JP3774638B2 - Circuit pattern forming method using inkjet printing method - Google Patents

Circuit pattern forming method using inkjet printing method Download PDF

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Publication number
JP3774638B2
JP3774638B2 JP2001125967A JP2001125967A JP3774638B2 JP 3774638 B2 JP3774638 B2 JP 3774638B2 JP 2001125967 A JP2001125967 A JP 2001125967A JP 2001125967 A JP2001125967 A JP 2001125967A JP 3774638 B2 JP3774638 B2 JP 3774638B2
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circuit pattern
particles
metal
conductive metal
ultrafine
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JP2002324966A (en
Inventor
雅行 上田
英之 後藤
頼重 松葉
憲明 畑
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ハリマ化成株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming a circuit pattern using a conductive metal paste using an inkjet printing method. More specifically, the present invention relates to digital high-density wiring on rigid and flexible printed boards, IC chips, glass substrates, ceramic substrates, and the like. The present invention relates to a method of forming an extremely fine circuit pattern with a low impedance corresponding to the above by using an inkjet printing method with a conductive metal paste for ultra fine printing.
[0002]
[Prior art]
As a method of drawing and forming a circuit pattern on a printed wiring board, in many cases, a screen printing, in particular, applying a conductive metal paste using a metal mask, and then heat-curing, is desired. A low resistance circuit pattern is formed. The drawing method using this screen printing method is widely applied to the field where the line width of the circuit pattern to be formed is not extremely narrow, and the conductive metal paste used is a metal powder having an average particle diameter of 0.5 to 20 μm. In general, those obtained by dispersing in a thermosetting resin composition are used. The film thickness of the circuit pattern to be drawn is selected in a range in which the ratio of the film thickness / minimum line width and the aspect ratio do not become extremely small according to the minimum line width to be formed.
[0003]
On the other hand, with the rapid miniaturization of information terminals in recent years, the wiring pitch of the printed wiring board mounted on the information terminal has also been narrowed. Specifically, it is formed on the printed wiring board as the circuit in the semiconductor becomes finer. The minimum line width and film thickness of the circuit pattern to be produced will become increasingly narrower. For example, when a conventional metal paste using a metal powder having an average particle diameter of 0.5 μm or more is used when the film thickness is about several microns, the particle diameter of the metal powder contained is relatively large. For this reason, sufficient response cannot be achieved. Specifically, in some cases, there are only two or three metal particles in the thickness direction of only a few microns, and as a result, the film thickness distribution is relatively large, and the conductivity variation is large. May become noticeable. In addition, when only a few metal particles are present, the conductivity may be greatly impaired when a defect occurs in the contact between the particles partially.
[0004]
In addition, the metal mask used for screen printing itself has a limited mechanical thinning in order to maintain the desired mechanical strength, and the width between adjacent circuits depends on the thickness of the metal mask itself. Naturally there are limits. For example, when aiming to mount a high-density electronic component with a distance between circuits of 0.3 mm or less, it becomes difficult to draw a circuit pattern using a screen printing method with high reproducibility. . On the other hand, in the ink jet drawing method or the method of discharging the metal paste using a nozzle or needle, the drawing is possible because the drawing is performed directly using the ejected minute liquid metal paste. The minimum line width and the minimum distance between circuits depend only on the amount of metal paste in the form of droplets applied by spraying. Therefore, if the droplet-like metal paste to be ejected is made finer, it can be selectively applied only to a very narrow range. For example, a high density with a distance between circuits of 0.3 mm or less is possible. It can also be applied to the production of circuit patterns.
[0005]
In addition, when an ink-jet drawing method is used, even when a circuit pattern has a complicated shape, for example, a thin line width portion and a wide solid print area are mixed, in principle, the film thickness is determined as a unit area. Since it is determined only by the amount of the droplet-shaped metal paste applied per hit, it is possible to achieve high film thickness uniformity. In this case, for example, when the film thickness is about several microns, using a conventional metal paste using metal powder having an average particle diameter of 0.5 μm or more is the same as when using the above-described screen printing method. Moreover, since the particle size of the metal powder contained is relatively large, it is not possible to cope with it sufficiently.
[0006]
[Problems to be solved by the invention]
In other words, when an inkjet drawing method is used to form a circuit pattern, the metal powder contained in the conductive metal paste to be used has a sufficiently fine particle size in order to fully exhibit its high drawing resolution. Need to be. For example, it is necessary to use a conductive metal paste that contains ultrafine metal particles having a very small particle diameter.
[0007]
As one method for producing ultrafine metal particles having a very small particle diameter, at least an ultrafine metal particle having an average particle diameter of 100 nm or less, Japanese Patent Application Laid-Open No. 3-34211 is prepared by using a gas evaporation method. Disclosed are colloidal dispersions of ultrafine metal particles of 10 nm or less and a method for producing the same. JP-A-11-319538 discloses a colloidal dispersion of ultrafine metal particles having an average particle diameter of several nanometers to several tens of nanometers using a reduction precipitation method using an amine compound for reduction. A manufacturing method is disclosed. The ultrafine metal particles having an average particle diameter of about several nanometers to several tens of nanometers disclosed in JP-A-11-319538 are coated with a polymer resin or the like in order to maintain a colloidal state. .
[0008]
When a metal paste composed of such fine metal particles having an average particle diameter of 1 to 100 nm is used, the metal particles used in principle can be used even when the fine line width and the corresponding thin film thickness are used. It is possible to greatly reduce the thickness non-uniformity caused by the particle diameter of the particles. Taking advantage of this advantage, it is desired to use a conductive metal paste containing metal ultrafine particles having an average particle size of several nanometers to several tens of nanometers in an ink jet drawing method for forming a circuit pattern. In other words, it is desired to develop a method for forming a circuit pattern using a conductive metal paste containing metal ultrafine particles in a form suitable for use in an ink jet drawing method and using an ink jet printing method using the conductive metal paste.
[0009]
In general, it is known that ultrafine metal particles having an average particle diameter of several nanometers to several tens of nanometers are sintered at a temperature much lower than the melting point (for example, 200 ° C. for silver). In this low-temperature sintering, if the particle size of metal ultrafine particles is sufficiently reduced, the proportion of the high energy state atoms present on the particle surface will increase and the surface diffusion of metal atoms will be ignored. This is because, as a result of being unacceptably large, due to the surface diffusion, the interface between the particles is stretched and sintered. On the other hand, this property causes a phenomenon that aggregates are formed when the surfaces of metal ultrafine particles are in direct contact with each other even near room temperature. The formation of the agglomerates is a factor that impairs the effect of improving the thickness uniformity, which is achieved as a result of extremely fine metal fine particles forming a dense packing state. Furthermore, by forming a densely packed state, the effect of achieving the desired conductivity as a whole is mixed with the structure in which the agglomerates are partially formed in advance. It becomes a cause that cannot be achieved.
[0010]
In addition, on the surface of ultrafine metal particles, not only is the surface diffusion of metal atoms more active than the surface of a normal metal lump, but also the chemical reactivity is increased. For example, it is more rapid when exposed to oxygen. Surface oxidation proceeds. In this case, the advantage of low-temperature sintering on the surface of ultrafine metal particles is lost, and for the first time, the heat treatment at a relatively high temperature necessary to eliminate the effect of the oxide film formed by surface oxidation is the first It will be in the state which can achieve mutual sintering of fine particles. Therefore, depending on the degree of the oxide film to be formed, it becomes a factor causing variation in conductivity.
[0011]
In particular, when the conductive metal paste containing ultrafine metal particles is sprayed and applied using the inkjet method, the uniformity of the ultrafine metal particles contained in the fine droplets to be ejected is essential. is there. That is, it is an essential requirement that the ultrafine metal particles contained in the conductive metal paste are in a state of being uniformly dispersed in the dispersion solvent. Specifically, it is necessary to suppress phenomena such as agglomeration and separation of ultrafine metal particles or sedimentation and separation while being held in a container attached to an inkjet printer head to be used. Needless to say, the above-mentioned aggregated ultrafine metal particles should not adhere to the tip of the discharge nozzle of an inkjet printer head. Use of conductive metal paste containing ultrafine metal particles that can avoid problems inherent in using the inkjet method described above, achieve high film thickness uniformity and, in addition, good conductivity Development of a method for forming a circuit pattern using an ink jet printing method is desired.
[0012]
The present invention solves the above-mentioned problems, and an object of the present invention is to aggregate the ultrafine metal particles contained even when stored using ultrafine metal particles as the conductive medium constituting the conductive metal paste. A conductive metal paste that uniformly disperses such ultrafine metal particles while suppressing aggregate formation or sedimentation separation is sprayed and applied onto a substrate using an ink-jet printing method, and when baked, adhesion force An object of the present invention is to provide a method for forming a circuit pattern using a novel ink jet printing method, which can form a circuit pattern with a smooth surface shape and a low resistance and an ultrafine pattern.
[0013]
[Means for Solving the Problems]
As a result of diligent research to solve the above-mentioned problems, the present inventors have found that when metal ultrafine particles having an average particle diameter of 1 to 100 nm are used as the conductive medium constituting the conductive metal paste, the conductivity is high. When preparing the metal paste itself, the stabilized colloidal state is preferable for improving the aggregation resistance, but the colloidal state is maintained when the thermosetting resin contained as the binder component is heat-cured. When the molecular layer that covers the surface of the ultrafine metal particles that contributes to the surface remains intact, sintering at a low temperature between the ultrafine metal particles is essential to achieve excellent electrical conductivity. It has been found that the fusion at the contact interface due to the above is inhibited. As a result of further research and examination based on this knowledge, the surface of the metal ultrafine particles that contribute to the maintenance of a stabilized colloidal state is prepared while the conductive metal paste itself is prepared and stored near room temperature. On the other hand, when the low temperature curable thermosetting resin is heated and cured, the molecular layer covering the surface can be effectively removed. The surface shape is smooth due to the use of ultrafine metal particles that have sufficient adhesion to the substrate and are uniformly dispersed in a colloidal form due to the thermosetting resin (organic binder) component. The conductivity imparted to the thin film wiring pattern to be formed is sufficiently high and the reproducibility of the thin film wiring pattern can be kept high while maintaining the advantages of ultra-fine circuit drawing by the method. It was heading.
[0014]
That is, a circuit pattern forming method using the inkjet printing method of the present invention is a method of drawing and forming a circuit pattern on a wiring board with a conductive metal paste using an inkjet method,
The conductive metal paste to be used is a conductive metal paste obtained by uniformly dispersing ultrafine metal particles having a fine average particle diameter in a resin composition containing an organic solvent,
The metal ultrafine particles having a fine average particle diameter are selected in the range of 1 to 100 nm in average particle diameter, and the surface of the metal ultrafine particles can be coordinated with the metal elements contained in the metal ultrafine particles. Covered with one or more compounds having groups containing nitrogen, oxygen, sulfur atoms as groups,
A step of drawing a circuit pattern composed of a coating film of the conductive metal paste by spraying and applying on a substrate as fine droplets by an ink jet drawing means;
A circuit pattern forming method using an inkjet printing method, comprising: a step of heat-treating the drawn conductive metal paste coating film at least at a temperature at which the thermosetting resin is thermally cured It is. At that time, the resin composition is a thermosetting resin component that functions as an organic binder. When heated, the resin composition is one or more compounds having a group containing nitrogen, oxygen, and sulfur atoms. It preferably contains a component having reactivity with a group containing an atom, and at least one organic solvent.
[0015]
Furthermore, in the process of drawing the circuit pattern,
A liquid obtained by dispersing ultrafine metal particles coated with one or more compounds having a group containing nitrogen, oxygen, and sulfur atoms in an organic solvent;
A thermosetting resin component that constitutes the resin composition, a component having reactivity with a group containing nitrogen, oxygen, and sulfur atoms, and a liquid containing an organic solvent,
A method of forming a circuit pattern, characterized in that an individual ink jet drawing means is used to spray and apply on a substrate, and both liquids are mixed on the substrate to form a coating film made of a conductive metal paste. It can also be. In addition, it is preferable to use an organic acid anhydride, a derivative thereof, or an organic acid as a component having reactivity with the group containing nitrogen, oxygen, or sulfur atoms.
[0016]
On the other hand, the metal ultrafine particles with a fine average particle diameter contained in the conductive metal paste are gold, silver, copper, platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium, The circuit pattern forming method may be fine particles made of one kind of metal selected from the group consisting of aluminum or fine particles of an alloy made of two or more kinds of metals.
[0017]
Further, in the circuit pattern forming method of the present invention, at least at a temperature at which the thermosetting resin is thermally cured,
Furthermore, the metal fine particles contained in the conductive metal paste in the drawn coating film can also be sintered and are preferable.
[0018]
For example, the ink jet drawing means is a thermal drawing means that generates bubbles by heating and foaming and discharges droplets.
One or more organic solvents contained in the conductive metal paste to be used may have a boiling point lower than the heating temperature of the heating foaming. Alternatively, the ink jet drawing means is a piezo drawing means for discharging droplets by compression using a piezo element,
One or more organic solvents contained in the conductive metal paste to be used have a boiling point equal to or lower than a temperature at which at least the thermosetting resin is thermally cured, and a circuit pattern forming method, You can also
[0019]
Preferably, in the conductive metal paste used for forming the circuit pattern, the resin composition containing the organic solvent is included in a range of 50 to 300 parts by mass per 100 parts by mass of the ultrafine metal particles,
Among these, it is preferable that the said organic solvent is contained in 20-270 mass parts.
[0020]
In the method for forming a circuit pattern of the present invention, for example, the thermosetting resin component functioning as an organic binder used in the resin composition is heated using the organic acid anhydride or a derivative thereof or an organic acid as a polymerization agent. It is more preferably a polymerizable thermosetting resin.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Below, the formation method of the circuit pattern using the inkjet printing method of this invention is demonstrated in detail.
[0022]
The circuit pattern forming method of the present invention is mainly used for digital high-density printing using minimum dot-like printing, which is not easy to draw with high reproducibility by the conventional screen printing method or dispense printing method. Because it is for ultra-fine printing, which is used for the formation of extremely fine circuits and interlayer junctions with low impedance corresponding to density wiring, the ultrafine metal particles contained as a conductive medium are the target for ultra-fine printing. The average particle diameter is selected in the range of 1 to 100 nm according to the width and the film thickness after heat curing. Preferably, the average particle size is selected in the range of 2 to 10 nm.
[0023]
Thus, when using extremely fine metal ultrafine particles, even when they are immersed in a dispersion solvent, when the metal particles come into contact with each other, the metal ultrafine particles adhere to each other, causing aggregation. Such agglomerates are not suitable for the ultra-fine printing intended by the present invention. In order to prevent these particles from aggregating, a coating layer made of low molecules is provided on the surface of the ultrafine metal particles, and the particles are dispersed in a solution that dissolves the thermosetting resin component.
[0024]
In addition, in the method for forming a circuit pattern of the present invention, when the thermosetting resin component contained in the conductive metal paste applied on the substrate is heat-cured, the metal ultrafine particles contained as the conductive medium are bonded together. In order to cause fusion at the contact interface, the surface of the ultrafine metal particles is used so that the oxide film is not substantially present. Specifically, although the surface of the ultrafine metal particle itself does not have an oxide film, a group containing nitrogen, oxygen, or sulfur atom is included as a group capable of coordinative bonding with the metal element contained in the ultrafine metal particle. By making it the state coat | covered with 1 or more types of compounds which have, it will be in the state which the metal surface does not mutually contact the metal ultrafine particle mutually.
[0025]
The compound used for coating the surface uses a group having a lone pair on a nitrogen, oxygen, or sulfur atom when forming a coordinate bond with a metal element, and includes, for example, a nitrogen atom. Examples of the group include an amino group. Examples of the group containing a sulfur atom include a sulfanyl group (—SH) and a sulfide type sulfanediyl group (—S—). Examples of the group containing an oxygen atom include a hydroxy group and an ether type oxy group (—O—).
[0026]
A representative example of the compound having an amino group that can be used is an alkylamine. Such an alkylamine is preferably one that does not desorb in a normal storage environment, specifically in a range not reaching 40 ° C., in a state in which a coordinate bond is formed with the metal element, and has a boiling point. A range of 60 ° C. or higher, preferably 100 ° C. or higher is preferable. However, when carrying out sintering / alloying, it is necessary to be able to detach from the surface promptly, at least in a range where the boiling point does not exceed 300 ° C., usually in the range of 250 ° C. or less. Is preferred. For example, as the alkylamine, C4 to C20 is used as the alkyl group, more preferably C8 to C18 is selected, and an alkyl group having an amino group at the terminal is used. For example, the alkylamine in the range of C8 to C18 has thermal stability and its vapor pressure is not so high, and when it is stored at room temperature or the like, its content is maintained and controlled within a desired range. It is preferably used from the viewpoint of handling properties. In general, in forming such a coordination bond, the primary amine type is preferable because it shows higher binding ability, but secondary amine type and tertiary amine type compounds can also be used. is there. In addition, compounds in which two or more adjacent amino groups are involved in bonding, such as 1,2-diamine type and 1,3-diamine type, can also be used.
[0027]
Moreover, alkanethiol can be mentioned as a typical example of a compound having a sulfanyl group (—SH) that can be used. In addition, such alkanethiol is preferably in a state in which a coordinate bond is formed with a metal element and does not desorb in a normal storage environment, specifically, in a range not reaching 40 ° C., and has a boiling point. A range of 60 ° C. or higher, preferably 100 ° C. or higher is preferable. However, when carrying out sintering / alloying, it is necessary to be able to detach from the surface promptly, at least in a range where the boiling point does not exceed 300 ° C., usually in the range of 250 ° C. or less. Is preferred. For example, as the alkanethiol, C4-C20 is used as the alkyl group, and more preferably C8-C18 is selected, and an alkyl chain having a sulfanyl group (—SH) is used. For example, the alkanethiol in the range of C8 to C18 has thermal stability and its vapor pressure is not so high, and when it is stored at room temperature or the like, the content rate is maintained and controlled within a desired range. It is preferably used from the viewpoint of handling properties. In general, primary thiol type compounds are preferred because they exhibit higher binding ability, but secondary thiol type and tertiary thiol type compounds can also be used. In addition, those in which two or more sulfanyl groups (—SH) are involved in binding, such as 1,2-dithiol type, can also be used.
[0028]
Moreover, alkanediol can be mentioned as a representative of the compound which has a hydroxyl group which can be utilized. In addition, such alkanediols are preferably those that do not desorb in a normal storage environment, specifically in a range that does not reach 40 ° C., in a state in which a coordinate bond is formed with the metal element. A range of 60 ° C. or higher, usually 100 ° C. or lower, is preferred. However, when carrying out sintering / alloying, it is necessary to be able to detach from the surface promptly, at least in a range where the boiling point does not exceed 300 ° C., usually in the range of 250 ° C. or less. Is preferred. For example, those involving two or more hydroxy groups, such as 1,2-diol type, can be used more suitably.
[0029]
In addition, in the method for forming a circuit pattern of the present invention, the conductive metal paste to be used contains a thermosetting resin component that functions as an organic binder as an essential component. Such a thermosetting resin component has a function of imparting contact with each other and adhesion to the substrate when the applied conductive metal paste is heated and cured. Therefore, an organic binder and a thermosetting resin that are used for general conductive metal pastes can be used. For example, from the thermosetting resin components exemplified below, one or more types of resin components that are sufficiently cured by heat treatment at such temperatures may be selected and used according to the target heating / curing temperature. . Specifically, as the thermosetting resin, phenol resin, epoxy resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, oligoester acrylate resin, xylene resin, bismaleimide triazine resin, furan resin, urea resin, A polyurethane resin, a melamine resin, a silicon resin, etc. can be mentioned. Among them, phenol resin and epoxy resin have good adhesion even when forming an ultrafine circuit, and of course, the cured material properties are also suitable for conductive pastes. It is preferable.
[0030]
The content of these thermosetting resin components should be appropriately selected according to the total volume of the metal ultrafine particles and the ratio of voids existing between the particles, but usually, per 100 parts by mass of the metal ultrafine particles, It is good to select in the range of 1-30 mass parts, preferably 3-20 mass parts. In addition to the thermosetting resin that functions as the organic binder, when heated, the compound has at least one compound having a group containing nitrogen, oxygen, and sulfur atoms that forms a molecular layer that covers the surface of the ultrafine metal particles. , A component having reactivity with a group containing nitrogen, oxygen and sulfur atoms, for example, an organic acid anhydride or a derivative thereof or an organic acid, preferably an acid anhydride or an acid anhydride derivative.
[0031]
The component having reactivity with a group containing nitrogen, oxygen, or sulfur atoms, such as an acid anhydride or an acid anhydride derivative, is mainly coordinated with a metal element that covers the surface of the metal ultrafine particles described above. It is used for removing an adhesion layer formed by a compound having a group containing a nitrogen, oxygen or sulfur atom as a group capable of bonding. That is, when heated, as a result of reacting with a group containing nitrogen, oxygen, and sulfur atoms in the compound forming the adhesion layer near room temperature, after the reaction, the group containing nitrogen, oxygen, and sulfur atoms is On the surface of the ultrafine metal particles, it becomes difficult to form coordinate bonds with the metal atoms on the surface, and as a result, removal is performed. This removal function is not exhibited until the formation of the coating film of the conductive metal paste is completed, and then is exhibited for the first time in the heating process in which the thermosetting resin component contained is thermally cured. In addition, when the thermosetting resin used is an epoxy resin or the like, the acid anhydride or acid anhydride derivative contained in such applications may be the curing agent. In this case, the acid anhydride or acid anhydride derivative reacts with a compound having a group containing nitrogen, oxygen, or sulfur atoms, for example, an amine compound, a thiol compound, a diol compound, etc., upon thermosetting, Besides being used to form amides, thioesters and esters, it is also consumed as a curing agent for epoxy resins and the like. Therefore, it is good to add exceeding the addition amount which becomes settled according to the sum total of the terminal amino group, sulfanyl group (-SH), and hydroxy group which are contained in the said amine compound, a thiol compound, a diol compound. For example, since the terminal amino group of the amine compound also reacts with an epoxy resin or the like, the content of the acid anhydride or acid anhydride derivative depends on the type of alkylamine used and the content thereof. Is appropriately selected in consideration of the type of thermosetting resin used and its reactivity.
[0032]
Therefore, the compound that coats the surface of the metal ultrafine particles is a component having reactivity with the group containing nitrogen, oxygen, and sulfur atoms in addition to thermal detachment during heat curing of the thermosetting resin component, for example, , Reacting with an acid anhydride or an acid anhydride derivative to efficiently eliminate such a coating layer and allow the metal ultrafine particles to directly contact each other. As a result, as the thermosetting resin component is cured, sintering at low temperature, which is a characteristic of the ultrafine metal particles themselves, progresses, and as a whole, fusion by sintering is achieved while the fine metal particles are closely packed. The dense network-like conduction path that can be formed provides good electrical conductivity.
[0033]
The organic acid anhydride or its derivative or organic acid to be used is not particularly limited as long as it exhibits the above reactivity. For example, usable organic acids include C1-C10 linear or branched saturated carboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, hexanoic acid, octylic acid, and acrylic acid, methacrylic acid, crotonic acid, In addition to various carboxylic acids such as unsaturated carboxylic acids such as cinnamic acid, benzoic acid, sorbic acid, and dibasic acids such as oxalic acid, malonic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, Instead of carboxyl groups, phosphate groups (-OP (O) (OH) 2 ) Or a sulfo group (—SO Three Mention may be made of other organic acids such as phosphate esters, sulfonic acids, etc. having H).
[0034]
In addition, organic acid anhydrides or acid anhydride derivatives that can be suitably used include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), Aromatic acid anhydrides such as glycerol tris (anhydro trimellitate), maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinic anhydride, hexahydrophthalic anhydride And cyclic aliphatic acid anhydrides such as methylhexahydrophthalic anhydride and methylcyclohexene tetracarboxylic acid anhydride, and aliphatic acid anhydrides such as polyadipic acid anhydride, polyazeline acid anhydride, and polysebacic acid anhydride. it can. Among these, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and derivatives thereof are, for example, for the terminal amino group of an amine compound, etc., even at a relatively low heat-curing temperature targeted by the present invention. Since it has moderate reactivity, it is preferably used.
[0035]
In the method for forming a circuit pattern of the present invention, the conductive metal paste to be used is heat-cured after coating, but when coating, the metal ultrafine particles having a molecular coating layer on the surface are used as a solution. Shaped resin composition, that is, a thermosetting resin component that functions as the organic binder, a component that is reactive with a group containing nitrogen, oxygen, or sulfur atoms when heated, such as an organic acid anhydride or a derivative thereof Alternatively, a solution containing an organic acid and at least one organic solvent is used as a dispersion medium and uniformly dispersed therein. The organic solvent used at that time has a function as a solvent when preparing the resin composition, and elutes an adhesion layer of a compound such as an amine compound covering the surface of the metal ultrafine particles to be used. The organic solvent which does not do is utilized suitably.
[0036]
Different organic solvents can be used for these two types of applications, but the same organic solvent is preferably used. The type is not limited as long as it can be used for the two types of applications described above, but the solubility of a compound that forms an adhesion layer on the surface of the ultrafine metal particles, such as alkylamine, is too high. It is preferable to select a non-polar solvent or a low-polar solvent instead of a solvent having a high polarity so that the adhesion layer on the surface of the metal ultrafine particles disappears. In addition, in the circuit pattern forming method of the present invention, the organic solvent can evaporate relatively quickly at the temperature at which the conductive metal paste is heat-cured after coating, and does not cause thermal decomposition or the like during that time. To the extent it is preferable to have thermal stability. In addition, when forming fine lines, the conductive metal paste is sprayed and applied as fine droplets using the inkjet method in the coating process, so the liquid viscosity range suitable for the above discharge is maintained. It is also necessary to do. Considering its handling characteristics, non-polar or low-polarity solvents with relatively high boiling points that do not easily evaporate near room temperature, such as terpineol, mineral spirits, xylene, toluene, ethylbenzene, mesitylene, etc. It can be suitably used, and hexane, heptane, octane, decane, dodecane, cyclohexane, cyclooctane and the like can also be used.
[0037]
The content of the organic solvent is selected based on the amount of the thermosetting resin component, organic acid anhydride or derivative thereof, organic acid or the like to be dissolved. In that case, the resin composition containing the organic solvent is usually 50 to 300 parts by mass per 100 parts by mass of the ultrafine metal particles in the conductive metal paste used for forming the circuit pattern. of Of these, the organic solvent is preferably contained in the range of 20 to 270 parts by mass. This resin composition can also contain said thermosetting resin as a thermosetting resin component, a hardening | curing agent, a hardening accelerator, and also the other general-purpose additive component as needed. For example, a thermosetting resin that can be polymerized by heating using an organic acid anhydride or a derivative thereof as a polymerization agent (curing agent) is also preferable.
[0038]
At that time, ultrafine metal particles with a fine average particle diameter contained in the conductive metal paste are gold, silver, copper, platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium. In addition, fine particles made of one kind of metal or alloy fine particles made of two or more metals selected from the group consisting of aluminum can be appropriately selected according to the purpose. For normal purposes, fine particles made of a metal having excellent electrical conductivity such as gold, silver, copper and platinum are often used. In addition, when using alloy fine particles, the effect of this invention will be exhibited when using what has melting | fusing point of this alloy higher than the thermosetting temperature of a thermosetting resin component normally.
[0039]
In the circuit pattern forming method of the present invention, a conductive metal paste containing these components is jetted and applied as fine droplets on the substrate so as to have a desired pattern shape by using an inkjet method. According to the target minimum line width and line interval, for example, the average diameter of the dots to be applied is selected in the range of 10 to 20 μm, and the fine droplets are selected in accordance with the selection of the average diameter of the dots. The amount is determined by itself. In other words, when ejecting minute droplets using the ink jet method, the minute droplet amount depends on the performance of the inkjet printer head itself to be used, so a printer that matches the target droplet amount.・ Select and use the head. For example, the discharge nozzle inner diameter is appropriately selected in accordance with the average droplet amount when the average droplet amount is in the range of 2 to 100 pl.
[0040]
The conductive metal paste for forming the coating film is a conductive metal paste obtained by uniformly dispersing ultrafine metal particles having a fine average particle diameter in a resin composition in advance, and then using an inkjet method. Of course, it is possible to take a form of drawing, for example, divided into a liquid in which ultrafine metal particles are dispersed in an organic solvent and a liquid containing components constituting other resin compositions. It is also possible to apply the two liquids individually as fine droplets and mix the two liquids to form a conductive metal paste coating film. When using this two-component mixed conductive metal paste coating film forming method, the nozzles for ejection of each inkjet printer head used are used so that close contact / superposition of both droplets is achieved. Alignment control is performed. Needless to say, the amount of droplets of both liquids is adjusted so that each component has a desired content ratio in a mixed state. After that, heating and thermosetting of the thermosetting resin component and low-temperature sintering / fusion of metal ultrafine particles are substantially the same as when using a pre-mixed one-pack type conductive metal paste. .
[0041]
In addition, when using such a two-component mixed type conductive metal paste, a liquid in which ultrafine metal particles are dispersed in an organic solvent and a liquid containing other components constituting the resin composition are individually injected. -In order to apply | coat, it is necessary to select each liquid viscosity in the range which can achieve appropriate discharge. In some cases, the total amount of the organic solvent contained in each may be larger than the amount of the organic solvent in the pre-mixed one-pack type conductive metal paste. In order to reduce the content ratio of the organic solvent to a suitable content ratio in the subsequent heating step during the formation of the coating film or after the formation of the coating film, it is preferable to provide a step of evaporating the organic solvent.
[0042]
In addition, there are two types of inkjet printer heads to be used: a thermal system that ejects ink using heat bubbles (bubbles) and a piezo system that ejects ink using piezoelectric elements. In the circuit pattern forming method, either the thermal method or the piezo method can be used for the drawing by the dot-like jetting / coating of the metal fine particle paste to be used. Depending on the method of the inkjet printer head to be used, it is necessary to adjust the liquid viscosity of the conductive metal paste to be used. For example, the final liquid viscosity is adjusted to 0.5 by adjusting the amount of organic solvent added. It is desirable to select in the range of ˜30 Pa · s, preferably in the range of 1 to 5 Pa · s. Moreover, when utilizing a thermal system, it is necessary to select the organic solvent which can be heated and foamed (bubble), specifically, the organic solvent whose boiling point is lower than the heating temperature of a thermal system.
[0043]
In the method for forming a circuit pattern of the present invention, a conductive metal paste having a composition suitable for use in the ink jet method described above is placed in a liquid reservoir (container) of an ink jet printer head, and is described above. By applying a fine dot-shaped coating so that the dots overlap each other, circuits can be formed with the same accuracy from the desired minimum line width to a wide range of patterns, regardless of the pattern shape. . In addition, the film thickness to be formed also has an advantage that the film thickness can be selected with a high degree of freedom by applying a plurality of layers. Furthermore, even when circuit patterns manufactured in the same process have regions with different design film thicknesses, they can be formed with the same accuracy.
[0044]
On the other hand, the conductive metal paste put in the liquid reservoir (container) of the ink jet printer head is made of the above-mentioned organic acid anhydride or the like and the metal fine particles at room temperature or in the range of the upper limit temperature expected for storage. Since the reaction with the terminal amino group of the compound that coats the surface does not proceed substantially, in the conductive metal paste of the present invention, the contained thermosetting resin component is heated and cured, so it is not heated to a predetermined temperature. As long as the surface of the metal ultrafine particles is densely coated, a molecular layer such as an amine compound is stably maintained. Due to this action, the aggregation resistance during storage is maintained high, and the formation of a natural oxide film on the surface of the metal ultrafine particles due to moisture and oxygen molecules in the atmosphere is also suppressed. In addition, since the contained ultrafine metal particles are maintained in a uniform dispersed state until they are ejected, they do not adhere to the ejection nozzle and cause variations in the amount of applied droplets. The dispersion concentration does not vary due to coagulation separation and sedimentation.
[0045]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. Although this example is an example of the best mode of the present invention, the present invention is not limited by this example.
[0046]
Example 1
Commercially available silver ultrafine particle dispersion (trade name: Independently dispersed ultrafine particle Perfect Silver, Vacuum Metallurgical Co., Ltd.), specifically, silver fine particles 100 parts by mass, alkylamine as dodecylamine 15 parts by mass, organic Using a dispersion of silver fine particles having an average particle diameter of 8 nm containing 75 parts by mass of terpineol as a solvent, a conductive metal paste (ink) having ultrafine silver particles was prepared.
[0047]
The conductive metal ink contains methyl hexahydrophthalic anhydride (Me-HHPA) as an acid anhydride as a component forming a resin composition per 100 parts by mass of silver fine particles in a dispersion of silver fine particles. ), 6.8 parts by mass, a thermosetting resin, 5 parts by mass of a resol type phenol resin (manufactured by Gunei Chemical Co., Ltd., PL-2211), an organic solvent, 35 parts by mass of toluene, and stirring. And uniformization was achieved. After the silver fine particles are uniformly dispersed in the resin composition obtained by mixing, the prepared conductive metal ink is filtered and mixed using a polytetraethylene filter having a mesh size of 0.5 μm. The processing which removes the bubble which is done was given. The liquid viscosity of the prepared conductive metal ink is 10 Pa · s.
[0048]
Next, the ink cartridge of the ink jet print head was filled with the conductive metal ink that had been subjected to the deaeration treatment. The print head filled with the conductive metal ink was mounted on a dedicated printer. In this example, the printability of each of the thermal method and the piezoelectric method was verified as the ink jet print head. In the thermal method and the piezo method, the average liquid volume of the ejected droplets is 4 pl and 4 pl, respectively. Accordingly, dot-like printing with an average outer diameter of 16 μm and 18 μm can be performed by spraying and applying the droplets. In each of the thermal method and piezo method, this conductive metal ink is used to form a film thickness on a glass substrate. 5 A linear pattern having a line width of μm and 100 μm was printed by an inkjet method. After this printing, the conductive metal ink on the glass substrate was subjected to a two-step heat treatment at 150 ° C. for 30 minutes and further at 210 ° C. for 60 minutes to cure the contained thermosetting resin.
[0049]
After the thermosetting treatment, items such as line width, line spacing, surface flatness after thermosetting, and film thickness were measured to evaluate the printability. The reproducibility of the shape and dimensions of the drawn pattern is very high, and it is stable without changing from the target. More specifically, the change in line width is a maximum of the dot diameter under the conditions of dot print density (resolution), 600 dpi and 720 dpi (dots / inch) in each of the thermal method and the piezo method. The average film thickness is 10% or less, and there is some shrinkage with thermosetting. 3 The variation in μm and film thickness is 20% or less. In addition, there was no clogging of the conductive metal ink in the discharge nozzle portion of the ink jet print head used. The specific resistance of the metal wiring pattern obtained by the two-step heat treatment is 2.8 × 10 -Five Good values such as Ω · cm were shown with high reproducibility.
[0050]
【The invention's effect】
In the method of forming a circuit pattern using the inkjet printing method of the present invention, the conductive metal paste to be used when drawing and forming the circuit pattern of the wiring board with the conductive metal paste using the inkjet method is a resin composition. It is a conductive metal paste in which ultrafine metal particles with a fine average particle diameter are uniformly dispersed, and the fine metal ultrafine particles with a fine average particle diameter are selected in the range of 1 to 100 nm in average particle diameter. The surface of the ultrafine metal particles is coated with one or more compounds having a group containing nitrogen, oxygen, or sulfur atoms as a group capable of coordinative bonding with the metal element contained in the ultrafine metal particles, On the other hand, the resin composition is a thermosetting resin component that functions as an organic binder, a component having reactivity with a group containing nitrogen, oxygen, or sulfur atoms when heated, for example, After containing an organic acid anhydride or its derivative or organic acid, and at least one organic solvent, the conductive metal paste is jetted onto the substrate as fine droplets by an ink jet drawing means. A circuit pattern is formed through a step of applying and drawing a circuit pattern, and a step of heat-treating the drawn conductive metal paste coating film at least at a temperature at which the thermosetting resin is thermally cured. As a result, in conjunction with the thermosetting of the thermosetting resin component, the compound molecular layer covering the surface of the metal ultrafine particles is removed, for example, by a reaction with an organic acid anhydride or a derivative thereof or an organic acid, and the metal ultrafine particles are removed. The use of ultrafine metal particles is necessary because mutual network fusion is performed at low temperatures to form a network-like conductive layer having close electrical contact. , A pattern with high accuracy fine line width, also has the advantage of producing a high reproducibility wiring circuit exhibits excellent conductivity. In addition, in connection with the use of the conductive metal paste having the above-described configuration, high conduction stability and reproducibility that can not be obtained in a conduction path by simple particle contact can be secured, and further, a heat-curing resin. Therefore, it is possible to easily print and fabricate an ultrafine circuit that has good adhesion to the substrate and that is substantially free from variations in film thickness.

Claims (10)

  1. A method of drawing and forming a circuit pattern of a wiring board using a conductive metal paste using an inkjet method,
    The conductive metal paste to be used is a conductive metal paste obtained by uniformly dispersing ultrafine metal particles having a fine average particle diameter in a resin composition containing a thermosetting resin and an organic solvent,
    The metal ultrafine particles having a fine average particle diameter are selected in the range of 1 to 100 nm in average particle diameter, and the surface of the metal ultrafine particles can be coordinated with the metal elements contained in the metal ultrafine particles. As a group, it is coated with one or more compounds having a group containing either nitrogen or oxygen atoms ,
    A step of drawing a circuit pattern composed of a coating film of the conductive metal paste by spraying and applying on a substrate as fine droplets by an ink jet drawing means;
    Heat-treating the drawn conductive metal paste coating film at least at a temperature at which the thermosetting resin is thermoset;
    The group containing any one of the nitrogen and oxygen atoms is selected from an amino group and a hydroxy group (-OH);
    The coating of the surface of the metal ultrafine particles with one or more compounds having a group containing any one of the nitrogen and oxygen atoms includes a group containing either the nitrogen or oxygen atoms for the metal element contained in the surface of the metal ultrafine particles, A circuit pattern forming method using an inkjet printing method, wherein the circuit pattern is formed through a coordinate bond .
  2. The resin composition is a thermosetting resin component that functions as an organic binder. When heated, one or more compounds having a group containing either nitrogen or oxygen atoms when heated are either nitrogen or oxygen atoms. component reactive with the group containing, and contains at least one kind of organic solvent,
    The organic acid anhydride or a derivative thereof, or an organic acid is used as a component having reactivity with a group containing any of the nitrogen and oxygen atoms. A circuit pattern forming method.
  3. In the process of drawing a circuit pattern,
    A liquid obtained by dispersing ultrafine metal particles coated with one or more compounds having a group containing either nitrogen or oxygen atom in an organic solvent;
    A thermosetting resin component that constitutes the resin composition, a component having reactivity with a group containing any of nitrogen and oxygen atoms , and a liquid containing an organic solvent,
    3. A coating film made of a conductive metal paste is formed by spraying and coating on a substrate using individual ink jet drawing means, and mixing both liquids on the substrate. Circuit pattern forming method.
  4. The method for forming a circuit pattern according to claim 2 or 3 , wherein an organic acid anhydride is used as the component having reactivity with the group containing either nitrogen or oxygen atoms. .
  5. The ultrafine metal particles with a fine average particle size contained in the conductive metal paste are gold, silver, copper, platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium, and aluminum. 4. The circuit pattern forming method according to claim 2, wherein the circuit pattern is selected from the group consisting of fine particles made of one kind of metal or fine particles of an alloy made of two or more kinds of metals.
  6. In the heat treatment step at least at a temperature at which the thermosetting resin is thermally cured,
    4. The method for forming a circuit pattern according to claim 2 , further comprising sintering the metal ultrafine particles contained in the conductive metal paste in the drawn coating film.
  7. The ink jet drawing means is a thermal drawing means that generates bubbles by heating and foaming and discharges droplets.
    4. The method for forming a circuit pattern according to claim 2 , wherein the one or more organic solvents contained in the conductive metal paste to be used have a boiling point lower than a heating temperature of the heating foaming. .
  8. The ink jet drawing means is a piezoelectric drawing means for discharging droplets by compression using a piezoelectric element,
    One or more organic solvents contained in the conductive metal paste used, the boiling point, in claim 2 or 3, wherein the thermal curing of said at least a thermosetting resin is below the temperature to be made A method of forming a circuit pattern to be described.
  9. In the conductive metal paste, per 100 parts by mass of ultrafine metal particles, the resin composition containing the organic solvent is included in a range of 50 to 300 parts by mass,
    Among these, the said organic solvent is contained in the range of 20-270 mass parts, The formation method of the circuit pattern described in Claim 2 or 3 characterized by the above-mentioned.
  10. The thermosetting resin component that functions as an organic binder used in the resin composition is a thermosetting resin that can be heat-polymerized using the organic acid anhydride or derivative thereof or an organic acid as a polymerization agent. A method of forming a circuit pattern according to claim 2 or 3 .
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