydroxyalkyl (meta Epoxy (meth) acrylate obtained by reaction with acrylate, urethane (meth) acrylate obtained by reaction of hydroxyalkyl (meth) acrylate and polyisocyanate, glycidyl (meth) acrylate and (meth) allyl glycidyl ether, etc. Epoxy group-containing unsaturated compounds, (meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β- (meth) acrylic Unsaturated acid compounds such as loxyethyl and hexahydrophthalic acid-β- (meth) acryloxyethyl, amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate, (meth) acrylamide and dimethyl (Meta) Examples include amide group-containing unsaturated compounds such as acrylamide, and hydroxyl-containing unsaturated compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

  Among these, butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, (meth) acrylic acid and hydroxyalkyl ( Particularly preferred are (meth) acrylates.

  As the other monomer, it is preferable to use at least one diene compound, specifically, butadiene. Such a diene compound is desirably used in an amount of 20 to 80% by weight, preferably 30 to 70% by weight, based on the total monomers used for copolymerization. When the diene compound is copolymerized in the amount as described above with respect to all monomers, soft fine particles are formed. Thereby, (B) polymer becomes a more effective component for making resistance characteristics and the adhesion | attachment to a board | substrate compatible in the copper film formed.

  The average particle diameter of the elastomer fine particles is usually about 30 nm to 500 nm. The average particle diameter of the elastomer fine particles is preferably 40 nm to 200 nm, more preferably 50 nm to 120 nm.

  The method of controlling the particle size of the elastomer fine particles is not particularly limited, but when the elastomer fine particles are synthesized by emulsion polymerization, the number of micelles during the emulsion polymerization is controlled by the amount of the emulsifier used to control the particle size. The method of doing can be illustrated.

  Among the elastomers listed above, it is more preferable to modify the phenol resin using an elastomer having a carbon-carbon double bond because the plasticized phenol resin is excellent in toughness and flexibility. Specifically, natural rubber, isoprene rubber (polyisoprene), butadiene rubber (polybutadiene), chloroprene rubber (polychloroprene), butyl rubber (poly (butylene-co-butadiene)), styrene-butadiene rubber (poly (styrene-co) -Butadiene)), nitrile rubber (poly (acrylonitrile-co-butadiene)), poly (dimethylsiloxane-co-methylvinylsiloxane)), styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer, styrene / butadiene / 2 to 2 carbon atoms such as methacrylate block polymer, dicyclopentadiene, 1,4-hexadiene, cyclooctanediene, methylene norbornene, ethylidene norbornene, butadiene, isoprene Of dienes and α-olefin, carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymer with methacrylic acid, ethylene-α-olefin-diene copolymer rubber, hydrogenated styrene-butadiene rubber (DYNABONHSBR) (Made by JSR)) and rubber-modified epoxy resins which have carbon-carbon double bonds are preferred. These elastomers are used alone or in combination of two or more.

  Furthermore, the composition for forming a copper film of the embodiment of the present invention may contain an elastomer hydrogenated product (component (B3)) as the polymer (B). A preferable elastomer hydrogenated product (B3) includes an elastomer hydrogenated product obtained by hydrogenating the elastomer as the component (B2).

  The polymer (B) contained in the composition for forming a copper film of the present embodiment is at least one selected from the group consisting of the components (B1) and (B2) described above, as described above. Furthermore, it is a relatively soft polymer having a glass transition temperature (Tg) of 50 ° C. or lower. (B) When the coating film of the composition for forming a copper film of the present embodiment is heated on a substrate, the polymer is a metal copper particle (hereinafter referred to as a fluid liquid) formed in the coating film. , Also simply referred to as copper particles), and can facilitate the fusion of the copper particles. Furthermore, (B) polymer suppresses that at least one part remains in the copper film formed in the board | substrate, and a clearance gap is formed in the interface of a board | substrate and a copper film, and a board | substrate and a copper film Adhesion can be increased. Therefore, the polymer (B) is a component for achieving both resistance characteristics and adhesion to the substrate in the formed copper film.

Therefore, the polymer (B) has a Tg of −70 ° C. to 25 ° C. from the viewpoint of achieving both the resistance characteristics of the copper film of the embodiment of the present invention formed on the substrate and the adhesion to the substrate. More preferred is a polymer in the range.
In the present invention, the glass transition temperature (Tg) is a value obtained by measuring the temperature with a temperature gradient of 10 ° C./min using differential scanning calorimetry (DSC).

  As content of (B) polymer in the composition for copper film formation of this embodiment, it is 0.001 mass% with respect to 100 mass% of all the components which the composition for copper film formation of this embodiment contains. It is -20 mass%, Preferably it is 0.005 mass%-10 mass%, More preferably, it is 0.01 mass%-8 mass%. (B) By making content of a polymer into the above-mentioned range, the copper film which was low resistance and excellent in the adhesiveness to a board | substrate can be formed.

[(C) amine compound]
The (C) amine compound contained in the composition for forming a copper film of the present embodiment is represented by at least one general formula of the following general formula (1), the following general formula (2), and the following general formula (3). Is an amine compound.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. R ³ represents a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an amino group, a dimethylamino group, or a diethylamino group.

In the general formula ^{(2), R 5, R} 6 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. R ⁷ represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group. R ⁸ represents an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. However, when R ⁵ and R ⁶ are hydrogen atoms, R ⁸ represents a group other than a methyl group and an ethyl group.

In the general formula (3), R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. R ¹¹ represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group. R ¹² and R ¹³ each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.

Examples of the groups R ¹ and R ² included in the amine compound represented by the general formula (1) include a hydrogen atom, a linear alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, Examples include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a stearyl group, and the branched ones include an isopropyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2 -Trimethylpropyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group Group, 2-heptyl group and the like, alicyclic hydrocarbon group, a cyclohexyl group, a cyclopentyl group.

Examples of the group R ⁴ contained in the amine compound represented by the general formula (1) include a hydrogen atom amino group, a dimethylamino group and a diethylamino group, as well as a linear alkyl group such as a methyl group, ethyl Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group, etc., and isopropyl group, sec-butyl as a branched one Group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethyl Propyl group, 1,2,2-trimethylpropyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethyl A hexyl group, a 2-ethylhexyl group, a 4-heptyl group, a 2-heptyl group, and the like can be given. Examples of the alicyclic hydrocarbon group include a cyclohexyl group and a cyclopentyl group.

  Specific examples of the amine compound represented by the general formula (1) include, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecyl. Amine, dodecylamine, stearylamine, isopropylamine, sec-butylamine, isobutylamine, tert-butylamine, isopentylamine, neopentylamine, tert-pentylamine, 1-ethylpropylamine, 1,1-dimethylpropylamine, 1 , 2-dimethylpropylamine, 1,1,2-trimethylpropylamine, 1,2,2-trimethylpropylamine, 1,3-dimethylbutylamine, neopentylamine, 1,5-dimethylhexylamine 2-ethylhexylamine, 4-heptylamine, 2-heptylamine, cyclohexylamine, cyclopentylamine, ethylenediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N-ethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, 1,4-butanediamine, N, N′-dimethyl-1, Examples include 4-butanediamine, 1,5-pentanediamine, N, N′-dimethyl-1,5-pentanediamine, 1,6-hexanediamine, N, N′-dimethyl-1,6-hexanediamine, and the like. .

Examples of the groups R ⁵ and R ⁶ included in the amine compound represented by the general formula (2) include a hydrogen atom, a linear alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, Examples include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a stearyl group, and the branched ones include an isopropyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2 -Trimethylpropyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group Group, 2-heptyl group and the like, alicyclic hydrocarbon group, a cyclohexyl group, a cyclopentyl group.

And, examples of groups R ⁸ to amine compound represented by the general formula (2) contains, as a linear alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group, etc., and isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group as branched ones Group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1 , 3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group Examples of the alicyclic hydrocarbon group include a cyclohexyl group and a cyclopentyl group. However, when R ⁵ and R ⁶ are both hydrogen atoms, R ⁸ is other than a methyl group or an ethyl group.

  Specific examples of the amine compound represented by the general formula (2) include, for example, propoxymethylamine, propoxyethylamine, isopropoxypropylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropyl. Examples include amine, (ethylhexyloxy) propylamine, isobutoxypropylamine, butoxybutylamine, oxybis (ethylamine) and the like.

Examples of the groups R ⁹ and R ¹⁰ contained in the amine compound represented by the general formula (3) include a hydrogen atom, a linear alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, Examples include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a stearyl group, and the branched ones include an isopropyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2 -Trimethylpropyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group Group, 2-heptyl group and the like, alicyclic hydrocarbon group, a cyclohexyl group, a cyclopentyl group.

Then, as examples of groups R ¹² and R ¹³ amine compound represented by the general formula (3) contains, as a linear alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group, etc. are mentioned, and isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl as branched ones Group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group Group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl , 2-heptyl group and the like, alicyclic hydrocarbon group, a cyclohexyl group, a cyclopentyl group.

  Specific examples of the amine compound represented by the general formula (3) include aminoacetaldehyde diethyl acetal and the like.

  The copper film-forming composition of the present embodiment is selected from the group consisting of amine compounds represented by at least one of the general formulas (1), (2), and (3). It is preferable to use it as a component (C) by combining one selected or two or more compatible with each other. These (C) amine compounds can use commercially available products, and the obtaining method and the like are not particularly limited.

  (C) The purity of the amine compound is not particularly limited, but it is preferably 95% or more so as to reduce the impure content in consideration that the copper film-forming composition is used in the field of electronic materials. 99% or more is more preferable.

  (C) As content of an amine compound, 0.1 mass%-99 mass% are preferable with respect to 100 mass% of all the components which the copper film formation composition of this Embodiment contains, 1 mass%-90 mass% % By mass is more preferable, and 2% by mass to 70% by mass is more preferable. By setting the content of the amine compound to 0.1% by mass to 99% by mass, a copper film having excellent conductivity can be formed. (C) By making content of an amine compound into 1 mass%-99 mass%, the copper film of a lower resistance value can be formed. By setting it as 2 mass%-70 mass%, while being able to achieve copper film formation of a low resistance value, the copper film formation composition excellent in productivity can be prepared.

[solvent]
In the composition for forming a copper film of the present embodiment, a solvent can be added as a component in addition to the components (A) to (C) described above. By adding a solvent to the composition for forming a copper film, it becomes easy to adjust the viscosity of the composition for forming a copper film corresponding to the coating method, and to form a stable and uniform copper film. Is possible.

  The solvent to be added is not particularly limited as long as it can dissolve or disperse each component in the composition for forming a copper film and does not participate in the reaction of the (A) copper salt. Examples thereof include one liquid selected from water, alcohols, ethers, esters, aliphatic hydrocarbons and aromatic hydrocarbons, or two or more compatible liquids.

  Regarding specific examples of the solvent, alcohols include methanol, ethanol, n-propyl alcohol (1-propanol), i-propyl alcohol, n-butyl alcohol (1-butanol), i-butyl alcohol, sec-butyl alcohol, Examples include pentanol, hexanol, heptanol, octanol, nonyl alcohol, decanol, cyclohexanol, benzyl alcohol, terpineol, dihydroterpineol and the like.

  Examples of ethers include hexyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n. -Propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, Tripropylene (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane.

  Examples of the esters include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and γ-butyrolactone.

  Examples of the aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, tetradecane, cyclohexane, decalin and the like. It is done.

  Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, dichlorobenzene, and the like.

  Of these organic solvents, ethers are particularly preferable from the viewpoint of easy adjustment of the viscosity of the composition for forming a copper film.

  The solvent contained in the composition for forming a copper film of this embodiment is an optional component, and the content thereof is 0% by mass to 95% with respect to 100% by mass of all the components of the composition for forming a copper film of this embodiment. It is the range of mass%, it is preferable that it is the range of 0 mass%-70 mass%, and it is more preferable that it is the range of 0 mass%-50 mass%.

[Metal fine particles and other optional components]
The composition for forming a copper film of the present embodiment contains metal fine particles as long as the effects of the present invention are not impaired in addition to the above-described (A) copper salt, (B) polymer and (C) amine compound. Can do. Further, the composition for forming a copper film of this embodiment can contain formic acid and / or ammonium formate as other optional components as long as the effects of the present invention are not impaired, and further, a dispersant, an antioxidant. It is possible to contain a concentration adjusting agent, a surface tension adjusting agent, a viscosity adjusting agent, and a coating film forming auxiliary agent.

  The metal fine particles that can be contained in the composition for forming a copper film of the present embodiment are not particularly limited, but are selected from the group consisting of gold, silver, copper, platinum, ruthenium, rhodium, osmium and palladium, for example. It is preferable that it contains at least one metal species. These metal species may be simple substances or alloys with other metals. When these metal species are a simple substance, preferable metal fine particles are at least one selected from the group consisting of gold fine particles, silver fine particles, copper fine particles, platinum fine particles, ruthenium fine particles, rhodium fine particles, osmium fine particles and palladium fine particles, or A combination of two or more.

  Among these, it is preferable to contain at least one metal species selected from the group consisting of silver, copper and palladium from the viewpoint of cost, availability, and catalytic ability when forming a copper film. Metal fine particles other than these may be used, but during copper film formation, the metal fine particles are not oxidized by the copper ions, or the catalytic ability is not reduced or expressed, and the rate of reduction deposition from copper compounds to copper metal Therefore, it is more preferable to use the metal fine particles described above.

  In the composition for forming a copper film of the present embodiment, the average particle diameter of the metal fine particles is preferably in the range of 0.005 μm to 5 μm. When the particle diameter of the metal fine particles is less than 0.005 μm, the activity of the metal surface becomes very high, which may cause an oxidation reaction and may be dissolved. On the other hand, when the thickness exceeds 5 μm, the metal fine particles may settle when stored for a long time. Therefore, the average particle diameter of the metal fine particles is preferably within the above range.

  In the embodiment of the present invention, as a method for measuring the particle diameter of the metal fine particles, a measurement method applied to general fine particles can be used. For example, a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a field emission scanning electron microscope (FE-SEM), or the like can be used as appropriate. The average particle size value is observed using the above-mentioned microscope, and three locations where the particle sizes are relatively uniform are selected from the observed field of view and photographed at a magnification most suitable for particle size measurement. . From each photograph obtained, select the 100 most likely particles, measure the diameter with a measuring instrument such as a ruler, and calculate the particle size by dividing the measurement magnification. Can be obtained by arithmetic averaging. Further, the standard deviation can be obtained from the particle diameter and number of individual metal fine particles during the above observation. The coefficient of variation can be calculated by the following formula based on the above average particle diameter and its standard deviation.

  In the composition for forming a copper film of the present embodiment, the metal fine particles may be commercially available or may be synthesized by a known method, and is not particularly limited. As a known synthesis method, for example, a gas phase method (dry method) in which a synthesis reaction is performed by a physical method such as a sputtering method or a gas evaporation method, or a metal compound solution is reduced in the presence of a surface protective agent. A liquid phase method (wet method) such as precipitation of metal fine particles is generally known.

  In the composition for forming a copper film of the present invention, the purity of the metal fine particles is not particularly limited. However, if the purity is low, the conductivity may be adversely affected when the conductive thin film is used. % Or more is preferable, and 99% or more is more preferable.

  Although there is no restriction | limiting in particular in the content of the metal microparticle in the composition for copper film formation of this embodiment, It is arbitrary components and is 100 mass% of all the components which the composition for copper film formation of this embodiment contains. The range is preferably 0% by mass to 50% by mass, and more preferably 0% by mass to 20% by mass. By making the content of the metal fine particles in the above range, an improvement in the reduction precipitation rate from the copper compound to the metal copper can be expected, but when the content of the metal fine particles is added to exceed 50% by mass, it is desirable. There is a possibility that a copper film having the resistance characteristic as described above cannot be formed.

  Next, in the composition for forming a copper film of the present embodiment, as long as the effects of the present invention are not impaired, at least one of formic acid and ammonium formate (hereinafter referred to as formic acid or the like for convenience) is used as another optional component. Can be contained. These formic acids and the like have an effect of promoting a reduction reaction when forming a copper film from the copper film forming composition of the present embodiment, and can promote the formation of a copper film having desired resistance characteristics.

  The formic acid and ammonium formate that can be contained in the composition for forming a copper film of the present embodiment can use commercially available products, and the obtaining method and the like are not particularly limited.

  The purity of formic acid and ammonium formate contained in the copper film forming composition of the present embodiment is not particularly limited. However, if the purity is low, there is a concern that the conductivity is lowered when a copper film is formed as the conductive thin film. Therefore, the purity of formic acid and ammonium formate is preferably 95% or more, and more preferably 99% or more.

  In the composition for forming a copper film of the present embodiment, the content of formic acid and the like is not particularly limited, but they are optional components, and 100 mass of all the components contained in the composition for forming a copper film of the present embodiment. % Is preferably in the range of 0% by mass to 50% by mass, and more preferably in the range of 0% by mass to 20% by mass. Even if the content of other optional components is added so as to exceed 50% by mass, an effect corresponding to the content cannot be obtained. Furthermore, the amount of metal copper formed per unit weight of the composition for forming a copper film decreases, and there is a possibility that a copper film having desired characteristics cannot be formed with high production efficiency.

  Moreover, the composition for copper film formation of this embodiment can also contain components other than the above-mentioned formic acid etc. as other arbitrary components, unless the effect of this invention is impaired. About other optional components other than formic acid and the like that can be contained in the composition for forming a copper film of the present embodiment, particularly if it has desired characteristics and does not inhibit the formation reaction of the copper film with a copper compound. It is not limited. For example, it is possible to select from organic solvents in which the above-described components are dissolved and do not react and to be contained as other optional components. And the composition for copper film formation can be prepared so that it may become a desired density | concentration, surface tension, and viscosity by adding the organic solvent.

  The content of other optional components other than formic acid and the like in the composition for forming a copper film of the present embodiment is not particularly limited, but these are optional components, and the composition for forming a copper film of the present embodiment contains. The range is preferably 0% by mass to 50% by mass and more preferably 0% by mass to 20% by mass with respect to 100% by mass of all components. Even if the content of other optional components is added so as to exceed 50% by mass, the effect of other optional components corresponding to the content cannot be obtained. Furthermore, the amount of metal copper formed per unit weight of the composition for forming a copper film decreases, and there is a possibility that a copper film having desired characteristics cannot be formed with high production efficiency.

<Preparation of composition for forming copper film>
[Preparation method]
The composition for forming a copper film of the present embodiment can be easily prepared and manufactured by mixing the above-described (A) copper salt, (B) polymer, and (C) amine compound. The order of mixing is not particularly limited.

  In the preparation of the composition for forming a copper film of this embodiment, it is possible to add a solvent as described above. The addition of the solvent can be performed, for example, after mixing the above-described (A) copper salt, (B) polymer, and (C) amine compound. As described above, the solvent to be added is not particularly limited as long as it dissolves or disperses (A) a copper salt, (B) a polymer, and (C) an amine compound.

  In the preparation of the copper film forming composition of the present embodiment, in addition to the metal fine particles described above, as other optional components, formic acid described above, dispersant, antioxidant, concentration adjusting agent, surface tension adjusting agent, viscosity adjustment An agent or the like can be added. The metal fine particles and other optional components can be added, for example, after mixing (A) a copper salt, (B) a polymer, and (C) an amine compound. And other optional components such as a dispersant, an antioxidant, a concentration adjusting agent, a surface tension adjusting agent, and a viscosity adjusting agent are used together with an essential component such as a copper compound, and the composition for forming a copper film of this embodiment is desired. The component concentration, surface tension, viscosity, and the like can be adjusted.

[Mixing method]
The mixing method in the preparation of the composition for forming a copper film of the present embodiment is not particularly limited, for example, stirring with a stirring blade, stirring with a stirrer and a stirring bar, stirring with a boiler, an ultrasonic homogenizer, Examples thereof include a method using a bead mill, a paint shaker or a stirring deaerator. As mixing conditions, for example, in the case of stirring with a stirring blade, the rotation speed of the stirring blade is usually in the range of 1 rpm to 4000 rpm, preferably in the range of 10 rpm to 2000 rpm.

<Copper film forming method and copper film>
The composition for forming a copper film of the embodiment of the present invention described above is applied onto a desired appropriate substrate to form a coating film of the composition for forming a copper film of the present embodiment. And the coating film of the composition for copper film formation of this embodiment is heated, and forms a copper film on a board | substrate. That is, the copper film formation method of the embodiment of the present invention uses the composition for forming a copper film of the embodiment of the present invention to form the copper film of the embodiment of the present invention. As a result, the wiring board of the embodiment of the present invention can be manufactured using the copper film of the embodiment of the present invention.

  At this time, the copper film forming method of the embodiment of the present invention uses an inert gas such as nitrogen gas, helium gas, and argon gas in the atmosphere by using the composition for forming a copper film of the present embodiment. A copper film can be formed by heating in a non-oxidizing atmosphere. That is, the copper film forming method of the embodiment of the present invention does not particularly require the formation of a reducing atmosphere using a reducing gas such as hydrogen gas, and heating for forming a copper film is simple and safe. A copper film can be formed.

  In the copper film forming method of the embodiment of the present invention, the copper ion of the copper salt (A) undergoes a reduction reaction by heating the coating film of the copper film forming composition of the present embodiment applied on the substrate. To produce copper particles. On the other hand, the polymer (B) in the coating film is heated to become a fluid liquid. Therefore, the copper particles produced in the coating film by heating are easily moved by the fluid liquid, and the fusion is promoted. Furthermore, (B) the polymer improves the adhesion between the copper film and the substrate by leaving at least a portion in the copper film formed on the substrate and entering between the substrate surface and the copper film without a gap. . As a result, the copper film of this embodiment has low resistance and can exhibit excellent adhesion to the substrate.

  Therefore, the copper film forming method of the embodiment of the present invention uses the composition for forming a copper film of the embodiment of the present invention including (1) (A) a copper salt, (B) a polymer, and (C) an amine compound. It is preferable to include a step of forming the coating film on the substrate and (2) a step of heating the coating film on the substrate in the air or in a non-oxidizing atmosphere.

  Hereinafter, the copper film forming method of the embodiment of the present invention will be described in more detail.

[substrate]
In the copper film forming method of the embodiment of the present invention, a known substrate can be used as the substrate for forming the coating film of the copper film forming composition of the present embodiment, and is not particularly limited.

  Examples of the material constituting the substrate include organic base materials such as resins and paper, inorganic base materials such as metals, metal alloys, non-metals, ceramics, and glass, and more specifically, low-density polyethylene resins, High density polyethylene resin, ABS resin (acrylonitrile / butadiene / styrene copolymer synthetic resin), acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene) Naphthalate), resin substrates such as polyacetal resin, cellulose derivatives, uncoated printing paper, fine coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), Unbleached wrapping paper (both kraft paper for heavy bags, both kraft paper ), Bleached wrapping paper (bleached kraft paper, pure white roll paper), coated paper, chipboard, cardboard, and other paper base materials, copper, iron, silver, gold, platinum, aluminum, nickel, titanium, tantalum, cobalt, tungsten, ruthenium Metal substrates such as lead, metal alloy substrates such as duralumin and stainless steel, nonmetal substrates such as carbon, silicon, gallium and zirconia, alumina, titania, tin oxide, yttrium oxide, barium titanate, strontium titanate , Sapphire, zirconia, gallium nitride, silicon nitride, titanium nitride, tantalum nitride, polysilicon, ceramic substrates such as ITO (indium tin oxide), soda glass, borosilicate glass, silica glass, quartz glass, chalcogen glass, etc. A base material is mentioned.

[Coating method]
Examples of the method for applying the composition for forming a copper film of the present embodiment in the method for forming a copper film of the present invention include printing methods such as inkjet printing, gravure printing, flexographic printing, (silk) screen printing, and relief printing. Examples of the coating method include spin coating, spray coating, bar coating, casting, dip coating, and roll coater. The coating amount for applying the composition for forming a copper film of the present embodiment to the substrate can be appropriately adjusted according to the desired film thickness of the copper film.

  The composition for forming a copper film of this embodiment can be applied to the coating method described above. Therefore, the copper film forming method of the embodiment of the present invention uses the composition for forming a copper film of the present embodiment to form a uniform solid coating film on the substrate to form the copper film of the present embodiment. Is possible. Furthermore, the coating film patterned into a desired shape by direct drawing using inkjet printing method, gravure printing method, gravure offset printing method, reverse offset printing method, flexographic printing method, (silk) screen printing method, letterpress printing, etc. It is also possible to form a patterned copper film directly on the substrate to be a wiring, electrode, terminal, or the like. As a result, the wiring board of the embodiment of the present invention can be manufactured using the patterned copper film of the embodiment of the present invention formed on a suitable substrate.

  In this case, the composition for forming a copper film of the present embodiment is suitable for the coating method to be used by adjusting the type and amount of the (C) amine compound, solvent, etc., corresponding to the selected coating method. It is preferable to adjust the viscosity of the composition for forming a copper film so that

[Heating conditions]
In the method for forming a copper film according to the embodiment of the present invention, the heating for forming the copper film from the composition for forming a copper film according to the present embodiment is reducible using a reducing gas such as hydrogen gas as described above. No special atmosphere is required. That is, in the method for forming a copper film according to the embodiment of the present invention, the heating for forming the copper film is performed in an atmosphere other than the atmosphere, for example, by using an inert gas such as nitrogen gas, helium gas, and argon gas. In a non-oxidizing atmosphere. That is, the copper film forming method of the present embodiment is a method of heating a coating film of the composition for forming a copper film of the present embodiment formed on a substrate in the air or in a non-oxidizing atmosphere, and forming a copper film on the substrate. A film can be formed.

  In addition, the copper film formation method of this embodiment heats the coating film of the composition for copper film formation of this embodiment formed on the board | substrate in reducing atmosphere using reducing gas, such as hydrogen gas. It is also possible to form a copper film on the substrate.

  In the copper film forming method of the present embodiment, the heating temperature is not particularly limited as long as the copper salt of the copper film forming composition of the present embodiment is reduced and unnecessary organic substances decompose and volatilize. Absent. For example, the heating temperature is preferably in the range of 50 ° C to 300 ° C, more preferably in the range of 50 ° C to 250 ° C, and still more preferably in the range of 50 ° C to 200 ° C. When the heating temperature is less than 50 ° C., the reduction reaction of the copper salt does not proceed completely, and the remaining of unnecessary organic substances may become remarkable. When the heating temperature exceeds 300 ° C., a substrate made of an organic material can be used. There is a risk of disappearing. If it is 250 degrees C or less, it will become possible to select and use the board | substrate which consists of organic materials. Moreover, if it is 200 degrees C or less, a desired board | substrate can be selected and used from the group of the more various board | substrates including the board | substrate which consists of organic materials.

  Incidentally, when the heating temperature is 250 ° C. or lower, particularly when it is 200 ° C. or lower, there is a concern in the prior art that the characteristics of the copper film are deteriorated due to so-called insufficient heating. However, the copper film forming method of the present embodiment forms a copper film using the composition for forming a copper film of the present embodiment, and the heating conditions are 250 ° C. or lower, and further 200 ° C. or lower. In addition, it is possible to form a copper film having a desired characteristic, particularly a copper film having a desired excellent resistance characteristic. Therefore, from the viewpoint of simplicity and the like, as described above, in the copper film forming method of the embodiment of the present invention, the heating temperature is preferably 250 ° C. or less, and more preferably 200 ° C. or less.

  The heating time may be appropriately selected in consideration of the type of each component such as (A) copper salt and (C) amine compound, and the desired conductivity (resistance value) of the copper film, and is particularly limited. is not. And when the comparatively low heating temperature of about 200 degreeC or less is selected, it is preferable that heating time shall be about 5 to 100 minutes.

  As described above, the copper film forming method according to the embodiment of the present invention uses the composition for forming a copper film according to the present embodiment, and does not particularly require a reducing atmosphere using a reducing gas such as hydrogen gas. In addition to the below, for example, a low resistance copper film can be easily formed by heating at a low temperature in a non-oxidizing atmosphere using an inert gas such as nitrogen gas, helium gas and argon gas. And the wiring board of embodiment of this invention can be provided using the copper film of embodiment of this invention on the obtained board | substrate.

<Electronic equipment>
The copper film formation method of embodiment of this invention mentioned above forms the copper film of embodiment of this invention using the composition for copper film formation of embodiment of this invention. And the electronic device of embodiment of this invention which uses the copper film of embodiment of this invention and uses it as a wiring, and uses it as a wiring, a plating electric power feeding film, an electrode, or a terminal can be provided. .

  Examples of the electronic apparatus according to the embodiment of the present invention include an antenna, a sensor, a capacitor, an arithmetic element, a touch panel, a liquid crystal display element, and an organic EL element. Moreover, the electronic device with a touchscreen provided with the touchscreen of embodiment of this invention can be mentioned as an input device.

  Hereinafter, the touch panel of the embodiment of the present invention exemplified as the electronic apparatus of the embodiment of the present invention will be described.

[Touch panel]
The touch panel according to the embodiment of the present invention is, for example, a touch panel having a light-transmissive insulating film formed on a substrate provided with a detection electrode and a lead-out wiring for extracting the detection electrode so as to cover the detection electrode. . This touch panel can be, for example, a capacitive touch panel.

  Note that the touch panel according to the embodiment of the present invention may have a structure in which the above-described insulating film is not provided.

  FIG. 1 is a plan view showing a touch panel according to an embodiment of the present invention.

  FIG. 2 is a sectional view taken along line B-B ′ of FIG. 1.

  As shown in FIG. 1, the touch panel 21 of the present embodiment includes a first detection electrode 23 extending in the X direction and a second detection electrode extending in the Y direction orthogonal to the X direction on the surface of the transparent substrate 22. 24.

  The transparent substrate 22 can be a glass substrate. The transparent substrate 22 can also be a resin substrate. In that case, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene film, a polypropylene film, a polyethersulfone film, a polycarbonate film, a polyacryl film, a polyvinyl chloride film, A polyimide film, a ring-opened polymer film of cyclic olefin, a film made of a hydrogenated product thereof, and the like can be used. The thickness of the transparent substrate 22 can be 0.1 mm to 3 mm in the case of a glass substrate. In the case of a resin substrate, it can be 10 μm to 3000 μm.

  A plurality of first detection electrodes 23 and second detection electrodes 24 are arranged. The first detection electrodes 23 and the second detection electrodes 24 are arranged in a matrix in the operation area of the touch panel 21. The first detection electrode 23 is used to detect the coordinate in the Y direction of the touch position by the operator. The second detection electrode 24 is used to detect the coordinate in the X direction of the touch position by the operator. The first detection electrode 23 and the second detection electrode 24 are provided in the same layer on the same surface of the transparent substrate 22. The number of the first detection electrodes 23 and the second detection electrodes 24 is not limited to the example shown in FIG. 1, but is preferably determined according to the size of the operation area and the required touch position detection accuracy. . That is, the touch panel 21 can be configured by using a larger number or a smaller number of the first detection electrodes 23 and the second detection electrodes 24.

  As shown in FIG. 1, each of the first detection electrode 23 and the second detection electrode 24 includes a plurality of rhomboid electrode pads 30. The first detection electrode 23 and the second detection electrode 24 are arranged such that the electrode pad 30 of the first detection electrode 23 is separated from the electrode pad 30 of the second detection electrode 24 adjacent thereto. At this time, the gap between the electrode pads 30 is very small enough to ensure insulation.

  And the 1st sensing electrode 23 and the 2nd sensing electrode 24 are arrange | positioned so that the part which mutually cross | intersects can be made as small as possible. Then, the electrode pads 30 constituting the first detection electrode 23 and the second detection electrode 24 are arranged over the entire operation area of the touch panel 21.

  As shown in FIG. 1, the electrode pad 30 may have a rhombus shape, but is not limited to such a shape, and may be a polygonal shape such as a hexagon, for example.

  Each of the first detection electrode 23 and the second detection electrode 24 is preferably a transparent electrode so as not to lower the visibility of a display such as a liquid crystal display element (not shown) disposed under the touch panel 21. Here, the transparent electrode is an electrode having high transparency to visible light. As the first detection electrode 23 and the second detection electrode 24, an electrode made of a transparent conductive material such as an electrode made of ITO or an electrode made of indium oxide and zinc oxide can be used. When the 1st sensing electrode 23 and the 2nd sensing electrode 24 consist of ITO, respectively, it is preferable that those thickness shall be 10 nm-100 nm so that sufficient electroconductivity can be ensured.

  The first detection electrode 23 and the second detection electrode 24 can be formed using a known method. For example, a film made of a transparent conductive material such as ITO is formed using a sputtering method or the like, and photolithography is performed. This can be done by patterning using a method or the like.

  As shown in FIGS. 1 and 2, the first detection electrode 23 and the second detection electrode 24 are formed on the same surface of the transparent substrate 22 and form the same layer. Therefore, the first detection electrode 23 and the second detection electrode 24 intersect at a plurality of locations in the operation region, and form an intersection 28.

  As shown in FIG. 2, the touch panel 21 of the present embodiment is divided so that one of the first detection electrode 23 and the second detection electrode 24 does not contact the other at the intersection 28. That is, the first detection electrode 23 is connected at the intersection 28, but the second detection electrode 24 extending in the left-right direction in FIG. 2 is divided and formed. A bridge electrode 32 is provided to electrically connect the disconnected portion of the second detection electrode 24. An interlayer insulating film 29 made of an insulating material is provided between the bridge electrode 32 and the first detection electrode 23.

As shown in FIG. 2, the interlayer insulating film 29 provided on the first detection electrode 23 at the intersection 28 is formed of a material having excellent light transmittance. The interlayer insulating film 29 can be formed by applying polysiloxane, acrylic resin, acrylic monomer, or the like by a printing method, performing patterning when necessary, and then heat-curing it. When formed using polysiloxane, the interlayer insulating film 29 is an inorganic insulating layer made of silicon oxide (SiO ₂ ). Further, when an acrylic resin and an acrylic monomer are used, the interlayer insulating film 29 is an organic insulating layer made of resin. In the case where SiO ₂ is used for the interlayer insulating film 29, for example, the SiO ₂ film is formed only on the first detection electrodes 23 at the intersections 28 by a sputtering method using a mask to form the interlayer insulating film 29. You can also

  A bridge electrode 32 is provided on the interlayer insulating film 29. As described above, the bridge electrode 32 functions to electrically connect the second detection electrodes 24 that are interrupted at the intersection 28. The bridge electrode 32 is preferably formed of a material having excellent light transmittance such as ITO. By providing the bridge electrode 32, the second detection electrode 24 can be electrically connected in the Y direction.

  As shown in FIG. 2, the first detection electrode 23 and the second detection electrode 24 have a shape in which a plurality of rhomboid electrode pads 30 are arranged vertically or horizontally as described above. In the first detection electrode 23, the connection portion located at the intersection 28 has a shape narrower than the rhomboid electrode pad 30 of the first detection electrode 23. The bridge electrode 32 is also narrower than the rhomboid electrode pad 30 and is formed in a strip shape.

  Terminals (not shown) are provided at the ends of the first detection electrode 23 and the second detection electrode 24 of the touch panel 21, respectively, and lead-out wirings 31 are drawn from the terminals. The lead wiring 31 can be a metal wiring using the copper film of the embodiment of the present invention described above. Similarly, the terminal can also be formed using the copper film of the embodiment of the present invention.

  That is, the lead-out wiring 31 and the like of the touch panel 21 can be formed according to the copper film forming method of the above-described embodiment of the present invention using the copper film forming composition of the above-described embodiment of the present invention.

  For example, by the coating method exemplified in the copper film forming method of the embodiment of the present invention, the coating film of the composition for forming a copper film of the present embodiment is made transparent such that the first detection electrode 23 and the second detection electrode 24 are formed. A wiring pattern is formed on the substrate 22. For example, a coating film is formed by direct drawing using an inkjet printing method, gravure printing method, gravure offset printing method, reverse offset printing method, flexographic printing method, (silk) screen printing method, letterpress printing, etc. Can be formed.

  And as above-mentioned, it can heat in non-oxidizing atmosphere using inert gas, such as nitrogen gas, helium gas, and argon gas other than air | atmosphere, for example, and the lead-out wiring 31 etc. can be formed.

  Note that, as described above, the coating film can be heated in a reducing atmosphere using a reducing gas such as hydrogen gas.

  The lead-out wiring 31 uses an external connection circuit (not shown) that detects the position of voltage application and touch operation to the first detection electrode 23 and the second detection electrode 24 using a connection terminal (not shown) at the end thereof. Is electrically connected.

  As shown in FIGS. 1 and 2, light is applied to the surface of the transparent substrate 22 on which the first detection electrode 23 and the second detection electrode 24 are disposed so as to cover the first detection electrode 23 and the second detection electrode 24. A transparent insulating film 25 is disposed.

  The insulating film 25 is formed by patterning so as to cover and protect the first detection electrode 23 and the second detection electrode 24 in the operation region of the touch panel 21. In addition, the insulating film 25 is formed by patterning so that the connection terminals (not shown) at the ends of the lead-out wirings 31 drawn from the first detection electrode 23 and the second detection electrode 24 are exposed.

  The insulating film 25 can be formed using a radiation-sensitive resin composition, and can be disposed on the first detection electrode 23 and the second detection electrode 24 by performing predetermined patterning.

  The touch panel 21 is a cover film made of a transparent resin using, for example, an adhesive layer (not shown) made of an acrylic transparent adhesive on the formation surface of the first detection electrode 23 and the second detection electrode 24 of the transparent substrate 22. (Not shown) can be provided.

  The touch panel 21 having the above configuration measures capacitance in an operation region in which the first detection electrodes 23 and the second detection electrodes 24 are arranged in a matrix, and when there is a touch operation such as an operator's finger. The contact position of a finger or the like can be detected from the change in capacitance that occurs. Then, it can be mounted on a display such as a liquid crystal display element or an organic EL element, and can be suitably used as an input device for a display of an electronic device.

  Therefore, using the composition for forming a copper film of the embodiment of the present invention, the lead-out wiring is configured using the copper film of the embodiment of the present invention formed according to the copper film forming method of the embodiment of the present invention described above. be able to. And a touch panel can be comprised using the lead-out wiring which consists of a copper film of the embodiment of the present invention. Furthermore, the electronic device of embodiment of this invention, such as a liquid crystal display element provided with the touch panel and an organic EL element, can be provided. Therefore, an electronic apparatus such as a liquid crystal display element with a touch panel according to an embodiment of the present invention is configured to include the copper film according to the embodiment of the present invention formed according to the copper film forming method according to the embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples.

<Examples 1-20 and Comparative Examples 1-4>
In Examples 1 to 20 and Comparative Examples 1 to 4, the compositions for forming a copper film of Examples 1 to 20 and Comparative Examples 1 to 4 were prepared by the method shown below. The copper films of Examples 1 to 20 and Comparative Examples 1 to 4 were formed using And as evaluation of these copper films, resistance characteristics (volume resistance value) were evaluated, and also adhesiveness was evaluated.

[Preparation of composition for forming copper film]
The types and addition amounts shown in Table 1 (A) copper salt, (B) polymer, (C) amine compound, and additives added as necessary are mixed at room temperature using a stirrer. The composition for forming a copper film was prepared by stirring at 200 rpm for 60 minutes.

  The copper salt (A) used for the preparation of each composition for forming a copper film in Examples 1 to 20 and Comparative Examples 1 to 4 was copper formate, and a commercially available product was used.

  The polymer (B) used for the preparation of each composition for forming a copper film in Examples 1 to 20 and Comparative Examples 1 to 4 was all an elastomer, and the polymer species shown in Table 1 were used. . Here, the polymers G-1000, Gl-1000, B-3000 and Bl-3000 shown in Table 1 are manufactured by Nippon Soda Co., Ltd., and L-SBR-820, L-SBR-841, LIR-310 and UC-203 is manufactured by Kuraray Co., Ltd., Poly ip and Poly bd are manufactured by Idemitsu Kosan Co., Ltd., Lucant HC-40 is manufactured by Mitsui Chemicals, and HV-1900 and HV-300 are manufactured by JX Nippon Mining & Energy Corporation. Both are commercially available products.

  Commercially available products were all used for the (C) amine compounds used in the preparation of the copper film forming compositions of Examples 1 to 20 and Comparative Examples 1 to 4.

  The additive HPM used in the preparation of the copper film forming compositions of Examples 3 and 4 and Comparative Examples 1 and 4 is hydroxypropylcellulose manufactured by Nippon Soda Co., Ltd. It is.

[Formation of copper film]
PET film with ITO having a square shape of 150 mm in length and 150 mm in width using the compositions for forming a copper film of Examples 1 to 20 and Comparative Examples 1 to 4 and having an ITO film formed on the surface thereof On top of, was applied using a bar coater. And the coating film of the composition for copper film formation which was patterned by the rectangular shape of 50 mm long and 100 mm wide, and whose film thickness is 100 micrometers was formed. Next, using a hot plate, the heating atmosphere was changed to a non-oxidizing atmosphere (nitrogen atmosphere) using nitrogen gas, and the ITO-coated PET film on which the aforementioned coating film was formed was heat-treated at a predetermined temperature for 10 minutes.

  As a result, copper films of Examples 1 to 20 and Comparative Examples 1 to 4 were obtained as thin films patterned into the above-described shape having a film thickness of about 0.1 μm to 20 μm.

  In addition, about formation of each copper film using the composition for copper film formation of Example 1- Example 20 and Comparative Example 1- Comparative Example 4, heating temperature and a heating atmosphere are put together in Table 2 mentioned later as heating conditions. Showed.

[Evaluation]
(Measurement of volume resistance)
Example 1 to Example 20 and Comparative Example 1 to Comparative Example 1 and Comparative Example 1 to Comparative Example 1 to Comparative Example 1 to Comparative Example 1 to Comparative Example 1 to Comparative Example 1 to Comparative Example 1 and Comparative Example 1 to Comparative Example Using the copper films of Example 4, their specific resistance values (volume resistance values) were measured using a four-probe resistance measuring machine (trade name: Model sigma-5, NPS). The measurement results are summarized in Table 2.

  As shown in Table 2, the volume resistance values of the copper films of Examples 1 to 20 obtained by the compositions for forming the copper films of Examples 1 to 20 are 30 μΩ / cm or less. Showed a low value. It was found that each of the compositions for forming a copper film of Examples 1 to 20 containing (B) a polymer together with (A) a copper salt and (C) an amine compound can form a low resistance copper film.

(Evaluation of adhesion)
Examples 1 to 20 formed on a PET film with ITO, which is a substrate, by using the copper film forming compositions of Examples 1 to 20 and Comparative Examples 1 to 4 by the copper film forming method described above. Using each copper film of Example 20 and Comparative Examples 1 to 4, the adhesion to the substrate was evaluated.

  The adhesion between the copper film and the substrate was evaluated by performing a tape peeling test using Scotch (registered trademark) # 600 Tape, which is an adhesive tape manufactured by 3M. Specifically, in the tape peeling test using the above-mentioned adhesive tape, when all or almost the copper film was peeled off from the ITO-attached PET film as the substrate, it was evaluated as defective (x). On the other hand, when peeling did not occur or when the peeled portion was about half or less of the entire copper film, it was evaluated as good (◯). The evaluation results are summarized in Table 2.

  As shown in Table 2, each of the copper films of Examples 1 to 20 has excellent adhesion to the substrate, while each of the copper films of Comparative Examples 1 to 4 has low adhesion to the substrate. I understood it.

  From the above evaluation results, the copper films of Examples 1 to 20 formed by the copper film forming method described above using the compositions for forming a copper film of Examples 1 to 20 were excellent in resistance. It has been found that both the characteristics and the adhesion to the excellent substrate are compatible.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention.

  The composition for forming a copper film of the present invention can be suitably used as a composition for forming a conductive pattern of a circuit board in the electronics field. And the copper film of this invention and the copper film formation method of this invention can be used for manufacture of an electronic component etc. in the electronics field | area. For example, the copper film of the present invention and the copper film forming method of the present invention can be used for the production of wirings, circuit boards, antennas, sensors, arithmetic elements and display elements. Furthermore, the composition for forming a copper film of the present invention includes various coating methods such as a spin coating method, a spray coating method, a bar coating method, a casting method, a dip coating method, and a roll coater method as a conductive ink, and inkjet printing. It can be suitably used for various types of printing such as screen printing, flexographic printing, gravure offset printing, and reverse offset printing.

21 Touch Panel 22 Transparent Substrate 23 First Sense Electrode 24 Second Sense Electrode 25 Insulating Film 28 Intersection 29 Interlayer Insulating Film 30 Electrode Pad 31 Lead-out Wire 32 Bridge Electrode

Claims (10)

(A) copper salt,
(B) A composition for forming a copper film, comprising a polymer having a glass transition temperature (Tg) of 50 ° C. or lower, and (C) an amine compound.   (A) Copper salt is copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper pivalate, copper formate, copper hydroxyacetate, copper glyoxylate, copper oxalate Acetylacetonato copper, 1,1,1-trifluoroacetylacetonatocopper and 1,1,1,5,5,5-hexafluoroacetylacetonatocopper at least one selected from the group consisting of The composition for forming a copper film according to claim 1.   (B) Tg of a polymer exists in the range of -70 to 25 degreeC, The composition for copper film formation of Claim 1 or 2 characterized by the above-mentioned.   The polymer (B) is at least one selected from the group consisting of a (meth) acrylic compound having a weight average molecular weight of 300,000 or less, an elastomer, and a hydrogenated product of the elastomer. The composition for copper film formation of any one of Claims.   The elastomer is at least one selected from the group consisting of natural rubber, styrene elastomer, olefin elastomer, urethane elastomer, polyester elastomer, acrylic elastomer, polyamide elastomer, silicone elastomer, chlorosulfonated polyethylene, fluororubber, and polysulfide elastomer. The composition for forming a copper film according to claim 4. The (C) amine compound is represented by at least one of the following general formula (1), the following general formula (2), and the following general formula (3). The composition for forming a copper film according to claim 1.
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having ³ to 18 carbon atoms. R ³ represents , A single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon having 3 to 18 carbon atoms. Group, amino group, dimethylamino group, or diethylamino group.)
(In General Formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. R ⁷ represents , A methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group, and R ⁸ represents an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. (However, when R ⁵ and R ⁶ are hydrogen atoms, R ⁸ represents a group other than a methyl group or an ethyl group.)
In (formula ^{(3), R 9, R} 10 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or,, ^{.R 11} of an alicyclic hydrocarbon group having 3 to 18 carbon atoms , A methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group, R ¹² and R ¹³ are each independently an alkyl group having 1 to 18 carbon atoms or an alicyclic ring having 3 to 18 carbon atoms. Represents a hydrocarbon group.)   It has a process of forming a coating film using the composition for copper film formation of any one of Claim 1 to 6, and heating the said coating film in air | atmosphere of 250 degrees C or less, or non-oxidizing atmosphere. A method for forming a copper film.   It forms using the composition for copper film formation of any one of Claim 1 to 6, The copper film characterized by the above-mentioned.   A wiring board comprising the copper film according to claim 8.   An electronic apparatus comprising the copper film according to claim 8.