CN100354380C - Conductive ink composition, reflective member, circuit substrate, and electronic apparatus - Google Patents

Abstract

A conductive ink composition is obtained by dispersing, in an organic solvent, a solid material made from metal fine particles each coated with protective colloids each made of at least two organic compounds, the metal fine particles consisting of an alloy containing at least a noble metal. Each of the protective colloids is made from, e.g., a raw material containing an (A) amine and a (B) carboxylic acid. By applying and baking the conductive ink composition, grain growth is restrained. This allows acquirement of a metal film whose surface smoothness is excellent, and whose adhesiveness to an application target is improved as compared with that of a metal film made from a conventional conductive ink composition.

Description

Conductive ink composition, reflection part, circuit substrate, electronic installation

Technical field

The present invention relates to use conductive ink composition, reflection part, circuit substrate, the electronic installation of metal particle, said in more detail, related to suppress the conductive ink composition of the particle growth of metal; And this conductive ink composition carried out drying or thermal treatment and the reflection part that forms; And above-mentioned conductive ink composition carried out drying or thermal treatment forms, has the circuit substrate of the metal level of distribution, electrode, reflection part etc.; And the electronic installations such as display unit that comprised this circuit substrate.

Background technology

Display unit such as liquid crystal indicator as one of electronic installation can be used in various fields such as PC, portable phone, digital camera, LCD TV.

Electronic installations such as these display unit comprise the circuit substrates such as tft array substrate that for example have a plurality of TFT (thin film transistor), distribution etc.

The sort circuit substrate normally forms by repeatedly carrying out operation as described below repeatedly, promptly adopts photolithography etc. will remove the operation of (etching) by the otiose part in the middle of the film forming films of vapour deposition process such as CVD (chemical vapor deposition) or sputter.

But, problem is that this manufacture method is in the past carried out film forming and etching repeatedly, so the service efficiency of raw material is poor, in addition, produce the etching solution the like waste in a large number, processing cost increases, manufacturing time prolongs simultaneously, and need be used for a plurality of vacuum units such as processing unit (plant) of the film deposition system of each film formation process and etching system etc., so for example require in recent years to have the problem that needs very large cost of equipment in the manufacturing of the circuit substrate that further maximizes at tft array substrate etc.

Therefore, in recent years, the so-called ink jet method (drop ejection method) that propose to adopt the zone that is sprayed onto needs by the fluent material that will contain electrically conductive microparticle to form the pattern that comprises the needs that are ejected thing forms the technology of the distribution on the foregoing circuit substrate etc.

For example, as day disclosure communique the spy opened the 2003-318192 communique (open day: on November 7th, 2003, No. the 2003219934th, corresponding U.S. Patent Application Publication, below note is done " patent documentation 1 ") in disclose: as containing an example that has comprised the fluent material of any metal particle in the middle of gold and silver, copper, barium, the nickel, use disperses particle diameter in organic solvent be the cream that the silver-colored particulate about 0.01 μ m forms, and forms distribution by ink jet method.

Usually forming under the situation of tft array substrate that circuit substrate for example is used for liquid crystal indicator, as the performance that requires distribution to have, can enumerate resistance low, have a level and smooth superficiality, good with the adaptation of base material such as glass.

But usually noble metal is more stable, thus with coating object substrate reactive low for example, lack and the adaptation of substrate for this reason.All the time, the printing ink of using as ink-jet (ink), as mentioned above, usually many uses dispersion particle diameter in organic solvent is the so-called silver-colored printing ink that the particulate of the silver about 0.01 μ m forms, for silver is used as film, require adaptation like this to the base materials such as coated face (coating object) of glass substrate or insulating material.In the methods such as sputter, sudden particle squeeze into the major cause that effect becomes the adaptation of improving noble metal (being silver this moment) and substrate, but as mentioned above, under the situation that for example will use the cream of silver particles to print as mentioned above or be coated with by ink-jetting style, can not expect in film process silver to substrate squeeze into effect etc., die down with the adaptation of base material such as above-mentioned glass substrate.In addition, no matter whether be silver particles, easier of strippable substrate when above-mentioned metal particle is low as the reactivity of noble metal and other materials, adaptation, in belt stripping test, simply peeled off.

And, when silver on glass substrate during film forming, firing temperature is that particle growth is remarkable about 250 ℃, level and smooth for this reason surface occurs coarse, and surface haze etc. occurs, the superficiality deterioration when high temperature burns till, the metallic membrane that obtains is difficult to directly as distribution.

Therefore, can think the improvement that realizes adaptation (sticking power) by annealing, but as seeing, owing to the particle growth characteristic of above-mentioned noble metal, the problem of film surface irregularity, surface smoothing deterioration appears under the situation of having used silver particles as mentioned above.

When the particle growth owing to noble metal like this made the smoothness deterioration on film surface, this coarse film surface caused variety of issue.For example, as shown in figure 28, when for example using above-mentioned printing ink to form bottom distribution 201, (wiring crossing portion) seen as the part that overlaps each other at distribution, the surface smoothing of bottom distribution 201 is poor, because might cause short circuit being formed at the uneven of insulation layer 202 on this bottom distribution 201 is defective L such as film fracture, become the reason of sewing (sewing up and down in the distribution up and down) with the top distribution 203 that forms by this insulation layer 202.For example, when forming tft array substrate as the foregoing circuit substrate, in TFT portion, gate electrode portion, clamping grid insulation layer and be formed with non-crystalline silicon (a-Si) layer (about 500 =about 50nm), because as the surface irregularity of the gate electrode of bottom distribution 201, cause the deterioration of TFT characteristic or as the film fracture of the gate insulating film of insulation layer 202.Similarly, in auxiliary capacitance electrode, because cause the film fracture of insulation layer 202 or sew up and down, so do not bring into play capacitor function sometimes.

Summary of the invention

The present invention just in view of above-mentioned in the past problem and the invention that proposes, its purpose is, provide with silver-colored monomers such as using silver particles and compare the conductive ink composition that more can suppress the particle growth of metal, and use this conductive ink composition and the reflection part and circuit substrate and the electronic installation that form as the conductive ink in the past of metal particle.In addition, another object of the present invention is, provide and for example as silver-colored printing ink, use the monomeric conductive ink composition in the past of noble metal to compare more to improve and be coated with the conductive ink composition of the adaptation of object, and use this conductive ink composition and the reflection part and circuit substrate and the electronic installation that form as metal particle.In addition, a further object of the present invention is, provides the particle growth that can form metal to be suppressed and the conductive ink composition of the film of surface smoothing excellence and particle growth with metal is suppressed and the circuit substrate of the metal level of surface smoothing excellence and electronic installation, reflection part.In addition, other purposes of the present invention also are, provide the particle growth that can form metal to be suppressed and the conductive ink composition of the film of reflection efficiency excellence and particle growth with metal is suppressed and the circuit substrate of the metal level of reflection efficiency excellence and electronic installation, reflection part.

The inventor etc. are in order to solve above-mentioned problem in the past; concentrate on studies; found that by the metal beyond the interpolation noble metal in noble metal and finally become alloy; the character that can suppress noble metal; and then, can suppress the particle growth that with on every side (periphery) compares the metal that produces in the many parts of precious metal amount by protective colloid.In addition, the inventor etc. also find, by using the protective colloid that is formed by two kinds of organic compound at least, suppress the effect height of metal particle growth, more can improve and the adaptation, the smoothness on film surface, the emission efficiency that are coated with object with comparing in the past.And; the inventor etc. have carried out further concentrating on studies; found that by further protective colloid and study conductive ink composition; even in the less zone of the content that adds metal and then using under the situation of noble metal monomer as metal particle; more in the past than the particle growth that more can suppress metal, can improve adaptation, the smoothness on film surface, reflection efficiency.

That is, in order to achieve the above object, conductive ink composition of the present invention is characterized in that, comprises with the protective colloid that is made of two kinds of organic compound at least to cover the metal particle surface that is made of the alloy that contains noble metal at least and the solid matter that forms.

Promptly; in order to achieve the above object; conductive ink composition of the present invention; it is characterized in that; it is the solid matter that forms by metal particle and the protective colloid that surrounds this metal particle; for the multiple metal of noble metal constitutes, and described protective colloid is made of two kinds of organic compound described metal particle at least by at least a, and this conductive ink composition can disperse in organic solvent.

In addition; in order to achieve the above object; conductive ink composition of the present invention is in order to solve above-mentioned problem; it is characterized in that, be to contain by at least a metal particle that forms for the multiple metal of noble metal and surround the protective colloid that is formed by two kinds of organic compound at least of this metal particle and the fluent meterial of organic solvent.

According to above-mentioned each formation; above-mentioned conductive ink composition; by comprising following solid matter; promptly for example cover the solid matter that the surface of the metal particle that is made of the alloy that contains noble metal at least forms with the protective colloid that constitutes by two kinds of organic compound at least by at least a metal particle that forms for the multiple metal of noble metal; used silver-colored monomeric conductive ink in the past to compare with silver-colored printing ink etc. as metal particle, the particle growth that can form metal is suppressed; surface smoothing is excellent and ratio more can improve in the past and the adaptation of coating object and the metal level (metallic membrane) of reflection efficiency.

Wherein, as above-mentioned protective colloid; preferably the compound that obtains by the raw material that contains (A) amine, (B) carboxylic acid and/mixture; the mixture of more preferably above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.In addition, above-mentioned (A) amine preferably carbonatoms be 5～20 alkylamine.

In addition; in order to achieve the above object; conductive ink composition of the present invention is characterised in that; contain useful protective colloid and cover the metal particle that constitutes by noble metal and the solid matter that forms; above-mentioned protective colloid is made of (A) amine, (B) carboxylic acid; the mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

In addition; in order to achieve the above object; conductive ink composition of the present invention is characterised in that; be to use the protective colloid that constitutes by (A) amine, (B) carboxylic acid to cover the metal particle that constitutes by noble metal and the solid matter that forms; can in organic solvent, disperse; the mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

In addition; in order to achieve the above object; conductive ink composition of the present invention is characterised in that; be to contain the metal particle that constitutes by noble metal, surround the protective colloid of this metal particle, the fluent meterial of organic solvent; above-mentioned protective colloid is to be made of (A) amine, (B) carboxylic acid; the mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

In addition, in the above-mentioned such conductive ink composition of use noble metal monomer as metal particle, it is 5～20 alkylamine that above-mentioned amine is preferably carbonatoms.

Above-mentioned protective colloid is very high to the inhibition effect of particle growth; in above-mentioned conductive ink composition of the present invention; even using under the situation of noble metal monomer as above-mentioned metal particle; compare with the conductive ink composition in the past of the so-called silver-colored printing ink that disperses to form as the noble metal of metal particle in organic solvent, it is excellent and more in the past than the metal level (metallic membrane) that more can improve with the adaptation of coating object to form the particle growth, the surface smoothing that suppress metal.Thus, according to above-mentioned each formation, can provide the conductive ink composition that can form particularly low-resistance distribution of low-resistance metal level and/or electrode.In addition, above-mentioned conductive ink composition suppresses the particle growth of metal, consequently can form the metal level of reflection efficiency excellence.Thus, constitute according to above-mentioned each, can provide can be formed in surface smoothing, with the adaptation of coating object, reflection efficiency aspect conductive ink composition of excellent reflection part all.Above-mentioned metal level can be particularly preferred for reflecting electrode etc.

In addition, in order to achieve the above object, reflection part of the present invention is characterised in that, is above-mentioned conductive ink composition of the present invention is carried out forming after drying or the thermal treatment.

In addition, in order to achieve the above object, circuit substrate of the present invention is characterised in that, has above-mentioned conductive ink composition of the present invention is carried out the metal level that forms after drying or the thermal treatment.

And then in order to achieve the above object, electronic installation of the present invention is characterised in that, comprises foregoing circuit substrate of the present invention.

Metal levels such as above-mentioned distribution or electrode, reflection part are above-mentioned conductive ink composition of the present invention is carried out drying or thermal treatment (for example burning till) and to form, so compare with the distribution that has used conductive inks in the past such as so-called silver-colored printing ink or the metal level of electrode, reflection part etc., the particle growth that can suppress metal, the surface smoothing excellence, with the coating object the adaptation excellence.And, as mentioned above, the metal level that forms with using conductive ink is in the past compared, the metal level that above-mentioned conductive ink composition is carried out drying or thermal treatment and form, the particle growth of its metal is suppressed, and surface smoothing, with the adaptation excellence of coating object, so the above-mentioned use of resistance ratio in the past conductive ink and the metal level that forms is lower, reflection efficiency is also more excellent in addition.Thus, constitute, can provide that the particle growth with metal is suppressed, surface smoothing excellent and than more improving with the metal level of the adaptation of coating object in the past, reflection part that reliability is high and circuit substrate and electronic installation according to above-mentioned each.

For other purposes of the present invention, feature and advantage, can fully understand by record as described below.In addition, can understand benefit of the present invention by the explanation of reference accompanying drawing.

Description of drawings

Fig. 1 will use the protective colloid shown in embodiment 2 and the ink film of silver-indium of forming with scanning electron microscope photo (30,000 times of multiplying powers) expression, at N ₂The figure of the state of the metallic film surface of carrying out annealing in 1 hour in the gas atmosphere under 300 ℃ and obtaining.

Fig. 2 (a)～Fig. 2 (c) is the figure of manufacturing process of the conductive ink composition of expression an embodiment of the invention.

Fig. 3 is the schematic configuration diagram that pattern that expression is used to make circuit substrate of the present invention forms an example of device.

Fig. 4 is the orthographic plan of schematic construction of the tft array substrate in the liquid crystal indicator of expression an embodiment of the invention.

Fig. 5 is the orthographic plan of the schematic construction of 1 pixel in the expression tft array substrate shown in Figure 4.

Fig. 6 is that A-A in as shown in Figure 5 the tft array substrate is to sectional view.

Fig. 7 (a) is the orthographic plan of the schematic construction of 1 portion of terminal in the tft array substrate of representing as shown in Figure 4.

Fig. 7 (b) is that the B-B of the portion of terminal shown in Fig. 7 (a) is to sectional view.

Fig. 8 is the process picture sheet of manufacturing process of the tft array substrate in the liquid crystal indicator of expression an embodiment of the invention.

Fig. 9 (a) is the orthographic plan of the schematic construction of the pixel portion in the tft array substrate of representing after the gate wirings pretreatment procedure finishes.

Fig. 9 (b) is the orthographic plan that the expression gate wirings forms the schematic construction of the pixel portion after treatment process finishes.

Fig. 9 (c) is that the C-C of Fig. 9 (b) is to sectional view.

Figure 10 (a) is the orthographic plan of the schematic construction of the terminal part in the tft array substrate of representing after the gate wirings pretreatment procedure finishes.

Figure 10 (b) is the orthographic plan that the expression gate wirings forms the schematic construction of the terminal part after treatment process finishes.

Figure 10 (c) is that the D-D of Figure 10 (b) is to sectional view.

Figure 11 (a)～Figure 11 (d) is the figure of the formation operation in close and distant water (close and distant liquid) zone in the expression gate wirings pretreatment procedure.

Figure 12 (a) is the schematic configuration diagram of the formation of the whole gate wirings of pattern ground expression.

The schematic configuration diagram of the structure of the gate electrode portion in the gate wirings of Figure 12 (b) pattern ground expression shown in Figure 12 (a).

The schematic configuration diagram of the structure of the terminal electrode portion in the gate wirings of Figure 12 (c) pattern ground expression shown in Figure 12 (a).

Figure 13 (a)～Figure 13 (e) is the wiring part of tft array substrate of expression shown in Figure 12 (a)～Figure 12 (c) and the figure of the formation operation of the portion of terminal of terminal electrode portion.

Figure 14 (a) and Figure 14 (b) are the only figure of the formation operation of the above-mentioned gate electrode under the conductive ink composition situation of using present embodiment on the gate electrode of expression.

Figure 15 is expression improves the flatness of distribution by the present invention the mode chart of state.

Figure 16 (a) is the orthographic plan of the schematic construction of the pixel portion in the tft array substrate of representing after gate insulating film, semiconductor film film formation process finish.

Figure 16 (b) is that the F-F of Figure 16 (a) is to sectional view.

Figure 17 (a) is the orthographic plan of the schematic construction of the terminal part in the tft array substrate of representing after gate insulating film, semiconductor film film formation process finish.

Figure 17 (b) is that the F-F of Figure 17 (a) is to sectional view.

Figure 18 (a) is the orthographic plan of the schematic construction of the pixel portion in the tft array substrate of representing after gate insulating film, semiconductor film manufacturing procedure finish.

Figure 18 (b) is that the G-G of Figure 18 (a) is to sectional view.

Figure 19 (a) is the orthographic plan of the schematic construction of the terminal part in the tft array substrate of representing after gate insulating film, semiconductor film manufacturing procedure finish.

Figure 19 (b) is that the H-H of Figure 19 (a) is to sectional view.

Figure 20 (a) is the orthographic plan of the schematic construction of the pixel portion after expression source, drain electrode distribution pretreatment procedure finish.

Figure 20 (b) is the orthographic plan that expression source, drain electrode distribution form the schematic construction of the pixel portion after operation finishes.

Figure 20 (c) is that the I-I of Figure 20 (b) is to sectional view.

Figure 21 represents the figure that the signal of the pixel portion after the groove manufacturing procedure finishes constitutes with the I-I among Figure 20 (b) to the cross section.

Figure 22 (a) is the orthographic plan of the schematic construction of the pixel portion after expression protective membrane, interlayer insulating film film formation process finish.

Figure 22 (b) is that the J-J of Figure 22 (a) is to sectional view.

Figure 23 (a) is the orthographic plan of the schematic construction of the terminal part after expression protective membrane, interlayer insulating film film formation process finish.

Figure 23 (b) is that the K-K of Figure 23 (a) is to sectional view.

Figure 24 (a) represents the figure that the signal of the pixel portion after the protective membrane manufacturing procedure finishes constitutes with the J-J among Figure 22 (a) to the cross section.

Figure 24 (b) represents the figure that the signal of the terminal part after the protective membrane manufacturing procedure finishes constitutes with the K-K among Figure 23 (a) to the cross section.

Figure 25 is illustrated in N with scanning electron microscope photo (30,000 times of multiplying powers) ₂The figure of the state on the monomer vapor-deposited film surface of the silver that carries out 1.5 hours thermal anneal process under 300 ℃ in the gas atmosphere and obtain.

Figure 26 is illustrated in N with scanning electron microscope photo (30,000 times of multiplying powers) ₂The figure of the state on the surface of the silver-indium vapor-deposited film that carries out 1.5 hours thermal anneal process under 300 ℃ in the gas atmosphere and obtain.

Figure 27 will use the protective colloid that is made of naphthenic acid and octylame and the ink film of the silver-indium that forms as protective colloid with scanning electron microscope photo (30,000 times of multiplying powers) expression, at N ₂The figure of the state of the metallic film surface of carrying out annealing in 1 hour in the gas atmosphere under 300 ℃ and obtaining.

Figure 28 is that expression is because the particle growth of noble metal produces the mode chart of the state of sewing between top distribution and bottom distribution.

The coverage diagram figure that concerns between reflectivity and the wavelength when Figure 29 is the indium content of representing to change like that in each metallic membrane shown in embodiment 13.

Figure 30 will use the protective colloid that is made of octadecadienoic acid, caproic acid and octylame and the ink film of the silver that forms with scanning electron microscope photo (30,000 times of multiplying powers) expression, at N ₂The figure of the state of the metallic film surface of carrying out annealing in 1 hour in the gas atmosphere under 300 ℃ and obtaining.

Figure 31 will use the protective colloid that is made of pentadecylic acid and octylame and the ink film of the silver that forms with scanning electron microscope photo (30,000 times of multiplying powers) expression, at N ₂The figure of the state of the metallic film surface of carrying out annealing in 1 hour in the gas atmosphere under 300 ℃ and obtaining.

Figure 32 will only use octylame to constitute protective colloid and the ink film of the silver that forms with scanning electron microscope photo (30,000 times of multiplying powers) expression, at N ₂The figure of the state of the metallic film surface of carrying out annealing in 30 minutes in the gas atmosphere under 300 ℃ and obtaining.

Figure 33 will use the protective colloid that is made of naphthenic acid and octylame and the ink film of the silver that forms with scanning electron microscope photo (30,000 times of multiplying powers) expression, at N ₂The figure of the state of the metallic film surface of carrying out annealing in 30 minutes in the gas atmosphere under 300 ℃ and obtaining.

Embodiment

The conductive ink composition of present embodiment; be by on the coating object, carrying out drying or thermal treatment (for example burning till) after the coating; can form the ink material of metallic film, comprise at least: contain the metal particle of noble metal at least and surround the protective colloid that is configured to by two kinds of organic compound at least of this metal particle.

The conductive ink composition of present embodiment for example comprises at least: by at least a be the metal particle that forms of the multiple metal of noble metal, the protective colloid that forms by two kinds of organic compound at least that surrounds this metal particle.

Say that more specifically for example above-mentioned conductive ink composition comprises that the metal particle surface that is made of the alloy that contains noble metal is at least covered (coating) by the protective colloid that is made of two kinds of organic compound at least and the solid matter that forms.

In addition; above-mentioned conductive ink composition is the solid matter that comprises by the protective colloid of metal particle and this metal particle of encirclement; described metal particle is made of for the multiple metal of noble metal at least a; and described protective colloid is made of two kinds of organic compound at least, and this conductive ink composition can disperse in organic solvent.

According to present embodiment, when the solid matter in the above-mentioned conductive ink composition (micelle) was carried out sintering, the protective colloid on above-mentioned metal particle surface was removed, and fuses between the above-mentioned metal particle, forms metallic membrane thus.So; as above-mentioned micelle; can have the structure that covers the particulate of the alloy that contains noble metal at least with above-mentioned protective colloid, can also have and cover at least a respectively with above-mentioned protective colloid to be the structure of particulate of the multiple metal of noble metal, can also to be its mixture.

In the above-mentioned solid matter; surround (covering) above-mentioned metal particle with protective colloid; therefore this solid matter can disperse in organic solvent, by interpolation, mixed organic solvents in this conductive ink composition, can not become dissolving or settled state in organic solvent.For this reason, above-mentioned conductive ink composition can be used as so-called printing ink (ink) by disperseing in organic solvent.

In the present embodiment; ratio with regard to metal particle and protective colloid shared in the above-mentioned solid matter; in the scope of preferable alloy particulate more than 60 quality %, below the 95 quality %, in the scope (both total amounts are 100 quality %) of protective colloid more than 5 quality %, below the 40 quality %.

In addition, above-mentioned conductive ink composition for example can be to comprise by at least a metal particle that constitutes for the multiple metal of noble metal, the protective colloid that is made of two kinds of organic compound at least that surrounds this metal particle, the fluent meterial of organic solvent.That is, above-mentioned conductive ink composition can be the fluent meterial that himself contains organic solvent.Promptly, above-mentioned conductive ink composition can be according to the content of the above-mentioned metal particle in this conductive ink composition etc., in other words for example add organic solvent in addition, perhaps directly as conductive ink (ink) according to the flowability of conductive ink composition etc.Wherein, the flowability of above-mentioned conductive ink composition can suitably be set in the scope of needs according to use or using method etc., is not particularly limited.

Ratio about above-mentioned metal particle, protective colloid and organic solvent (dispersion medium) in the above-mentioned fluent meterial; in the scope of preferred above-mentioned metal particle more than 15 quality %, below the 95 quality %; in the scope of protective colloid more than 1 quality %, below the 50 quality %, in the scope (wherein their total amount is 100 quality %) of organic solvent more than 1 quality %, below the 60 quality %.

The above-mentioned metal particle of Shi Yonging is the so-called ultra micron (nanoparticle) of particle diameter for number nm～hundreds of nm in the present embodiment, and concrete preferred use for example has the metal particle of the particle diameter in the scope that 1nm is above, 100nm is following.

In addition, the above-mentioned metal particle of Shi Yonging contains noble metal at least and gets final product in the present embodiment, when using the particulate that constitutes by multiple metal as metal particle, as long as wherein at least a is noble metal, just be not particularly limited, but when with above-mentioned conductive ink composition as the wiring material in the circuit substrate (wiring substrate) etc., promptly the material of distribution that forms on the insulativity substrates such as glass substrate and/or electrode (below, gather and be called wiring material) time, above-mentioned metal particle is preferably by low resistance and thermotolerance, sticking power to glass substrate, anti-isoiony (promptly, even for example exposed to the open air in the plasma atmosphere in operations such as dry-etching operation, condition of surface and characteristic do not change yet) etc. the high metal of anti-operation constitute.

As above-mentioned noble metal, can specifically be exemplified as gold and silver, ruthenium, rhodium, palladium, osmium, iridium, platinum etc., but be not particularly limited.These noble metals can only use a kind of, can also appropriate combination use.In the middle of above-mentioned noble metal, preferred gold and silver, platinum etc., further more preferably silver-colored.

As the metal that uses except above-mentioned noble metal and in the present embodiment, for example, preferably use standard oxidation also original unit be-0.45～+ metal of 1.5V/VHE.

In addition, as the metal that uses except above-mentioned noble metal and in the present embodiment, the preferred at least a metal of from the group that constitutes by iron, cobalt, nickel, copper, cadmium, indium, tin, thallium, lead, molybdenum and bismuth, selecting, for example, when using silver as above-mentioned noble metal, as the metal except above-mentioned noble metal, preferred especially indium.In addition, these illustrative metals all satisfy also original unit of above-mentioned standard oxidation.

Contain above-mentioned metal at above-mentioned metal particle as the metal outside the noble metal, and with above-mentioned conductive ink composition during as the above-mentioned wiring material on the circuit substrate, with with noble metal as metal particle be dispersed in the silver-colored printing ink that forms in the organic solvent such, use noble metal monomer (being specially silver-colored monomer) to compare as the conductive ink in the past of metal particle, can easily form the particle growth that can suppress metal and improve low-resistance distribution and/or electrode with the adaptation of insulativity substrates such as glass substrate.

Particularly at above-mentioned conductive ink composition to be that ratio more than the 0.5 quality %, below the 5 quality % contains under the situation of indium with respect to silver, can obtain having concurrently the distribution and/or the electrode of low resistive and anti-isoiony.In addition, above-mentioned conductive ink composition with respect to silver for containing under the situation of indium less than the ratio of 0.5 quality %, can obtain the resistivity of general 4～10 μ Ω cm according to the kind of protective colloid.Therefore, the manufacturing of the circuit substrate used of the above-mentioned conductive ink composition liquid crystal indicator that can be particularly preferred in liquid crystal TV etc., using.

Wherein, above-mentioned resistivity can be obtained by face resistance value of obtaining with four probe method after the thermal anneal process and the thickness of measuring in addition.Wherein, in the present embodiment, in the mensuration of above-mentioned resistance value, use the mensuration machine " ロ レ ス one GP (trade(brand)name) " of Mitsubishi chemical Co., Ltd's system.In addition, in the evaluation of anti-isoiony, use dry-etching device (RIE, active-ion-etch (reactive ionetching) mode).

In the present embodiment, ratio about noble metal in the above-mentioned metal particle and the metal outside the noble metal, can suitably set according to the kind of the metal of the rerum natura of the purposes of above-mentioned conductive ink composition or needs and combination etc., be not particularly limited, when under with the situation of above-mentioned conductive ink composition as the wiring material in the circuit substrates such as tft array substrate for example, above-mentioned metal particle preferably with above-mentioned noble metal as main component.But, when using copper, can use copper as main component as the metal outside the above-mentioned noble metal.

As above-mentioned conductive ink composition, can use that to contain the metal particle that is made of for example silver-colored monomer of noble metal be conductive ink composition as the silver of micelle, but as above-mentioned conductive ink composition, when the silver-indium that uses the metal particle that will be formed by silver and indium as micelle is conductive ink composition, indium with respect to the ratio (indium/silver (quality %)) of silver as mentioned above in above-mentioned metal particle, preferably, for example be configured to ratio as follows according to the purposes of above-mentioned conductive ink composition or the rerum natura of needs etc.For example, when above-mentioned conductive ink composition is used as distribution and/or electrode, in above-mentioned metal particle indium with respect to the ratio (indium/silver (quality %)) of silver preferably in the scope of (promptly surpass 0 quality % and below 6 quality %) below the 6 quality %, more preferably in the scope of (promptly surpass 0 quality % and below 2 quality %) below the 2 quality %.In addition, when above-mentioned conductive ink composition is used as reflection part, in above-mentioned metal particle indium with respect to the ratio (indium/silver (quality %)) of silver preferably in the scope of (promptly surpass 0 quality % and below 0.4 quality %) below the 0.4 quality %, more preferably in the scope of (promptly surpass 0 quality % and below 0.2 quality %) below the 0.2 quality %.

If increase the content (indium concentration) of the indium in the metallic membrane that the usage quantity of above-mentioned indium promptly obtains, can improve anti-isoiony.In addition, if the content of the indium in the metallic membrane that reduces to obtain (indium concentration), anti-isoiony reduces, but can reduce resistance value, improves reflection characteristic simultaneously.Wherein, if increase the content of the indium in the metallic membrane that obtains; although resistance value raises; but the conductive ink composition of present embodiment is by making alloy with silver; the character that suppresses silver; the silver-colored printing ink that forms with disperse silver-colored particulate in organic solvent is compared the particle growth that more can suppress metal; and can suppress the particle growth that with on every side (periphery) compares the metal that produces in the part more than the precious metal amount by protective colloid; simultaneously by using the protective colloid that forms by two kinds of organic compound at least, than the adaptation that more can improve and be coated with object in the past.In addition, reflection characteristic is subjected to the influence of above-mentioned indium concentration, and indium concentration is big more, and reflectivity is low more.Particularly when comparing, shown in the embodiment, can see as described later in low wavelength one lateral reflection rate downward trend with vapor-deposited film.But; as mentioned above; by in silver, adding indium; promptly by use metallic membrane by sosoloid (alloy) formation of silver and indium as reflection part particularly as reflecting electrode; not only can realize high-reflectivity and low resistanceization simultaneously; and as described later shown in the embodiment; by in silver, adding an amount of indium; promptly silver-the indium that comprises above-mentioned protective colloid by use be conductive ink composition as above-mentioned conductive ink composition, for example can realize surpassing the high reflectivity of reflectivity of the aluminium of spatter film forming in one side from 450nm to long wavelength.

The above-mentioned solid matter of present embodiment is that the surface of above-mentioned metal particle is covered the micelle (metal micelle) of (coating) by above-mentioned protective colloid, and when the particle diameter with above-mentioned metallics was made as Ynm, the particle diameter of above-mentioned micelle was about about Y+2～5nm.

Wherein, in the present embodiment, as concrete embodiment, short of special record all use median size to be the metal particle in the scope more than the 2nm, below the 5nm, but the present invention is not limited to this.The particle diameter of such particulate (ultra micron) is less, so its point of contact increases when contact coating object, the while is filming further, can easily give surface smoothing to the distribution and/or the electrode that obtain.

In addition, as the above-mentioned protective colloid that uses in the present embodiment, so long as the protective colloid that is made of two kinds of organic compound at least just has no particular limits.Above-mentioned protective colloid specifically has following form; promptly; compound that obtains as raw material with at least two kinds of organic compound (low molecular material) and/or mixture (that is, compound that obtains by the raw material that constitutes with at least two kinds of organic compound (low molecular material) or the mixture (mixture of organic compound) that obtains by the raw material that constitutes with at least two kinds of organic compound or the mixture of above-claimed cpd and mixture).

As above-mentioned protective colloid; so long as satisfy just having no particular limits of above-mentioned condition; but preferably by contain (A) amine and (B) compound and/or the mixture that form of the raw material of carboxylic acid (monomer composition) as main component (effective constituent); wherein; more preferably by containing (A) amine and (B) carboxylic acid; and above-mentioned (B) carboxylic acid be by the less relatively carboxylic acid of molecular weight (below; be designated as the low molecular weight carboxylic acid) and the relatively large carboxylic acid of molecular weight (below; be designated as high molecular weight carboxylic) compound and/or mixture that the raw material that constituted forms, further preferably use by the low molecular weight carboxylic acid; the raw material that high molecular weight carboxylic and amine constituted and the compound and/or the mixture that form.

In the present embodiment, as above-mentioned low molecular weight carboxylic acid, using carbonatoms is 4～9 carboxylic acid (that is at least a carboxylic acid of selecting from carbonatoms is 4～9 carboxylic acid).As above-mentioned high molecular weight carboxylic, using carbonatoms is 10～30 carboxylic acid (that is at least a carboxylic acid of selecting from carbonatoms is 10～30 carboxylic acid).

That is, be used for above-mentioned (B) carboxylic acid of above-mentioned protective colloid, preferably the mixture of (I) at least a carboxylic acid from carbonatoms is 4～9 carboxylic acid, selected and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected.In addition, the average carbon atom number of preferably above-mentioned (B) carboxylic acid is 5～25.

The inventor etc. concentrate on studies; found that; as above-mentioned protective colloid; use by (A) amine and (B) carboxylic acid constitute; the mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected; and the average carbon atom number of above-mentioned (B) carboxylic acid is under the situation of 5～25 protective colloid; even the less zone of content of the metal outside above-mentioned noble metal (interpolation metal); even and then using under the situation of noble metal monomer as metal particle; also can improve and the adaptation that is coated with object, can suppress the particle growth of above-mentioned noble metal simultaneously.

In addition, as above-mentioned low molecular weight carboxylic acid, preferred (i) carbonatoms is 4～8 carboxylic acid (that is at least a carboxylic acid of selecting from carbonatoms is 4～8 carboxylic acid).In addition, as above-mentioned high molecular weight carboxylic, preferred (ii) carbonatoms be 20～30 carboxylic acid (promptly, at least a carboxylic acid of selecting from carbonatoms is 20～30 carboxylic acid) or (iii) carbonatoms is the mixture of 10～30 carboxylic acid, and more preferably average carbon atom number is the mixture of 15～25 carboxylic acid.

In the present embodiment, above-mentioned (B) carboxylic acid be (i) carbonatoms be 4～8 carboxylic acid and (ii) carbonatoms be 20～30 carboxylic acid or (iii) carbonatoms be the mixture of 10～30 carboxylic acid, can be to be the material that the mixture of 15～25 carboxylic acid forms by average carbon atom number.

About (A) amine and (B) ratio of carboxylic acid in above-mentioned raw materials, be not particularly limited, but preferably above-mentioned (A) amine is in 40 moles more than the %, the 79 moles scopes below the %, above-mentioned (B) carboxylic acid is in 21 moles more than the %, the 60 moles scopes below the % (wherein, both total amounts are 100 moles of %).As above-mentioned (B) carboxylic acid, under the situation of the mixture that uses low molecular weight carboxylic acid and high molecular weight carboxylic, about the ratio of above-mentioned each composition in above-mentioned raw materials, preferred low molecular weight carboxylic acid (is specially at least a carboxylic acid of selecting from carbonatoms is 4～9 carboxylic acid, the preferred at least a carboxylic acid of from carbonatoms is 4～8 carboxylic acid, selecting) at 2 mole more than the %, in the following scope of 40 moles of %, high molecular weight carboxylic (is specially at least a carboxylic acid of selecting from carbonatoms is 10～30 carboxylic acid, the preferred at least a carboxylic acid of from carbonatoms is 20～30 carboxylic acid, selecting, perhaps carbonatoms is the mixture of 10～30 carboxylic acid, average carbon atom number is the mixture of 15～25 carboxylic acid) at 1 mole more than the %, in the following scope of 20 moles of %, preferably above-mentioned (A) amine is at 40 moles more than the %, 79 moles of scopes interior (wherein, their total amount is 100 moles of %) that % is following.

In addition, contain under the situation of dystectic solid carboxylic acid at above-mentioned (B) carboxylic acid, preferably on the basis of the relation of the mol ratio of considering above-mentioned low molecular weight carboxylic acid and high molecular weight carboxylic, by adding the carboxylic acid that carbonatoms lacks than above-mentioned dystectic solid carboxylic acid, and make above-mentioned dystectic solid carboxylic acid dissolving.

As the object lesson of above-mentioned high molecular weight carboxylic, can be exemplified as capric acid, dodecylic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid, octadecanoic acid, octadecenoic acid, octadecadienoic acid, docosoic acid etc.These high molecular weight carboxylics can only use a kind of, can also suitably mix two or more uses.In addition,, can suitably mix high molecular weight carboxylic as mentioned above and use, can also use the high molecular weight carboxylic with molecular weight distribution of the acidic substance mixture naphthenic acid that is present in the petroleum crude oil etc. as above-mentioned high molecular weight carboxylic.Wherein, above-mentioned naphthenic acid can also use with other carboxylic acids are suitably mixed.In addition; in commercially available naphthenic acid, also contain carboxylic acid composition in addition; but in the middle of these compositions; as protective colloid play a role composition (effective constituent) outside composition; can from system, remove by cleaning, for example in removing the operation of remaining protective colloid, cleaning, so can from the application's of finally obtaining conductive ink composition, be removed.Therefore, in above-mentioned raw materials,, can contain above-mentioned (A) amine and (B) composition beyond the carboxylic acid as the composition beyond the above-mentioned effective constituent.

On the other hand, as above-mentioned low molecular weight carboxylic acid's object lesson, can be exemplified as butyric acid, valeric acid, caproic acid, sad etc.These low molecular weight carboxylic acids can only use a kind, also can suitably mix two or more uses.

In addition, in the present embodiment, as above-mentioned (A) amine, preferably use alkylamine, especially preferably using carbonatoms is 5～20 alkylamine.

In the middle of above-mentioned protective colloid, the preferred especially protective colloid that naphthenic acid, caproic acid and octylame are obtained as raw material that uses constitutes protective colloid by octadecadienoic acid, caproic acid and octylame.Wherein, in the present embodiment, as easy acquisition and high molecular weight carboxylic with molecular weight distribution, use naphthenic acid, and this naphthenic acid, use weight-average molecular weight to be about 270 the commercially available naphthenic acid that contains naphthenic, unsaturated carboxylic acid class, ester class, di-alcohols, alkane etc., but the present invention is not limited to this, can use as long as satisfy the material of above-mentioned condition.

In the present embodiment, as above-mentioned (B) carboxylic acid, as mentioned above, can be the chain type carboxylic acid, also can be the ring type carboxylic acid, in addition, so the still many rings of monocycle are not particularly limited.

In the present embodiment; as above-mentioned metal particle; as previously mentioned; when using the metal particle that constitutes by the alloy that contains noble metal at least; as above-mentioned protective colloid; be that the protective colloid that is made of two kinds of organic compound at least gets final product; in above-mentioned protective colloid, can contain above-mentioned (A) amine and (B) composition beyond the carboxylic acid; to these A) amine and (B) composition and the content thereof beyond the carboxylic acid be not particularly limited; but as mentioned above; as above-mentioned protective colloid, preferably contain (A) amine and (B) carboxylic acid as main component, preferably by (A) amine and (B) carboxylic acid constitute.

In addition, as above-mentioned organic solvent (dispersion medium), preferred carbonatoms is 10～35 hydro carbons, and wherein, more preferably using the carbonatoms with side chain is 16～30 aliphatic hydrocarbon.As above-mentioned organic solvent, can be exemplified as non-polar solvents such as the tetradecane, heptamethylnonane, tetramethyl-pentadecane, but be not limited in this.These organic solvents can only use a kind of, can also suitably mix two or more uses.

Above-mentioned organic solvent ratio is easier to obtain, and the dispersion stabilization of the metal particle that covers with above-mentioned protective colloid is better and boiling point is lower simultaneously, so by drying or thermal treatment (for example burning till), can easily remove.

In the present embodiment, proportional about containing of the metal particle in the conductive ink composition of final use, promptly about proportional as containing of the above-mentioned metal particle in the conductive ink composition of conductive ink, be not particularly limited, but in the preferred scope more than 30 quality %, below the 70 quality %.Wherein, in the present embodiment, as concrete form, short of special record used the conductive ink composition that contains above-mentioned metal particle in the scope more than the 30 quality %, below the 40 quality %, but the present invention is not limited to this.The ratio of the above-mentioned metal particle in the preferred above-mentioned conductive ink composition is high as far as possible, and above-mentioned conductive ink composition preferably uses above-mentioned metal particle with high density as far as possible.

In addition, proportional as containing of the protective colloid in the above-mentioned conductive ink composition of conductive ink, preferably proportional and in the scope more than 8 quality %, below the 27 quality % according to containing of above-mentioned metal particle.The usage quantity of above-mentioned protective colloid is excessive with respect to above-mentioned metal particle.In the present embodiment, for example with respect to above-mentioned metal particle, the usage quantity of above-mentioned protective colloid is the amount of 15 times of molar ratios, but with respect to above-mentioned metal particle, the usage quantity of above-mentioned protective colloid is that the above amount of 1 times of mole gets final product.Forming micelle (metal micelle) afterwards, remaining protective colloid can be removed from system (conductive ink composition) by cleaning.

Then, about above-mentioned micelle and the making method that contains the conductive ink composition of this micelle, be that example is carried out following explanation with the situation of making the metal particle that constitutes by the metal that contains silver and indium.

Above-mentioned conductive ink composition is easily to obtain according to following method; promptly metal-salt (metal ion) being reduced to handle in the presence of above-mentioned protective colloid separates out above-mentioned micelle; remove remaining protective colloid and cleaning then, be replaced as target organic solvent (dispersion medium).The conductive ink composition of present embodiment (conductive ink) is that the state with colloidal metal solution is used by disperse above-mentioned micelle in organic solvent (dispersion medium).

Say that more specifically for example, at first shown in Fig. 2 (a), the raw material 302 of pack into solvent, metal-salt and protective colloid is modulated metal salt solution in reaction vessel 301.In addition; above-mentioned metal salt solution can be according to after being dissolved in metal-salt in the solvent; in this solution, add of the method modulation of the raw material 302 of above-mentioned protective colloid as the dispersion agent that prevents the metal particle cohesion, also can be according to the method modulation of the above-mentioned metal-salt of dissolving in containing as the solvent of the raw material 302 of the above-mentioned protective colloid of above-mentioned dispersion agent.In addition, above-mentioned metal-salt becomes coordination ion (silver complex compound, indium coordination compound) in metal salt solution (metal ion solution).

Subsequently, shown in Fig. 2 (b), in above-mentioned metal salt solution, add reductive agent 303, make silver and two kinds of metallic reducings of indium and in the particle growth process, form alloy, separate out silver-indium alloy particle.Thus, in the solvent in above-mentioned reaction vessel 301, except having silver-colored particulate, indium particulate, also there is the alloy particle that constitutes by silver-indium alloy as metal particle 304 (with reference to Fig. 2 (c)).

Shown in 2 (c), be attached on the protective colloid 305 according to the promptly for example above-mentioned alloy particle of the above-mentioned metal particle of separating out like this 304, can obtain the micelle that the surface of above-mentioned metal particle 304 is covered by above-mentioned protective colloid 305 thus.Subsequently, remove the remaining protective colloid 305 that does not form above-mentioned micelle and clean, the solvent exchange in the above-mentioned reaction vessel 301 is become target organic solvent (dispersion agent), thereby can obtain the conductive ink composition of present embodiment.

Also have, the particle diameter of above-mentioned metal particle 304 can be controlled by the control of above-mentioned reduction reaction and the selection of above-mentioned protective colloid.

In addition, according to above-mentioned method, nature can be expected making the reduction of silver ions and indium ion and carrying out alloying in the particle growth process as mentioned above, thereby in the particle set that the is reduced process together, existence becomes the material of micelle with free state, even and form alloy but its ratio is also different because of particle.But, in aforesaid method, the ratio of the multiple metal ingredient that contains in the micelle (being the silver-colored composition that contains in each micelle and the ratio of indium composition in above-mentioned example) is all consistent in all micelles, this is unimportant, importantly when finally becoming membrane stage, can obtain multiple Metal Distribution and nonmetal monomeric alloy effect.

In the present embodiment, as the solvent that is used to modulate above-mentioned metal salt solution (organic solvent), can specifically be exemplified as toluene, dimethylbenzene, hexane, pure isooctane etc., but be not limited to this.As above-mentioned solvent, because dissolve and remove raw material 302, metal-salt, the reductive agent 303 (reductant solution) of above-mentioned protective colloid easily, so preferably use pure isooctane.

But, because above-mentioned protective colloid is a liquid, above-mentioned metal salt solution can not use the solvent of dissolved metal salt, and only modulates with protective colloid.

Above-mentioned metal-salt (metallic compound) as being used for present embodiment can be exemplified as Silver monoacetate and indium acetate, but present embodiment is not limited to this.Silver compound as beyond the above-mentioned Silver monoacetate can be exemplified as Silver Nitrate, silver perchlorate, silver benzoate, silver formate, silver propionate etc.In addition, as the indium compound outside the indium acetate, can enumerate indium nitrate, indium sulfate, Indium Tris acetylacetonate, indium hydroxide, 2 ethyl hexanoic acid indium etc.These metal-salts can only use a kind of, also can the two or more uses of appropriate combination.When preparing the metal particle that constitutes by silver,, for example can use at least a silver compound of from above-mentioned illustrative silver compound, selecting as above-mentioned metal-salt as above-mentioned metal particle.Wherein, above-mentioned metal-salt is not limited to silver compound, indium compound, for the metal particle that needing to obtain, can suitably select, be used in combination.

As the concentration of above-mentioned metal-salt, for example setting becomes 15～500mmol/L, but as mentioned above, above-mentioned solvent is also inessential, and above-mentioned metal salt concentrations has more than and is limited in the above-mentioned scope.

In addition, as mentioned above, add above-mentioned protective colloid (raw material 302 of protective colloid), the amount that to make its above-mentioned relatively metal particle be metal is 1 times more than the mole, for example is 15 times of moles.

In addition, as above-mentioned reductive agent 303, for example can use sodium borohydride.Above-mentioned sodium borohydride for example uses as 2-propanol solution (30mmol/L), but is not limited to this, can also dissolve use in above-mentioned illustrative solvents (organic solvent) such as pure isooctane.

In addition, as above-mentioned reductive agent 303, except above-mentioned sodium borohydride, for example also preferred stronger reductive agent relatively such as lithium borohydride, hydrazine, aluminium isopropoxide that uses.

Above-mentioned reductive agent 303 for example uses 1～4 times of equivalent with respect to the equivalent of metal particle (metal).

The speed of dripping of above-mentioned reductive agent 303 is for example set and is become 5～100mL/ minute.Like this, not once to add reductive agent 303 but drip (interpolation) with fixing speed, perhaps divide and add several times, stir, can control the particle diameter of the metal particle that obtains thus.

Temperature of reaction in the above-mentioned reaction, reaction pressure, reaction times are not particularly limited, after the reductive agent that for example in atmosphere, drips, at room temperature carry out stirring in 1 hour, and can carry out above-mentioned reaction.

In addition, in above-mentioned reaction solution, amines such as octylame are with respect to above-mentioned metal particle 304 excessive existence.For this reason, the pH of above-mentioned reaction solution was about 10～11 before cleaning.

In addition, above-mentioned purging method is not particularly limited, after the colloidal solution that contains the micelle after above-mentioned reduction is handled is concentrated, adds excessive methyl alcohol or ethanol, and filtration and can cleaning.

In addition, in the present embodiment, handle as above-mentioned reduction, method with interpolation reductive agent 303 in above-mentioned metal salt solution is that example is illustrated, but also can use the above-mentioned reductive agents 303 of replacement such as UV-light, electron rays, heat energy to reduce, as long as can reduce above-mentioned metal ion, then above-mentioned method of reduction treatment just is not particularly limited.

According to present embodiment; as mentioned above; cover metal particle and be dispersed in the organic solvent (dispersion medium) with protective colloid; after being coated on the coating object then; for example under 250～350 ℃, burn till by drying or thermal treatment, and can easily form the metallic membrane (metallic film) that constitutes by above-mentioned metal.

Promptly, used the distribution of above-mentioned conductive ink composition, can be according on the real estate that is becoming the coating object, above-mentioned conductive ink composition is dispersed in after the state coating in the above-mentioned organic solvent with above-mentioned solid matter, the method of for example burning till easily forms.

According to present embodiment; when the solid matter in the above-mentioned conductive ink composition is that above-mentioned micelle is when being sintered; the protective colloid on above-mentioned metal particle surface is that organic materials is removed, thereby above-mentioned metal particle fuses each other, can form low-resistance metallic membrane thus.

In addition, promptly to burn till film with respect to the metallic membrane that obtains be below the 5 quality % to the residual volume of the protective colloid after burning till.By for example the forming of silver-indium alloy of forming of the metallic membrane that is fired into, for example can carry out quantitative analysis, can estimate thus by ultimate analyses such as EDS (energy dispersion type X-ray analysis) or EPMA (X-ray microanalyzer) analysis or ICP (inductively coupled plasma) luminescence analysis etc.In addition, about residual organic composition, can estimate by the analysis of TG heat such as (thermogravimetries).

Method as above-mentioned conductive ink composition being coated on the coating object can be exemplified as ink jet method or spin-coating method etc.

When stating conductive ink composition formation metallic membrane in the use, for example can be with above-mentioned conductive ink composition the solid matter in this conductive ink composition is scattered in the state in the above-mentioned organic solvent (dispersion medium), be coated on the glass substrate by spin-coating method, carry out drying or thermal treatment (for example burning till) then.

As the spin coating condition, be not particularly limited, for example can in the scope of 500rpm～2000rpm, set.For example, by carrying out 30 seconds spin coating, can obtain thickness and be the film (conductive ink composition film) that constitutes by above-mentioned conductive ink composition of 2500  (250nm) with 1000rpm.Wherein, above-mentioned spin coating condition can suitably be adjusted by thickness as required, is not particularly limited.

And then, to above-mentioned conductive ink composition film burn till pressure and firing temperature is not particularly limited, but in the burning till in atmosphere, in 250～350 ℃ scope, set usually.Wherein, firing time can suitably be set according to the thickness of above-mentioned conductive ink composition film or firing temperature etc., is not particularly limited.

For example, be that the conductive ink composition film of 1 atom % (1.06 quality %) burns till the metallic membrane (burning till film) that obtained in 1 hour in atmosphere, under 300 ℃ resistance value is about 10 μ Ω cm with indium with respect to the ratio of silver.

Surface smoothing for above-mentioned metallic membrane is the state of particle growth, for example observes the multiplying power of for example using about 10,000 times～30,000 times by SEM (scanning electron microscope), can easily observe.But, even do not use SEM, under the situation of visual observation, not having the film surface under the particle growth situation is minute surface, relative therewith, is having under the situation of particle growth, the film surface appears to have white casse, so according to the degree of particle growth, also can confirm particle growth down visual.

Usually, noble metal is stable, so therefore reactive low with substrate lack and the adaptation of substrate.The effect of squeezing into of sudden particle is to improve the major cause of the adaptation of noble metal and substrate in the methods such as sputter, but when coating, can not expect has such effect of squeezing into, and can only obtain adaptation by the avidity with substrate.For this reason, configuration easily and oxygen bonded metal to the combining or avidity that diffusion causes of the avidity of oxygen and noble metal and metal, makes noble metal and substrate adherence by substrate between substrate and noble metal usually.

In the past, the printing ink of using as ink-jet (ink) usually used silver-colored printing ink more, but former silver-colored printing ink is except the character with aforesaid noble metal, and it is remarkable especially to burn till the particle growth that causes by high temperature, and the metallic membrane that obtains is difficult to directly as distribution.

For this reason, when with silver when the wiring material, be necessary implementing to be used to improve the processing of sticking power on the substrate, perhaps on silver-colored distribution, form the film deterioration that causes with the deterioration that prevents the surface smoothing that heat causes or etching gas as the film of protective membrane, peel off.That is, make the thin-film multilayerization on the substrate, consequently the worker ordinal number of circuit substrate increases, and cost also raises.

Therefore, the inventor etc. concentrate on studies, found that, when for example forming alloy when the metal beyond the noble metals such as interpolation indium in silver, can reduce the particle growth of silver, adaptation becomes well, prevents the multiple stratification of film, the increase of the worker ordinal number of inhibition circuit substrate and the increase of cost.

But, the inventor etc. are found that of research further, as described above with silvery precedent such as silver-indium alloy, compare with the silver-colored monomeric situation of use, although improve, burn till by high temperature and many diameters, height still to occur and all be about 1000 ～5000  (projection (particle growth) of about 100nm～500nm) the adaptation of glass, superficiality when high temperature burns till.

Therefore; the inventor etc. have carried out further research again; found that; as mentioned above; by noble metal is made alloy with silver this moment; the character that suppresses silver, and can suppress the particle growth that with on every side (periphery) compares the metal that produces in the part more than the precious metal amount by protective colloid.In addition, the inventor etc. also find, by using the protective colloid that constitutes by two kinds of organic compound at least, and can be more in the past than the adaptation that more can improve with the coating object.

Particularly when using silver, above-mentioned effect is remarkable, clear and definite can significantly suppress particle growth by above-mentioned protective colloid.

In addition, the inventor etc. are found that of research further, by further trying every possible means on protective colloid, can obtain suppressing more significantly the effect of particle growth.Particularly by using from (A) amine and (B) raw material of carboxylic acid of aforesaid containing; especially from (B) carboxylic acid of aforesaid low molecular weight carboxylic acid of comprising and high molecular weight carboxylic and (A) amine and the specific protective colloid that obtains; even the less zone of content of the interpolation metal in the film of making by conductive ink composition; for example in zone that the indium content of silver-indium metal film reduces; also can improve adaptation with the coating object; and then; even using under the situation of noble metal monomer as metal particle, still can improve above-mentioned adaptation and suppress particle growth.That is, also can solve the problem that in indium content is 0 silver-colored monomeric film, exists.

Fig. 1 is the ink film that will use silver-indium that the protective colloid shown in the embodiment 2 as described later (protective colloid that is made of caproic acid, naphthenic acid, octylame) forms as above-mentioned protective colloid with scanning electron microscope photo (30,000 times of multiplying powers) expression, at N ₂The state of the metallic film surface of carrying out annealing in 1 hour in the gas atmosphere under 300 ℃ and obtaining.Wherein, in the ink film of above-mentioned silver-indium, indium is set with respect to the ratio of silver becomes 1 atom %.In addition, scanning electron microscope uses the SEM (scanning electron microscope) " S-4100 (trade(brand)name) " of Hitachi's system.Wherein, indium (In) the 1 atom % in silver-indium alloy (AgIn) is equivalent to indium (In) 1.06 quality %.

And then, in order to compare, in Figure 25, use scanning electron microscope photo (30,000 times of multiplying powers) to be illustrated in N equally ₂The state on the monomer vapor-deposited film surface of the silver that carries out 1.5 hours thermal anneal process under 300 ℃ in the gas atmosphere and obtain.Wherein, the film forming of the monomer vapor-deposited film of above-mentioned silver is to utilize " high vacuum vapor deposition device EBX-10D (trade(brand)name) " (ULVAC Corp's system electron beam evaporation plating machine) and adopt vapour deposition method to carry out.

In addition, in Figure 26, use scanning electron microscope photo (30,000 times of multiplying powers) to be illustrated in N equally ₂The state on the surface of the silver-indium vapor-deposited film (the indium add-on is 3.0 quality %) that carries out 1.5 hours thermal anneal process under 300 ℃ in the gas atmosphere and obtain.

And then; in Figure 27; same with scanning electron microscope photo (30,000 times of multiplying powers) expression use by with protective colloid shown in Figure 1 in identical naphthenic acid and the octylame protective colloid that constitute, shown in embodiment 6 of naphthenic acid that use; the ink film of the silver-indium that forms as protective colloid is at N ₂The state of the metallic film surface of carrying out annealing in 1 hour in the gas atmosphere under 300 ℃ and obtaining.

In addition, for relatively, in Figure 32, use scanning electron microscope photo (30,000 times of multiplying powers) expression only to use octylame and the ink film of the silver that forms equally, at N as protective colloid ₂The state of the metallic film surface of carrying out annealing in 30 minutes in the gas atmosphere under 300 ℃ and obtaining.In addition, in Figure 33, use scanning electron microscope photo (30,000 times of multiplying powers) expression to use the protective colloid that constitutes by naphthenic acid and octylame and the ink film of the silver that forms equally, at N as protective colloid ₂The state of the metallic film surface of carrying out annealing in 30 minutes in the gas atmosphere under 300 ℃ and obtaining.

And, except above-mentioned each condition,, follow condition and the method in explanation described later and embodiment, enumerated for the concrete manufacturing conditions and the creating method of these ink films.Coating condition when in addition, the base plate coating as the coating object being used to make each conductive ink composition of each above-mentioned ink film is all identical.

Shown in figure 32; if will as silver-colored printing ink in the past, use silver-colored monomer as metal particle, in addition be conductive ink composition in order to compare the silver that only uses a kind of organic compound to form as protective colloid; be applied on the substrate as the coating object; anneal as mentioned above then; then silver-colored nanoparticle fused, grew this moment, can observe the state of network-like connection.

In addition, as can be seen from Figure 32, as above-mentioned, be the ink film that conductive ink composition constitutes by the silver that only uses a kind of protective colloid, on film surface and film cross section, bigger emptying aperture is arranged all, face is coarse remarkable, and light can see through film.Therefore, reflection efficiency is poor.And, think that light is that the reason of the ink film that constitutes of conductive ink composition is above-mentioned emptying aperture by this by the silver that only uses a kind of protective colloid.

In addition, with regard to ink film shown in figure 32, face is coarse significantly as mentioned above, on whole face, be formed with by the particle growth of silver and fusion produce uneven, to the sticking power (adaptation) of substrate very a little less than.

And ink film is shown in figure 32 compared with ink film shown in Figure 1 with Figure 27, at first sight comes thickness thicker.This is because ink film shown in Figure 32 contains the emptying aperture of a great deal of in film.

In addition; as shown in figure 33; if will use silver-colored monomer to use the protective colloid that constitutes by naphthenic acid and octylame and the silver that forms is conductive ink composition as metal particle and as protective colloid; be applied on the substrate as the coating object; carry out aforesaid annealing then, then at this moment the same with ink film shown in Figure 32, even carry out 30 minutes annealing; particle growth (height of particulate is more than the 500nm) fierceness of silver, the thickness of the ink film that obtains is obviously inhomogeneous.Specifically, as mentioned above, the height of the particulate that is produced by the particle growth of silver in the ink film shown in Figure 33 is more than the 500nm, and the thickness of the ink film below the particulate is about 100nm, and is thinner.This is the thickness attenuation that causes the ink film of the part outside the particle growth in the particle growth of silver because of the silver around taking in.In addition, ink film shown in Figure 33 has pore on film surface and film cross section.

Therefore, at first, the additive effect of indium should be confirmed, when Figure 25 relatively and vapor-deposited film shown in Figure 26, under the monomeric situation of silver, coarse film surface can be improved by adding indium as shown in figure 26.

Then; when comparing ink film; as shown in figure 33; with respect to using silver-colored monomer as metal particle and using the protective colloid that constitutes by naphthenic acid and octylame and the ink film of the silver that forms as protective colloid; as shown in figure 27; add indium and use equally the protective colloid that constitutes by naphthenic acid and octylame and the ink film of the silver-indium that forms with the ratio of silver-colored relatively 1 atom % as metal particle as protective colloid; it utilizes the additive effect of indium to suppress the particle growth of silver; the size of particulate with use silver-colored monomeric situation to compare obviously to reduce as metal particle, simultaneously not as the pore of on ink film as shown in figure 33, seeing.In addition, the same with Figure 27 for ink film as shown in Figure 1, obviously reduce with the size of using silver-colored monomer to compare particulate, simultaneously as can be known not as the pore of on ink film as shown in figure 33, seeing as the situation of metal particle.

In addition; when the ink film that more only uses silver a kind of protective colloid, shown in Figure 32 and Fig. 1 and ink film shown in Figure 27; as Fig. 1 and shown in Figure 27; as can be known by using the conductive ink composition of present embodiment; the particle growth that can suppress metal is to a great extent improved the surface smoothing of the ink film obtain greatly.And then, as Fig. 1 and shown in Figure 27,, can suppress the particle growth of metal, and can prevent to peel off (decortication) as the film of in Figure 32, seeing by using the conductive ink composition of present embodiment.Therefore as can be known, the ink film that obtains by the conductive ink composition that uses present embodiment and the adaptation of substrate, compared with the past being much improved.

In addition, as Fig. 1 and shown in Figure 27, by using the conductive ink composition of present embodiment, can prevent forming as the emptying aperture of in ink film shown in Figure 32, seeing, cause by the particle growth and the fusion of metal, so can prevent seeing through of the light that causes by such emptying aperture, can be than more can improve reflection efficiency in the past.

And then, as shown in figure 27, in the ink film of silver-indium; although find out the effect of improving on rough textured film surface that interpolation and protective colloid by indium cause; but find out to still have particle growth, as can be known as shown in Figure 1, can significantly suppress particle growth by selecting protective colloid.

As can be known from the above results; with the conductive ink composition of present embodiment, particularly will use the conductive ink composition of protective colloid to carry out drying or thermal treatment (for example burning till) and the metallic membrane that obtains as protective colloid with above-mentioned molecular weight distribution; its surface smoothing (flatness) excellence is even be configured in aforesaid bottom distribution (downside distribution) or be subjected to the condition of surface of bottom distribution (downside distribution) or the following of elements such as TFT of surface roughness affect not influenced by it.That is, even above-mentioned metallic membrane is used as bottom distribution (downside distribution) in wiring crossing portion, sewing of can reducing also that film fracture by the fracture of top distribution (upside distribution) or the insulation layer between above-mentioned bottom distribution and the top distribution causes is bad etc.

Thus, be used for printing ink (conductive ink), can form the good and low-resistance coating distribution of superficiality as wiring material by the conductive ink composition that will use above-mentioned protective colloid.

Above-mentioned conductive ink composition can be preferred for the distribution among the FPD (flat pannel display), the electrode etc. that is particularly preferred for wiring crossing portion and is subjected to the substrate that becomes elements such as TFT of surface roughness affect easily.

The distribution that is made of above-mentioned conductive ink composition for example forms by step as follows.

(1) at first on substrate, forms the pattern that forms by cofferdam (partition wall).Be specially, on substrate, after the spin-coating erosion resistant agent, this resist carried out prebake, after pattern exposure, develop, after cure.

Wherein, the distribution width in the above-mentioned pattern and the height in above-mentioned cofferdam are not particularly limited, but for example can be distribution width 30 μ m, cofferdam height 2 μ m.

(2) then, to having formed the substrate of above-mentioned pattern, at for example CF ₄Carry out plasma treatment under the gas atmosphere.Thus, when the surface in cofferdam being carried out the fluorine processing, decompose the organism of removing on the substrate.

(3) then, by ink discharge device, above-mentioned conductive ink composition is coated on the Wiring pattern by the cofferdam clamping.Wherein, the size based on the drop of above-mentioned ink discharge device is not particularly limited, but, sets for about 6pl as an example.

(4) as mentioned above, for example under 300 ℃, burn till after above-mentioned conductive ink composition being coated on the face of distribution, metallize.

Below, the formation of concrete distribution is described in detail.

, preferably use by so-called ink jet method (drop ejection method) ejection or drip the ink discharge device (pattern formation device) of wiring material or electrode materials etc. promptly in the pattern of this circuit substrate forms in the manufacturing of the circuit substrate of present embodiment.Fig. 3 represents that this pattern forms the signal formation of device.

Pattern shown in Figure 3 forms mounting table 32 that device 81 comprises mounting substrate 31, as making this ink gun 33 among the ink gun 33 of drop generator (drop ejection mechanism), Fig. 3 at the directions X driving part 34 that moves on the directions X, the Y direction driving part 35 that on the Y direction, moves.Above-mentioned ink gun 33 is configured to, and the substrate on the mounting table 32 31 is sprayed the conductive ink composition of present embodiment in the mode of the drop of the flowability that contains wiring material or electrode materials.

In addition, above-mentioned pattern forms device 81 and is provided with to ink gun 33 and provides printing ink as the conductive ink composition (ink) of the present embodiment of mobile wiring material that system 36 is provided, carry out the control unit 37 of various controls such as driving control of ejection control, directions X driving part 34 and the Y direction driving part 35 of ink gun 33.To directions X driving part 34 and Y direction driving part 35 output coating positional informations, export ejection information from control unit 37 to the shower nozzle driving mechanism (not shown) of ink gun 33.Thus, directions X driving part 34 and Y direction driving part 35 carry out interlock makes ink gun 33 work, and the target location on substrate 31 provides the drop (conductive ink composition) of aim parameter.

As above-mentioned ink gun 33, can be to use the ink gun of the piezoelectricity mode of piezoelectric actuator, can also be the ink gun of foaming (bubble) mode that in ink gun, has well heater or the ink gun of other modes.To control, prepare according to needed spray volume and the ink gun of design optimization just can be realized, but the diameter that also can change nozzle bore is simply realized from the quantity of ink of ink gun 33 ejection.In addition,, replace ink gun 33, can provide the device of drop just to be not particularly limited so long as only drip the device etc. of the mode of drop as above-mentioned drop generator.

The conductive ink composition of present embodiment is preferably used as the formation material of distribution of the circuit substrate that requires surface smoothing etc.In addition, the sort circuit substrate is preferred for electronic installations such as display unit.

Below, as follows, the circuit substrate and the electronic installation of present embodiment are described according to Fig. 4～Fig. 7 (a) and Fig. 7 (b).

And, in the following description, as the circuit substrate and the electronic installation of present embodiment, with tft array substrate and used the liquid crystal indicator of this tft array substrate to describe as example, but the present invention and not all be limited to this.

Fig. 4 is the orthographic plan of schematic construction of tft array substrate of the liquid crystal indicator of expression present embodiment, and Fig. 5 is the orthographic plan of the schematic construction of 1 pixel in the expression tft array substrate shown in Figure 4.In addition, Fig. 6 is that A-A in as shown in Figure 5 the tft array substrate is to sectional view, Fig. 7 (a) is the orthographic plan of the schematic construction of 1 portion of terminal in the tft array substrate of representing as shown in Figure 4, and Fig. 7 (b) is that the B-B of the portion of terminal shown in Fig. 7 (a) is to sectional view.

As shown in Figure 4, the structure that the tft array substrate 11 of present embodiment is had is: glass substrate 12 is provided with the pixel that has formed a plurality of pixels as shown in Figure 5 and forms zone 61, simultaneously this pixel form zone 61 around and above-mentioned tft array substrate 11 be provided with the portion of terminal that has formed a plurality of portion of terminal 28 as Fig. 7 (a) and Fig. 7 (b) shown in and form regional 62 ...

As shown in Figure 5 and Figure 6, the structure that the tft array substrate 11 of present embodiment has is: gate wirings 13 and source electrode distribution 14 are configured to rectangularly on glass substrate 12 (insulativity substrate) 12, are provided with the TFT15 as switching element near the cross part of these gate wirings 13 and source electrode distribution 14.In addition, between contiguous gate wirings 13,13, be provided with auxiliary capacitor distribution 16 (memory capacitance distribution).

As shown in Figure 6, on glass substrate 12, formed the gate electrode 17 and the above-mentioned auxiliary capacitor distribution 16 that form from gate wirings 13 branches, also be formed with gate insulator 18 in the mode that covers these gate electrodes 17 and auxiliary capacitor distribution 16.

In addition, on above-mentioned gate electrode 17, be formed with semiconductor layer 27, source electrode 21, the drain electrode distribution 22 that constitutes by amorphous silicon layer 19 and n+ type silicon layer 20, thus, form above-mentioned TFT15 by above-mentioned gate insulator 18.Here, source electrode 21 forms from source electrode distribution 14 branches.

In addition, drain electrode distribution 22 is 23 extend to be provided with from TFT15 to contact hole, have function as the drain electrode of TFT15, be electrically connected TFT15 and pixel electrode 24 function and by contact hole 23 and and auxiliary capacitor distribution 16 between form the function of electric capacity.And then, be formed with the protective layer 25 that covers TFT15 in order on the upper strata of above-mentioned drain electrode distribution 22, be used for planarization etc. interlayer insulating film 26, be used for liquid crystal etc. is applied the pixel electrode 24 of voltage.

And then shown in Fig. 7 (a) and Fig. 7 (b), the structure that portion of terminal 28 has is, begins to dispose in order terminal distribution 30 and terminal electrode 29, gate insulator 18 from glass substrate 12 1 sides.That is, above-mentioned portion of terminal 28 has the structure that covers the part of above-mentioned terminal distribution 30 and above-mentioned terminal electrode 29 with above-mentioned gate insulator 18.Portion of terminal 28 is to be used for being electrically connected external circuit substrate on tft array substrate, to drive the connection section with driver IC etc., and the purpose that disposes above-mentioned terminal electrode 29 is to make external circuit substrate, it is good etc. with the electrical connection of driver IC to drive.In addition, terminal distribution 30 and above-mentioned pixel form gate wirings 13 on the zone 61, source electrode distribution 14 etc. and are connected.

In addition, in the present embodiment, above-mentioned terminal distribution 30 and terminal electrode 29 all are formed on the glass substrate 12, all are made of the AI alloy as the same silver alloy of forming.But, in terminal distribution 30 and terminal electrode 29, indium is with respect to containing of silver of proportional difference.Here, regulate proportioning so that in terminal distribution 30 indium proportional proportional with respect to containing of silver with respect to containing of silver less than indium in terminal electrode 29.

Then, according to Fig. 3～Figure 24, the method for using above-mentioned conductive ink composition to make the above-mentioned tft array substrate 11 of present embodiment is carried out following explanation.

In the present embodiment; as shown in Figure 8, above-mentioned tft array substrate 11 is by gate wirings pretreatment procedure 101, and gate wirings forms operation 102; gate insulating film, semiconductor film film formation process 103; gate insulating film, semiconductor film manufacturing procedure 104, source, drain electrode distribution pretreatment procedure 105, source, drain electrode distribution form operation 106; groove manufacturing procedure 107; protective membrane, interlayer insulating film film formation process 108, protective membrane manufacturing procedure 109, and pixel electrode forms operation 110 and forms.

(gate wirings pretreatment procedure 101)

In above-mentioned gate wirings pretreatment procedure 101, use pattern shown in Figure 3 to form device 81, be used to form the pre-treatment of gate wirings 13, gate electrode 17, auxiliary capacitor distribution 16 etc.The pixel portion in the tft array substrate 11 after Fig. 9 (a) and Figure 10 (a) expression gate wirings pretreatment procedure 101 finishes and the orthographic plan of terminal part, Fig. 9 (a) and Figure 10 (a) are respectively that the pixel on the glass substrate 12 shown in Figure 4 forms the orthographic plan that zone 61 (pixel portion), portion of terminal form regional 62 (terminal parts).

In above-mentioned gate wirings pretreatment procedure 101, in order to form the Wiring pattern that needs, be used to form the pre-treatment of distribution, the wiring material that forms the flowability of device 81 ejections (drippage) by above-mentioned pattern is applied on the zone of needs.

As above-mentioned pre-treatment, roughly be divided into two kinds of methods.

The 1st method is by the distribution shown in Fig. 9 (a) and Figure 10 (a) being formed the zone as hydrophilic region (lyophily zone), non-distributions beyond these zones are formed the zone as the close and distant water treatment (close and distant liquid processing) of hydrophobic region (lyophobic areas) and the method for patterning, wherein, distribution form the zone comprise the gate wirings that is used to form gate wirings 13 form the zone 41, the gate electrode that is used to form gate electrode 17 forms zone 42, the auxiliary capacity that is used to form auxiliary capacitor distribution 16 forms zone 43, and the terminal distribution that is used to form terminal distribution 30 and terminal electrode 29 (portion of terminal 28) forms zone 44.

The 2nd method is to form as the guide part (dividing plate) of restriction liquid stream to form zone 41, gate electrode along above-mentioned gate wirings and form zone 42, auxiliary capacitor distribution and form the method that zone 43 and terminal distribution form the guide part in zone 44.

As above-mentioned the 1st method, be treated to representative with the close and distant water (close and distant liquid) of the photocatalyst that used titanium dioxide.On the other hand, as above-mentioned the 2nd method, be representative to use erosion resistant and to carry out the method that guide part forms by photolithography.And then, in order to give close and distant water (liquid) property, carry out sometimes above-mentioned guide part or exposure of substrates in having imported CF to above-mentioned guide part or real estate ₄Gas, O ₂Processing in the plasma atmosphere of gas.Etchant resist used herein is peeled off after distribution forms.

In the present embodiment, as above-mentioned pre-treatment, use the photocatalyst treatment of titanium dioxide.That is, on the glass substrate 12 of tft array substrate 11, be coated in the aqueous isopropanol that to mix as fluorine be the liquid that " ZONYL FSN " (trade(brand)name, E.I.Du Pont Company's system) back of nonionic surface active agent forms.In addition, on the mask of gate wirings pattern etc., adopt the liquid that in ethanol disperseed titanium dioxide fine particles of spin-coating method coating, under 150 ℃, burn till as photocatalyst layer.Then, use above-mentioned mask, to glass substrate 12 with 70mW/cm ²The UV-light 2 minutes of intensity irradiation 365nm, carry out the exposure (UV exposure) of above-mentioned glass substrate 12 thus.

Here, with reference to Figure 11 (a)～Figure 11 (d) to carrying out following explanation based on the formation in the close and distant water (close and distant liquid) of titanium dioxide zone.

Figure 11 (a) is illustrated on the glass substrate 1 that use spin-coating method etc. to be coated on to mix as fluorine in the aqueous isopropanol be " ZONYL FSN " (trade(brand)name of nonionic surface active agent, E.I.Du Pont Company's system) liquid of back formation, the state of formation the 1st film 2 on above-mentioned glass substrate 1 thus.

In addition, Figure 11 (b) expression utilizes the masks 4 such as gate wirings pattern that are provided with on transparent glass substrate 3 to carry out the state of UV exposure.On the pattern plane of above-mentioned mask 4, be coated on the liquid that has disperseed above-mentioned titanium dioxide fine particles in the ethanol, under 150 ℃, heat-treat as photocatalyst layer 5.

After exposure based on above-mentioned condition, shown in Figure 11 (c) and Figure 11 (d), only improve in part 6 wettabilitys of being exposed by UV, form hydrophilic (liquid) pattern.

(gate wirings forms operation 102)

Then, with reference to Fig. 9 (b), Fig. 9 (c), Figure 10 (b) and Figure 10 (c) gate wirings is formed operation 102 and carry out following explanation.

Fig. 9 (b), Fig. 9 (c), Figure 10 (b) and Figure 10 (c) are the orthographic plans that gate wirings forms the glass substrate 12 after operation 102 finishes.Fig. 9 (b) and Figure 10 (b) are respectively that the pixel on the glass substrate 12 shown in Figure 4 forms the orthographic plan that zone 61 (pixel portion), portion of terminal form zone 62 (terminal parts).Fig. 9 (c), Figure 10 (c) are respectively that the C-C of Fig. 9 (b), Figure 10 (b) looks sectional view, D-D to sectional view.

Form in the operation 102 in above-mentioned gate wirings, use above-mentioned pattern to form device 81, and use above-mentioned glass substrate 12 as aforesaid substrate 31, gate wirings on the glass substrate 12 shown in Fig. 9 (a) and Figure 10 (a) forms zone 41, gate electrode forms zone 42, the auxiliary capacitor distribution forms zone 43, form on regional 44 hydrophilic regions such as grade (lyophily zone) with the terminal distribution, the conductive ink composition of present embodiment is coated with as mobile wiring material, thus, as Fig. 9 (b), Fig. 9 (c), shown in Figure 10 (b) and Figure 10 (c), form gate wirings 13, gate electrode 17, auxiliary capacitor distribution 16, terminal distribution 30 distributions such as grade.

In above-mentioned wiring material; conductive ink composition as present embodiment; for example use and in organic solvent, disperse the silver-indium alloy particulate that covers with above-mentioned protective colloid (that is, being specially the protective colloid of putting down in writing at embodiment 2 described later) and the liquid that forms.And, in the present embodiment, regulate the silver that contains in the above-mentioned conductive ink composition and indium aptly so that indium is about below the 5 atom % with respect to the ratio of silver.Setting distribution width is about 50 μ m, above-mentioned conductive ink composition is 5pl from the spray volume of ink gun 33.

In addition; about the silver that contains and the ratio of indium in the conductive ink composition of ejection; consider gate insulating film afterwards; semiconductor film manufacturing procedure 104; groove manufacturing procedure 107; carry out dry-etching in the protective membrane manufacturing procedure 109; thereby the adjusting indium is with respect to the ratio of silver; the part that makes this ratio be exposed in operation in the plasma body is 5 atom %; on the other hand; consider and require gate wirings 13 to be low resistance; thereby regulate the ratio of indium with respect to silver, the part that makes this ratio directly not be exposed in the plasma body being covered by gate insulator 18 and protective layer 25 is 1 atom %.

This is because the tolerance of article on plasma body is improved when the increasing proportion of indium.In addition, in the operation of carrying out subsequently is gate insulating film, during semiconductor film film formation process 103, gate wirings 13 applied 300 ℃ heat, even if but under such temperature, gate wirings 13 can not become coarse because of surfaces such as crystal growths yet, and the time that applies signal to gate wirings 13 is tens of μ sec, time is shorter, so need to reduce as far as possible since the resistance of gate wirings 13 and from drive the TFT15 near with driver IC and away from the locational TFT15 that drives with driver IC between the response characteristics that signal delay the caused variation that produces, for this reason, require the resistance of above-mentioned gate wirings 13 low.

But above-mentioned ratio can suitably be selected according to performance of the tft array substrate 11 of manufacturing process and needs etc.

On the face of being handled by hydrophilic (liquid), form zone 41 from the wiring material of the flowability of ink gun 33 ejections along gate wirings and launch, probably be that the interval of 10～100 μ m is coated with at interval so suitably regulate ejection.The coating back carries out burning till in 1 hour under 300 ℃, forms the gate wirings 13, gate electrode 17, auxiliary capacitor distribution 16, the terminal distribution 30 that are made of silver and indium.

Here, these gate wirings 13, gate electrode 17, auxiliary capacitor distribution 16, terminal distribution 30 use the conductive ink composition of present embodiment as above-mentioned mobile wiring material, so do not appear at the particle growth of seeing in the identical wiring material in the past, condition with respect to 300 ℃ has sufficient thermotolerance, does not lose surface smoothing.Relative therewith, in silver-colored mobile wiring material in the past,, out of condition so easy appearance is sewed up and down by having burnt till particle growth.

In addition, why firing temperature being set becomes 300 ℃, is because apply about 300 ℃ processing heat in the gate insulating film of next stage, semiconductor film film formation process 103.Therefore, firing temperature is not limited to this temperature.

Then, the concrete grammar that utilizes ink jet method to form above-mentioned gate wirings 13 is described.Figure 12 (a) is the schematic configuration diagram of the formation of the whole gate wirings of pattern ground expression, the schematic construction of the structure of the gate electrode portion in the gate wirings of Figure 12 (b) pattern ground expression shown in Figure 12 (a), Figure 12 (c) is the schematic configuration diagram of the structure of the terminal electrode portion in the gate wirings of pattern ground expression shown in Figure 12 (a).The wiring part 71 of above-mentioned tft array substrate 11 comprises gate wirings 13, auxiliary capacitor distribution 16, terminal distribution 30.In addition, gate wirings 13 links to each other with the not shown driving terminal electrode with driver IC in terminal electrode portion 72 by terminal wiring part 74 in the end of glass substrate 12.In addition, auxiliary capacitor distribution 16 links to each other with terminal distribution 30 in the opposing party's of above-mentioned glass substrate 12 end.

In the present embodiment, is silver-indium alloy formation wiring part 71 of 1 atom % in order to utilize aforesaid indium with respect to the ratio of silver, and to utilize indium be the terminal electrode 29 that silver-indium alloy of 5 atom % forms terminal electrode portion 73 with respect to the ratio of silver, forms at pattern shown in Figure 3 on the ink gun 33 of device 81 and carry the different conductive ink composition of above-mentioned cooperation ratio respectively.Wherein, 33 quantity of having prepared above-mentioned conductive ink composition kind of ink gun.In the present embodiment, shown in Figure 12 (a) and Figure 12 (b), the preparation indium is 2 shower nozzles (with reference to Figure 13 (a) and Figure 13 (b)) that 1 atom % uses and 5 atom % use with respect to the ratio of silver.

Promptly, in the present embodiment, shown in Fig. 7 (b), if want terminal distribution 30 and terminal electrode 29 all to be formed on the glass substrate 12, and these terminal distributions 30 and terminal electrode 29 respectively by indium content mutually different silver alloys forms, then ink gun 33 is necessary to have at least the mechanism of the wiring material that can spray the flowability that is made of the different silver alloy of cooperation ratio.

Therefore, in the present embodiment, for example, shown in Figure 13 (a) and Figure 13 (b), direct of travel (direction of arrow among Figure 13 (a) and Figure 13 (b)) along ink gun 33, possess in order and be used to spray as the wiring part of the wiring material of flowability with the 1st shower nozzle 33a of low electrical resistant material be used to spray the 2nd shower nozzle 33b of same portion of terminal as mobile wiring material with anti-plasma material, by these the 1st shower nozzle 33a of suitable switching and the 2nd shower nozzle 33b, ejection has the wiring material of the flowability that needs.

Figure 13 (a)～Figure 13 (e) is the wiring part 71 of tft array substrate 11 of expression shown in Figure 12 (a)～Figure 12 (c) and the figure of the formation operation of the portion of terminal 28 of terminal electrode portion 73.

Here, at first, shown in Figure 13 (a), the terminal distribution 30 that the terminal distribution that forms zone 41 and Figure 10 (a) in the gate wirings that wiring part 71 is specially Fig. 9 (a) forms zone 44 forms on the zones, and using as the 1st shower nozzle 33a indium coating of the shower nozzle of this conductive ink composition special use is the conductive ink composition (wiring part low electrical resistant material) of 1 atom % with respect to the ratio of silver.Then, shown in Figure 13 (b), the terminal distribution that is specially Figure 10 (a) in terminal electrode portion 73 forms on the terminal electrode 29 formation zones in zone 44, and use is the conductive ink composition (the anti-plasma material of portion of terminal) of 5 atom % as the ratio of the 2nd shower nozzle 33b silver coating of the shower nozzle of this conductive ink composition special use.

At this moment, two kinds of conductive ink compositions are mobile materials, so mix on glass substrate 12 the ejection back, so after firing process afterwards, the terminal distribution 30 and the terminal electrode 29 that are made of above-mentioned two kinds of conductive ink compositions become electrical connection.Shown in Fig. 7 (a) and Figure 13 (b), above-mentioned two kinds of conductive ink compositions contact and blended zone (below be designated as boundary member) mutually, the part becomes the intermediateness of two kinds of liquid (conductive ink composition), but this moment, to flow into above-mentioned terminal electrode 29 as above-mentioned wiring part with the conductive ink composition of low electrical resistant material and form the zone in order not make, can form very close place, zone with above-mentioned terminal electrode 29, the shower nozzle of ejection conductive ink composition is switched to the 2nd shower nozzle 33b from above-mentioned the 1st shower nozzle 33a, for example above-mentioned conductive ink composition is switched in the place about the hundreds of μ m in front of terminal electrode 29 forms the zone, and is then enough.Certainly, can form the zone from portion of terminal 28 earlier and carry out the coating (ejection) of above-mentioned conductive ink composition.

Thus, in the present embodiment, make the characteristic at the position, at least 2 place on the same distribution different respectively, that is, shown in Figure 12 (c) and Figure 13 (b), make the characteristic of terminal distribution 30 and terminal electrode 29 different respectively here.Similarly, according to present embodiment,, shown in Figure 12 (b), make the gate wirings 13 of gate electrode portion 75 and the characteristic of gate electrode 17 distinguish different by the ratio difference of indium in the silver-indium alloy that makes employed conductive ink composition with respect to silver.

In above-mentioned tft array substrate 11, paid attention to for above-mentioned terminal distribution 30 and gate wirings 13 low resistance of going to the capital city, and obtain paying attention to for the tolerance of terminal electrode 29 plasma etchings, on the other hand, for above-mentioned gate electrode 17, as mentioned above owing on this gate electrode 17, being formed with semiconductor layer 27, so the surface smoothing (flatness) of heat is paid attention to by gate insulator 18.

The thickness of above-mentioned semiconductor layer 27 is approximately 500  (50nm), and (3000～5000  promptly 300～500nm) compare, and it as thin as a wafer with each distribution that constitutes above-mentioned wiring part 71.And the characteristic of TFT15 is by above-mentioned semiconductor layer 27 decisions, so above-mentioned semiconductor layer 27 is extremely important films.

Gate electrode 17 desired flatness preferably are no more than the thickness of above-mentioned semiconductor layer 27.For this reason, below the concavo-convex 50nm of being preferably that forms on the surface of above-mentioned gate electrode 17, more preferably below the 10nm.

Formation is of a size of several nm as the above-mentioned metal particle of the above-mentioned conductive ink composition of coating material (printing ink), so can not deny at above-mentioned gate electrode 17 or even be formed at having formed the concavo-convex of the particle diameter that reflected above-mentioned metal particle on the surface of the semiconductor layer 27 on this gate electrode 17, but occur to surpass under the situation of particle growth of 50nm by burning till (about 300 ℃), gate electrode 17 as the lower floor of above-mentioned semiconductor layer 27 might not have sufficient characteristic.

For this reason, in above-mentioned gate wirings 13,, then there is no need to use the conductive ink composition of present embodiment if remove the cross part of gate wirings 13 and source electrode distribution 14, but in above-mentioned gate electrode 17, need flatness, so preferably use the conductive ink composition of present embodiment.That is, for example in above-mentioned wiring part 71, can only use the conductive ink composition of present embodiment to gate electrode 17.Certainly, can form with the conductive ink composition of present embodiment.

When only gate electrode 17 being used the conductive ink composition of present embodiment, for example shown in Figure 14 (a) and Figure 14 (b), above-mentioned the 1st shower nozzle 33a and the 2nd shower nozzle 33b be can in above-mentioned ink gun 33, replace and the 1st shower nozzle 91 and the 2nd shower nozzle 92 used, paying attention to low-resistance known mobile wiring material M from above-mentioned the 1st shower nozzle 33a ejection, form after the above-mentioned gate wirings 13, switch to above-mentioned the 1st shower nozzle 91 and the 2nd shower nozzle 92, conductive ink composition N from above-mentioned the 2nd shower nozzle 92 ejection present embodiments forms gate electrode 17.

As mentioned above, if when forming above-mentioned gate electrode 17, use the conductive ink composition of present embodiment, then particle growth is inhibited, the flatness that becomes the gate electrode 17 of bottom distribution 201 as shown in figure 15 improves, so the film fracture does not take place in the gate insulator 18 as insulation layer 202, is not take place to sew up and down between above-mentioned gate electrode 17 and the semiconductor layer 27 that becomes above-mentioned distribution 203 at above-mentioned bottom distribution 201.For this reason, when improving yield rate, the TFT characteristic is also stable.

Here, illustrate that with reference to Figure 13 (a)～Figure 13 (e) above-mentioned gate wirings forms the flow process of operation 102.Wherein, the mobile wiring material of Shi Yonging in the present embodiment, the protective colloid that has present embodiment as mentioned above, its effect be not subjected to indium content about.

At first, shown in Figure 13 (a), in gate wirings pretreatment procedure 101, distribution at the glass substrate 12 of the surface having been implemented close and distant water (close and distant liquid) processing forms on the zone, here be to form on the zone 44 at the terminal distribution, utilize the mobile wiring material of the 1st shower nozzle 33a ejection wiring part of ink gun 33, form terminal distribution 30 with low electrical resistant material.

Then, shown in Figure 13 (b), terminal electrode 29 on the glass substrate 12 after forming terminal distribution 30 forms on the zone, utilize the 2nd shower nozzle 33b ejection of ink gun 33 to compare with low electrical resistant material and have mobile wiring materials (the anti-plasma material of portion of terminal) more excellent anti-isoiony, that indium content is many, formation terminal electrode 29 with above-mentioned wiring part.

Then, shown in Figure 13 (c), after terminal distribution 30 that will form and terminal electrode 29 burn till, form gate insulating film 45 on glass substrate 12 as protective membrane in the mode that covers terminal distribution 30 and terminal electrode 29.

Then, shown in Figure 13 (d), in order to carry out terminal processing, so that have the mode of opening to be provided as the erosion resistant 100 of mask, form pattern by mask exposure etc. with the gate insulating film 45 of terminal electrode 29 corresponding parts.

At last, shown in Figure 13 (e), will carry out etching with the zone of terminal electrode 29 corresponding gate insulating films 45 after, peel off erosion resistant 100, form portion of terminal 28.

Thus, 2 different shower nozzles of function are set on ink gun 33, when the wiring material of two kinds of flowabilities is handled, are necessary to make itself and printing ink to provide system 36, control unit 37, ejection positional information etc. corresponding.

The portion of terminal 28 of Xing Chenging is shown in Fig. 7 (a) and Fig. 7 (b) like this.In addition, terminal distribution 30 links to each other with terminal electrode 29, and they have and conduct.

Because terminal distribution 30 covered by gate insulator 18, make it have the thermotolerance in the middle of the anti-operation when therefore selecting above-mentioned wiring material and the sticking power of glass substrate got final product.This is because above-mentioned terminal distribution 30 is not exposed in the middle of the dry-etching environment, so do not need anti-isoiony especially.

In the present embodiment, be that the mode of 1 atom % has been modulated above-mentioned conductive ink composition (wiring part low electrical resistant material) according to indium in above-mentioned terminal distribution 30 with respect to the content of silver.At this moment, the resistivity of above-mentioned terminal distribution 30 is about 7 μ Ω cm.In addition, in the present embodiment, gate wirings 13, gate electrode 17, auxiliary capacitor distribution 16 that pixel forms in the zone 61 are also the same with terminal distribution 30, is the mode of 1 atom % according to indium with respect to the content of silver, has modulated the conductive ink composition (wiring part low electrical resistant material) that is used to form above-mentioned distribution and/or electrode.

On the other hand, terminal electrode 29 is electrically connected in order to obtain, and in the etching work procedure of the insulating film on removing terminal, by removing insulating film etching excessively afterwards, is exposed in the dry-etching atmosphere., pay attention to not by the anti-isoiony of these dry-etching atmosphere invasion and attack, be that the mode of 5 atom % is modulated above-mentioned conductive ink composition (the anti-plasma material of portion of terminal) according to indium with respect to the content of silver for this reason.This terminal electrode 29 is than the gate wirings on the tft array substrate 11 13, source electrode distribution 14, terminal distribution 30 much shorters, and resistivity can be greater than other parts.

In the present embodiment, above-mentioned ink gun 33 uses the 1st shower nozzle 33a and the 2nd shower nozzle 33b, and the wiring material of two kinds of flowabilities that the ejection indium is different with respect to the content of silver forms terminal distribution 30 and terminal electrode 29.Be specially, when (that is, the formation zone of terminal distribution 30) go up to form terminal distribution 30 in the zone that is used to form terminal distribution 30, the ejection indium was that the conductive ink composition of 1 atom % is as above-mentioned wiring material with respect to the content of silver.On the other hand, when (that is, terminal electrode 29 forms the zone) goes up when forming terminal electrode 29 in the zone that is used to form terminal electrode 29, the ejection indium is that the conductive ink composition of 5 atom % is as above-mentioned wiring material with respect to the content of silver.

In addition, form on the zone that is used to form gate wirings 13, gate electrode 17, auxiliary capacitor distribution 16 of zone in 61 in pixel, the same conductive ink composition of ejection and terminal distribution 30 is as above-mentioned wiring material.After the ejection, under 300 ℃, carry out burning till in 1 hour the terminal distribution 30 that obtains stipulating, terminal electrode 29 etc.Thus, be the wiring material of the flowability of 1 atom % by using the content of indium in the wiring part that forms zone 61 in above-mentioned pixel, can form low-resistance distribution.(gate insulating film, semiconductor film film formation process 103)

Then, with reference to Figure 16 (a), Figure 16 (b), Figure 17 (a) and Figure 17 (b) gate insulating film, semiconductor film film formation process 103 are carried out following explanation.

Figure 16 (a), Figure 16 (b), Figure 17 (a) and Figure 17 (b) are the figure of the glass substrate 12 under the state that finished of expression gate insulating film, semiconductor film film formation process 103.Figure 16 (a), Figure 17 (a) represent that respectively above-mentioned pixel on the glass substrate 12 forms the orthographic plan that zone 61 (pixel portion), portion of terminal form zone 62 (terminal parts).Figure 16 (b), Figure 17 (b) be respectively the expression Figure 16 (a), Figure 17 (a) E-E to sectional view, F-F to sectional view.

In above-mentioned gate insulating film, semiconductor film film formation process 103, shown in Figure 16 (a), Figure 16 (b), Figure 17 (a) and Figure 17 (b), forming through gate wirings on the glass substrate 12 of operation 102, will become the gate insulating film 45 of gate insulator 18, the n+ type silicon fiml 47 difference continuous film formings that become the amorphous silicon film 46 of amorphous silicon layer 19 and become n+ type silicon layer 20 afterwards.Here, gate insulating film 45 is the films that are made of silicon nitride.These films all adopt CVD method film forming, and thickness separately for example is 0.3 μ m, 0.15 μ m, 0.04 μ m in order.In addition, film-forming temperature is 300 ℃.

In gate wirings 13, described as former operation, the conductive ink composition of use present embodiment, for this reason, particle growth is suppressed.,, compare for this reason, can obtain the good gate wirings of superficiality 13 with the situation of the protective colloid that does not use silver-colored monomer or present embodiment even its surface can be not coarse yet under 300 ℃ hot conditions.For this reason, not can with by gate insulator 18 and on formed semiconductor layer 27 or source electrode 21 sew, when improving yield rate, the characteristic of TFT is also stable.

(gate insulating film, semiconductor film manufacturing procedure 104)

Then, with reference to Figure 18 (a), Figure 18 (b), Figure 19 (a) and Figure 19 (b) gate insulating film, semiconductor film manufacturing procedure 104 are carried out following explanation.

Figure 18 (a), Figure 18 (b), Figure 19 (a) and Figure 19 (b) are the figure of the state that finished of expression gate insulating film, semiconductor film manufacturing procedure 104.Figure 18 (a), Figure 19 (a) represent that respectively above-mentioned pixel on the glass substrate 12 forms the orthographic plan that zone 61 (pixel portion), portion of terminal form zone 62 (terminal parts).Figure 18 (b), Figure 19 (b) be respectively the expression Figure 18 (a), Figure 19 (a) G-G to sectional view, H-H to sectional view.

In above-mentioned gate insulating film, semiconductor film manufacturing procedure 104, at first, utilize amorphous silicon film 46 and the n+ type silicon fiml 47 shown in the 1st photolithography processing Figure 16 (b) and Figure 17 (b).From Figure 18 (a), Figure 18 (b), Figure 19 (a) and Figure 19 (b) as can be known, these amorphous silicon films 46 and n+ type silicon fiml 47 are processed to, the amorphous silicon layer 19 that constitutes by above-mentioned amorphous silicon film 46 and by n+ type silicon fiml 47 constitute and after to become the n+ type silicon processing of films 48 of n+ type silicon layer 20, pixel form in the zone 61 remain in island gate electrode 17 above and portion of terminal form do not have in the zone 62 residual.In addition, carrying out the above-mentioned man-hour that adds, etching is adopted the dry-etching method to import the mixed gas of sulfur hexafluoride (SF6) gas, hydrogenchloride (HCl) gas and is carried out.And, so far, because gate insulating film 45 covers whole glass substrate 12, so terminal distribution 30 grades can not be exposed in the dry-etching atmosphere.

Then, utilize the 2nd photolithography, the gate insulating film 45 shown in processing Figure 16 (b) and Figure 17 (b).Form in the zone 62 in portion of terminal, gate insulating film 45 is partially-etched, obtain gate insulator 18, peristome 49.Etching adopts the dry-etching method to import CF ₄Gas, O ₂The mixed gas of gas and carrying out.

In addition, consider anti-isoiony here, above-mentioned portion of terminal forms zone 62 and is configured to indium in advance with respect to the about 5 atom % of the ratio of silver.

(source, drain electrode distribution pretreatment procedure 105)

Then, with reference to accompanying drawing 20 (a) source, drain electrode distribution pretreatment procedure 105 are carried out following explanation.Figure 20 (a) is the orthographic plan that expression source, drain electrode distribution pretreatment procedure 105 finish the schematic construction of back pixel portion, is representing to have formed on the glass substrate 12 that has passed through gate insulating film, semiconductor film manufacturing procedure 104 state of the distribution guide part (wire guide) 52 that is used to form source electrode distribution 14, source electrode 21 and drain electrode distribution 22.

And, in source described later, drain electrode distribution formation operation 106, do not form distribution etc. owing to forming on the zone 62 in portion of terminal, describe so only pixel is formed zone 61 here.

In this operation, the part outside the zone that forms source electrode distribution 14, source electrode 21 and drain electrode distribution 22 (source, drain electrode form zone 53) forms distribution guide part 52.Distribution guide part 52 is to use erosion resistant to form.Promptly on the glass substrate 12 that has passed through gate insulating film, semiconductor film manufacturing procedure 104 the coating photoresist material and carry out prebake after, use photomask to expose, develop, cure after then carrying out.Here the distribution guide part 52 of Xing Chenging forms, and the live width that forms the zone of source electrode distribution 14, source electrode 21 is 10 μ m, and the live width in the zone of formation drain electrode distribution 22 is 10 μ m to 40 μ m.The interval of source electrode 21, drain electrode distribution 22, promptly the length of the groove 51 of TFT is 4 μ m.

In addition, with the face that becomes basal surface good binding is arranged, gate insulator 18 top implemented hydrophilic (liquid) with oxygen plasma handle in order to make the wiring material that forms device coating by pattern, simultaneously can be with being exposed to CF ₄Method in the plasma body is implemented hydrophobic (liquid) to distribution guide part 52 and is handled.

In addition, replace the formation of above-mentioned distribution guide part 52, can adopt close and distant water (close and distant liquid) treatment process of the photocatalyst that utilization uses when forming above-mentioned gate electrode, implement and the corresponding close and distant water treatment of distribution electrode pattern.

(source, drain electrode distribution form operation 106)

Then, with reference to Figure 20 (b) and Figure 20 (c) source, drain electrode distribution formation operation 106 are carried out following explanation.The figure of the state that Figure 20 (a) and Figure 20 (c) are the above-mentioned sources of expression, the distribution formation operation 106 that drains has finished.Figure 20 (b) is the orthographic plan that the pixel on the glass substrate 12 forms zone (pixel portion).Figure 20 (c) is that I-I in expression Figure 20 (b) is to sectional view.

In addition, in the following description since as mentioned above in the source, the drain electrode distribution forms and not form zone 62 in portion of terminal in the operation 106 and form distributions etc., thereby only pixel is formed zone 61 and describes.

In above-mentioned source, drain electrode distribution formation operation 106, utilize the distribution guide part 52 that in preceding operation, is provided with, shown in Figure 20 (b) and Figure 20 (c), form source electrode distribution 14, source electrode 21 and drain electrode distribution 22.And apparatus for coating has used pattern as shown in Figure 3 to form device 81.

As wiring material, for example used the conductive ink composition of the silver-present embodiment of indium alloy microparticulate in organic solvent that will cover with above-mentioned protective colloid (that is, being specially the protective colloid described in the embodiment 2 described later).In addition; for silver that in above-mentioned conductive ink composition, contains and indium; consider in follow-up groove manufacturing procedure 107, protective membrane manufacturing procedure 109 and carry out dry-etching that in order to have anti-isoiony, indium set with respect to the ratio of silver becomes about 5 atom %.

But aforementioned proportion can suitably be selected according to performance of the tft array substrate 11 of manufacturing process or needs etc.

In addition, in above-mentioned source, drain electrode distribution formation operation 106, will form spray volume setting the becoming 2pl of the above-mentioned conductive ink composition of the ink gun 33 in the device 81, and form thickness and be set at 0.3 μ m from above-mentioned pattern.In addition, because amorphous silicon film 46 grades are in about 300 ℃ of following film forming, so firing temperature is set at than also low 250 ℃ of this temperature.With an organic solvent removed distribution guide part 52.

(groove manufacturing procedure 107)

Then, with reference to Figure 21 groove manufacturing procedure 107 is carried out following explanation.Figure 21 is the figure that represents the state that above-mentioned groove manufacturing procedure 107 has finished with the I-I among Figure 20 (b) to the cross section.

In above-mentioned groove manufacturing procedure 107, carry out the processing of the groove 51 of TFT shown in Figure 21.This processing is to be undertaken by the dry-etching that has used chlorine, but does not carry out new photoetching this moment, utilizes the pattern of source electrode 21, drain electrode distribution 22 to process.

(protective membrane, interlayer insulating film film formation process 108)

Then, with reference to Figure 22 (a), Figure 22 (b), Figure 23 (a) and Figure 23 (b) protective membrane, interlayer insulating film film formation process 108 are carried out following explanation.Figure 22 (a), Figure 22 (b), Figure 23 (a) and Figure 23 (b) are the figure of the state that finished of expression said protection film, interlayer insulating film film formation process 108.Figure 22 (a), Figure 23 (a) represent that respectively above-mentioned pixel on the glass substrate 12 forms the orthographic plan that zone 61 (pixel portion), portion of terminal form zone 62 (terminal parts).Figure 22 (b), Figure 23 (b) be respectively the J-J of Figure 22 (a), Figure 23 (a) to sectional view, K-K to sectional view.

In said protection film, interlayer insulating film film formation process 108, shown in Figure 22 (a), Figure 22 (b), Figure 23 (a) and Figure 23 (b), at first, through on the glass substrate 12 of preceding operation, adopt the CVD method to make silicon nitride film 55 film forming and with it as protective membrane.The substrate temperature of this moment is set becomes 200 ℃.

Then, coating photosensitivity acrylic materials on this silicon nitride film 55.Then, the exposure by having used mask, develop, burn till, obtain having the interlayer insulating film 26 of predetermined pattern.At this moment, drain electrode distribution 22 and auxiliary capacitor distribution 16 eclipsed partly are provided with peristome 56.On the other hand, by Figure 23 (b) as can be known, form the zone in portion of terminal and do not form interlayer insulating film 26 on 62.

(protective membrane manufacturing procedure 109)

Then, with reference to Figure 24 (a) and Figure 24 (b) protective membrane manufacturing procedure 109 is carried out following explanation.Figure 24 (a) and Figure 24 (b) use J-J among Figure 22 (a), Figure 23 (a) to represent the figure of the state after said protection film manufacturing procedure 109 finishes to the cross section to cross section, K-K respectively.

In said protection film manufacturing procedure 109, utilize the pattern of interlayer insulating film 26, the silicon nitride film 55 that processing forms in protective membrane, interlayer insulating film film formation process 108.Form in the zone 61 in pixel, be positioned at silicon nitride film 55 (with reference to Figure 22 (a), Figure 22 (b), Figure 23 (a) and Figure 23 (b)) under the peristome 56 by etching, shown in Figure 24 (a), layer 25 (protective membrane) and contact hole 23 are protected.On the other hand, form zone 62, by Figure 24 (b) as can be known, form regional 62 silicon nitride films, 55 etched removing in whole portion of terminal for portion of terminal.In addition, above-mentioned etching is to be used in the formula etching method to import CF ₄Gas, O ₂The mixed gas of gas carries out.

(pixel electrode forms operation 110)

As last operation, forming on the substrate shown in Figure 24 (a) and Figure 24 (b) of above-mentioned interlayer insulating film 26, utilizing sputtering method to form the pixel electrode 24 shown in Fig. 6, Fig. 7 (a) and Fig. 7 (b), ITO (indium tin oxide) film of terminal electrode 29.The substrate temperature of this moment is set at 200 ℃.Then, use photolithography, obtain the tft array substrate 11 shown in Fig. 4～Fig. 7 (a) and Fig. 7 (b) this ITO film composition.

The conductive ink composition of present embodiment, be difficult in sintering process, occur particle growth, and then has an excellent specific property (thermotolerance) that does not cause particle growth and in wiring material in the past, do not have like this, even so under the situation of exposure base under the hot conditions of 200 ℃ or 300 ℃, also can obtain the surface is not coarse, surface smoothing is good distribution and/or electrode, specifically can obtain gate wirings 13, auxiliary capacitor distribution 16, gate electrode 17 etc.Particularly above-mentioned gate wirings 13, auxiliary capacitor distribution 16 and gate electrode 17, by the gate insulator 18 that on these gate wirings 13, auxiliary capacitor distribution 16 and gate electrode 17, forms, be respectively gate electrode 17 and semiconductor layer 27 subtends, auxiliary capacitor distribution 16 and drain electrode distribution 22 subtends, and in the cross part of source electrode distribution 14 and gate wirings 13 (overlapping portion), the above-mentioned gate insulator 18 of clamping, gate wirings 13 and source electrode distribution 14 subtends.In the past, because the particle growth that produces when burning till the wiring material that is used to form these distributions and/or electrode, at these positions, gate insulator 18 caused the film fracture, and distribution is short-circuited up and down, promptly for example produced sewing up and down as shown in figure 28.

But, if the conductive ink composition of present embodiment is used as above-mentioned wiring material (coating material), can suppress particle growth and the smoothness (flatness) on coated film surface is improved, thus at the film that forms on the above-mentioned coated film promptly as shown in figure 15 on the insulation layer 202 that forms on the bottom distribution 201, do not occur rupturing, defective L shown in Figure 28 (short circuit) do not occur because of the uneven caused film that particle growth causes.Therefore, as mentioned above, if the distribution (bottom distribution 201, top distribution 203) of insulation layer 202 in middle clamping, particularly bottom distribution 201 is used conductive ink composition of the present invention as above-mentioned wiring material, to be very effective, yield rate improves.In addition, as mentioned above, when the conductive ink composition with present embodiment is used for the distribution of above-mentioned liquid crystal indicator (LCD), can avoid the sewing up and down of cross part of above-mentioned gate wirings 13 and source electrode distribution 14, the film fracture of the semiconductor layer 27 on the gate electrode 17, the TFT characteristic is also stable.

In addition, as mentioned above in wiring crossing portion, if the superficiality of bottom distribution 201 (downside distribution) is relatively poor, then become by the insulation layer 202 above this bottom distribution 201 and and top distribution 203 between produce the reason of sewing up and down.In addition, in the formation part of the formation of TFT15 part (TFT portion) and gate electrode 17 (gate electrode portion 75, with reference to Figure 12 (a) and Figure 12 (c)), be provided with clamping grid insulation layer 18 and possess the semiconductor layer 27 (about 500 =about 50nm) of amorphous silicon layer 19, the surface irregularity of gate electrode 17 causes the deterioration of TFT characteristic and the film fracture of gate insulator 18.

In addition, in the formation part (auxiliary capacitor wiring part) of auxiliary capacitor distribution 16, similarly, if the superficiality of bottom distribution 201 (downside distribution) is relatively poor, can cause the film fracture of gate insulator 18 and sewing of distribution up and down, not bring into play the function of electrical condenser sometimes.

For this reason, preferably possess above-mentioned semiconductor layer 27 (a-Si layer) and be the following flatness of 150nm for other parts below the 50nm (distribution and/or electrode).

Particularly in above-mentioned auxiliary capacitor distribution 16 (auxiliary capacitor wiring part), because need form electric capacity, so require flatness than gate electrode 17 (gate electrode portion 75, with reference to Figure 12 (a) and Figure 12 (c)) wider scope by drain electrode distribution 22 and gate insulator 18.Therefore, when above-mentioned auxiliary capacitor distribution 16 was formed by the conductive ink composition of present embodiment, superficiality was good, so very effective aspect the formation of carrying out electric capacity.And in the case, as mentioned above, every kind of different conductive ink composition uses different shower nozzles, for example can only use the conductive ink composition of present embodiment to above-mentioned auxiliary capacitor distribution 16.Certainly, as mentioned above, can be all form by the conductive ink composition of present embodiment.

In the tft array substrate 11 of present embodiment, the part of special requirement flatness is represented with regional W in Fig. 5 and Fig. 6.

In addition; in the present embodiment; used following conductive ink composition in the above-mentioned wiring material; promptly this conductive ink composition has applied the protective colloid of present embodiment and this conductive ink composition as organic membrane and disperses silver-indium alloy particulate and form in organic solvent; and silver that contains in above-mentioned conductive ink composition and indium suitably are set at the ratio of indium with respect to silver and are about below the 5 atom %.But, as mentioned above, indium can suitably be selected according to performance of the tft array substrate 11 of manufacturing process or needs etc. with respect to the ratio of silver.

As mentioned above; according to present embodiment; above-mentioned conductive ink composition contains following solid matter; promptly this solid matter be with the protective colloid that constitutes by two kinds of organic compound at least cover by at least a be the surface of the metal particle that constitutes of the multiple metal of noble metal; more specifically say so and for example cover the surface of the metal particle that constitutes by the alloy that contains noble metal at least and form with this protective colloid; compare as the situation of metal particle with using silver-colored monomer thus, it is excellent also more in the past than the film (metallic membrane) that more can improve and be coated with the adaptation of object to form the particle growth and the surface smoothing that more can suppress metal.

That is,, can provide the particle growth that can form metal to be suppressed and surface smoothing is excellent and more in the past than the conductive ink composition that more can improve with the film of the adaptation that is coated with object according to present embodiment.In addition, according to present embodiment, can also provide the electrode or distribution, film formation substrate or circuit substrate, the electronic installation etc. that have used above-mentioned conductive ink composition.In other words, according to present embodiment, can provide the particle growth of metal to be suppressed, the surface smoothing excellence, with the also excellent electrode or the distribution of adaptation of coating object, film forms substrate, and then have the active-matrix substrate circuit substrates such as (tft array substrates) of above-mentioned electrode and/or electrode and electronic installations such as (liquid crystal) display unit that use these circuit substrates.

That is,, for example can provide by above-mentioned conductive ink composition being carried out film formation substrate or the circuit substrate that drying or thermal treatment (for example burning till) obtain according to present embodiment.

For example, in the present embodiment, the conductive ink composition that uses in aforesaid substrate, distribution, electrode, active-matrix substrate, circuit substrate can be to accept 250 ℃～350 ℃ heat treated formation.

And,, can be provided in matrix (as the substrate of substrate) and go up distribution or the electrode that forms by above-mentioned conductive ink composition according to present embodiment.

And then, according to present embodiment, can be provided in many signal line and form rectangular and have near the active-matrix substrate of the switching element that the cross part of each signal wire, forms the active-matrix substrate that each signal wire is formed by above-mentioned conductive ink composition.

In addition, according to present embodiment, can be provided in many signal line forms rectangular and has near the active-matrix substrate of the switching element that forms the cross part of each signal wire, in the middle of above-mentioned signal wire, be formed at the active-matrix substrate that the signal wire (that is the bottom distribution of the cross part of signal wire) of bottom is formed by above-mentioned conductive ink composition.

And then, according to present embodiment, can be provided in many signal line and form rectangular and have near the active-matrix substrate of the switching element that the cross part of each signal wire, forms, be positioned at the bottom of above-mentioned switching element and control the active-matrix substrate that the electrode (for example gate electrode) of the ON/OFF of above-mentioned switching element is formed by above-mentioned conductive ink composition.

In addition, above-mentioned conductive ink composition can also contain known in the past various additives such as dispersion agent, tensio-active agent, viscosity modifier, surface tension modifier in the scope of the effect that does not hinder above-mentioned conductive ink composition to have except containing above-mentioned organic solvent (dispersion agent).

The conductive ink composition of present embodiment also can be used for similar reflection parts such as light reflective electrode (below, only be designated as reflecting electrode) on the tft array substrate that reflection-type TFT liquid crystal indicator etc. uses.At this moment, because above-mentioned conductive ink composition has excellent thermotolerance,, can not form and lose surface smoothing the film as the silver-colored printing ink of use in the past and by silver-colored monomer even during for example the heat under the high temperature of 200 ℃ or 300 ℃ is burnt till.For this reason, can give full play to the characteristic as tft array substrate as described below, promptly not cause scattering of light outside the design, can keep sufficient luminous reflectance factor etc. as the light reflective electrode.

And self-evident, above-mentioned conductive ink composition not only can be used for the reflection part that forms at circuit substrates such as tft array substrates, but also can be used for the emission element of reflector of existing with monomeric form etc.That is, the reflection part of present embodiment and nonessential being present in the circuit substrate, also can use with monomeric form.

Having used in reflecting electrode (reflector, pixel electrode) by the silver-indium as the conductive ink composition of present embodiment is the tft array substrate 11 of the metallic membrane that constitutes of conductive ink composition, for example can be by method manufacturing as follows.

In addition, be used for the tft array substrate 11 of reflection-type TFT liquid crystal indicator, till groove manufacturing procedure 107, can adopt method manufacturing same as described above.Therefore, in following explanation, protective membrane, interlayer insulating film film formation process 108 later operations are described.

(protective membrane, interlayer insulating film film formation process 108)

In this protective membrane, interlayer insulating film film formation process 108, coating has used the application type insulating material (sol gel film) of sol-gel method to replace coating photosensitivity acrylic materials on above-mentioned silicon nitride film 55.Sol gel film has the thermotolerance higher than photosensitivity acrylic materials (high thermal resistance) in burning till the operation that silver-indium is a conductive ink composition.In addition, by using sol gel film, can carry out planarization to the difference of altitude of the TFT15 formation portion (TFT portion) that forms above-mentioned silicon nitride film 55.

In addition, in this protective membrane, interlayer insulating film film formation process 108, consider the firing process of above-mentioned sol gel film, form silicon nitride film down at 250 ℃.In addition, after forming silicon nitride film 55, the above-mentioned sol gel film of coating burns till under 250 ℃ equally on this silicon nitride film 55.

Wherein, sol gel film self does not have photosensitivity.Therefore; in this protective membrane, interlayer insulating film film formation process 108, on the sol gel film of coating on the above-mentioned silicon nitride film 55, further painting erosion resistant agent; use exposure, the development of mask and burnt till, obtained having the interlayer insulating film 26 of the pattern of regulation.

(protective membrane manufacturing procedure 109)

Then, the same with said protection film manufacturing procedure 109 above-mentioned silicon nitride film 55 is carried out dry-etching, form protective layer 25 and contact hole 23 thus.

In above-mentioned dry-etching, the same with said protection film manufacturing procedure 109, use CF ₄Gas and O ₂The mixed gas of gas.Then, peel off resist layer, obtain and Figure 24 (a) and Figure 24 (b) identical construction.In addition, when the dry-etching of the layer that forms by above-mentioned sol gel film, also be etched in the silicon nitride film 55 that this sol gel film below forms simultaneously.

(pixel electrode forms operation 110)

Then, at the aforesaid substrate that has formed interlayer insulating film 26 (promptly, substrate shown in Figure 24 (a) and Figure 24 (b)) on, the conductive ink composition of present embodiment is carried out 30 seconds spin coating with 1500rpm, obtain the film (conductive ink composition film) that constitutes by above-mentioned conductive ink composition of thickness 250nm.

In above-mentioned conductive ink composition, using indium is 0.1 atom % with respect to the ratio of silver, and uses the conductive ink composition (reflecting electrode low electrical resistant material) of the protective colloid of record among the embodiment 11 described later as protective colloid.

Then, in atmosphere, above-mentioned conductive ink composition film was burnt till 1 hour under 250 ℃.The reflectivity of the metallic membrane (burning till film) that is made of above-mentioned conductive ink composition is 94% at the wavelength place of 550nm.

Then, use metallic membrane (the burn till film) composition of photolithography to constituting by above-mentioned conductive ink composition.Thus, can obtain tft array substrate as follows 11, promptly be formed with on the substrate shown in Figure 24 (a) and Figure 24 (b) of above-mentioned interlayer insulating film 26, shown in Fig. 6, Fig. 7 (a) and Fig. 7 (b), formed pixel electrode 24 and the terminal electrode 29 that constitutes by above-mentioned conductive ink composition as reflecting electrode.Promptly, according to above-mentioned method, can obtain on interlayer insulating film 26, having formed the pixel electrode 24 (reflecting electrode) that constitutes by above-mentioned conductive ink composition, have and the tft array substrate 11 of tft array substrate 11 identical construction shown in Fig. 4～Fig. 7 (a) and Fig. 7 (b).

In addition, form in the operation at above-mentioned reflecting electrode, formed above-mentioned interlayer insulating film 26, have on the substrate of the structure shown in Figure 24 (a) and Figure 24 (b), the employing spin-coating method is coated with above-mentioned conductive ink composition and burns till, composition and form above-mentioned reflecting electrode then, but the formation method as above-mentioned reflecting electrode is not limited to this, can use additive method.For example, formed above-mentioned interlayer insulating film 26, have on the substrate of the structure shown in Figure 24 (a) and Figure 24 (b), painting erosion resistant agent, composition, be formed for the guide part (guide) of composition reflecting electrode, be coated with the above-mentioned conductive ink composition of present embodiment then and burn till, remove above-mentioned guide part, also can form above-mentioned reflecting electrode thus with organic solvent.And, as above-mentioned organic solvent, can suitably select to make this organic solvent can dissolve above-mentioned reflecting electrode according to the resist that uses, have no particular limits for this organic solvent.

The reflecting electrode that obtains thus is because of the excellent heat resistance of above-mentioned conductive ink composition, even under 200 ℃ or 300 ℃ of firing temperatures, also can not lose surface smoothing as film in the past use silver printing ink, that formed by silver-colored monomer.According to above-mentioned method, can provide scattering of light that does not cause outside the design and the tft array substrate 11 that can keep sufficient luminous reflectance factor as the light reflective electrode.

In addition, in above-mentioned concrete example, conductive ink composition as present embodiment, having used silver-indium is conductive ink composition, but present embodiment is not limited to this, as mentioned above, can use the silver of the present embodiment that silver-colored monomer forms as metal particle is conductive ink composition.

As mentioned above; according to present embodiment; use specific protective colloid; promptly; by using by (A) amine; (B) carboxylic acid constitutes; and the mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected; and (B) average carbon atom number of carboxylic acid is 5～25 protective colloid; thus; even the poor zone of the interpolation metal in the film of making by conductive ink composition; for example in zone that the indium content of silver-indium metal film reduces; also can improve adaptation with the coating object; even and if then using under the situation of noble metal monomer as metal particle; the particle growth that also can suppress metal is improved the adaptation with the coating object.

In Figure 30, represented to use the protective colloid shown in embodiment 11 that constitutes by octadecadienoic acid, caproic acid and octylame and the ink film of the silver that forms with scanning electron microscope photo (30,000 times of multiplying powers), at N ₂The state of the metallic film surface of carrying out annealing in 1 hour in the gas atmosphere under 300 ℃ and obtaining.

In addition, in Figure 31,, represented and to have used the protective colloid that constitutes by pentadecylic acid and octylame and the ink film of the silver that forms as above-mentioned protective colloid with scanning electron microscope photo (30,000 times of multiplying powers), at N for relatively ₂The state of the metallic film surface of carrying out annealing in 1 hour in the gas atmosphere under 300 ℃ and obtaining.

As shown in figure 31; when using silver-colored monomer; as protective colloid; if use the protective colloid that constitutes by pentadecylic acid and octylame; then as shown in figure 33, compare, although the particle growth of silver is less with use the ink film of the silver of the protective colloid that constitutes by naphthenic acid and octylame as protective colloid; but uneven or particle growth on the film surface of the metallic membrane that obtains, occurs, on film surface and film cross section, pore is arranged simultaneously.In addition, by the result of Figure 31 as can be known, when using silver-colored monomer,, use the protective colloid that forms by pentadecylic acid and octylame, the ink film of silver shown in Figure 32 is not had to suppress significantly the effect of silver-colored particle growth even as protective colloid.In addition, in the ink film of as shown in figure 31 silver, also near truncation surface, peel off and make film as can be seen from peel adaptation (sticking power) reduction as the base material (base material) of coating object owing to film.

Relative therewith, as shown in figure 30,, to compare with the metallic membrane shown in Figure 31～33 as can be known by using specific protective colloid, the particle growth on film surface is subjected to remarkable inhibition, does not also see the pore in film surface or film cross section, and superficiality is very good.In addition, according to Figure 30 as can be known,, film do not occur and peel off, improve yet with the adaptation (sticking power) of base material near truncation surface.

Therefore, according to present embodiment, by using specific protective colloid, even using under the situation of noble metal monomer as metal particle, also can provide have following distribution or electrode, the active-matrix substrate circuit substrates such as (tft array substrates) of reflection part, and electronic installations such as (liquid crystal) display unit that use these circuit substrates; Described distribution or electrode, reflection part be, the particle growth of metal is suppressed, surface smoothing, with adaptation, reflection characteristic (reflection efficiency) excellence of coating object, and low-resistance distribution or electrode, reflection part.

And then the conductive ink composition of present embodiment and the formation of distribution, distribution formation method also can be used to constitute bus electrode, data electrode on the glass substrate of PDP (plasma display panel).These electrodes are configured on front glass substrate or the back side glass substrate to drive PDP, these electrodes constitute silver, chromium/copper/chromium, aluminium/chromium in the past, as improving copper or aluminium to the sticking power of substrate and the measure that coefficient of expansion difference is taked, as mentioned above, above-mentioned electrode must be taked the structure of clamping chromium layer between glass substrate, otherwise can't use.On the other hand, as the wiring material of flowability and known in the past silver has problem aspect thermotolerance, be to burn till fine-grained growth thereby unworkable material by high temperature.

Relative therewith, the conductive ink composition of present embodiment has excellent thermotolerance and to the sticking power of glass substrate, thus replace silver etc. in the past material and be useful as bus electrode, data electrode.

In addition, the conductive ink composition of present embodiment and the formation of distribution, distribution formation method also can be used in the display unit of having used EL (electroluminescent).The same with liquid crystal indicator, the circuit substrate that drives EL element has been to use the circuit of tft array to form mostly, can make via the operation identical with the operation shown in the present embodiment.Therefore, can apply the present invention to use the display unit of EL.

As mentioned above, the conductive ink composition of present embodiment is applicable to the manufacturing of various circuit substrates such as the tft array substrate that is used for liquid crystal indicator etc., the electrode base board that is used for PDP (plasma display panel), printed wiring board, flexible wiring substrate.In addition, such circuit substrate can be applicable to following electronic installation, be display unit such as liquid crystal indicator, PDP (plasma display panel), organic EL (electroluminescent) panel, inorganic EL panel, and be the image-input devices such as two dimensional image input unit of representative with fingerprint sensor, X ray camera head etc.

The present invention is not limited to each above-mentioned embodiment, can carry out various changes in the scope shown in the technical scheme, will be in different embodiments disclosed respectively technological method combination and the embodiment that obtains is also included within the technical scope of the present invention.

Below, further describe the present invention by embodiment, but the present invention is not limited to these embodiment.

[embodiment 1]

(caproic acid+docosoic acid+octylame)

In 2-propyl alcohol 550ml, add sodium borohydride 15mmol, under 80 ℃, carry out 3 hours stirring, modulate sodium borohydride-2-propanol solution.

In addition, will be as the caproic acid 68mmol of the octylame 150mmol of (A) amine, conduct (B) carboxylic acid and docosoic acid 8mmol, add to as 2 of organic solvent as the indium acetate 0.3mmol and the Silver monoacetate 15mmol of metallic compound, 2, among the 4-trimethylpentane 1.05L, make its dissolving, the modulation metal salt solution.

Then, in above-mentioned metal salt solution with the 10ml/min above-mentioned sodium borohydride-2-propanol solution of dripping.After dripping, stirred 60 minutes, concentrate with vaporizer then, obtain the liquid of brown.Add methyl alcohol 1L in this liquid, the throw out that generates brown is a conductive ink composition, reclaims throw out by suction strainer then.

Is that the mode of 35 quality % is dispersed in the tetradecane with the conductive ink composition that obtains by the weight (quality) of metal, and obtaining silver-indium is conductive ink.Use ultra-violet and visible spectrophotometer and infiltration type electron microscope, confirm the nanoparticle in the conductive ink.Adopt spin-coating method to be coated on the alkali-free glass substrate conductive ink composition that obtains, under 300 ℃, carry out 30 minutes burn till (thermal annealing) with retort furnace.The film forming thickness of the burning that obtains is 273nm, and volume specific resistance is 8.4 μ Ω cm.The adaptation of film and substrate (sticking power) is estimated by belt stripping test.In belt stripping test, after thermal annealing, on the face that specification cuts out in accordance with regulations, the release adhesive band is with the face of tearing with adhesive tape joining, peels off then to bad as the fruit part face, if do not peel off fully then for good.Film that obtains in the present embodiment and the adaptation of substrate (sticking power) are good, have passed through belt stripping test.In addition, adopt the fluorescent X-ray light-dividing device to measure and form, the ratio of the indium in the film is 0.78 atom % as a result.Measure and observe this with scanning electron microscope and burn till film with the contact pin type film thickness gauge, center line average roughness Ra is 3.2nm as a result, is level and smooth film.In addition, at N ₂Under the gas atmosphere, even kept 60 minutes at 300 ℃, the form on film surface does not change, excellent heat resistance.

[embodiment 2]

(caproic acid+naphthenic acid+octylame)

Under the condition of embodiment 1, in the middle of (B) carboxylic acid, replace docosoic acid 8mmol and use naphthenic acid (molecular-weight average=about 270) 2.025g (being equivalent to about 8mmol), in addition, be conductive ink with the embodiment 1 the same silver-indium of making, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 355nm, and volume specific resistance is 9.8 μ Ω cm.The adaptation of film and substrate is good, has passed through belt stripping test.The ratio of the indium in the film is 1.0 atom %.Center line average roughness Ra is 3.2nm, is level and smooth film.In addition, at N ₂Under the gas atmosphere, even kept 60 minutes down at 300 ℃, the form on film surface does not change, excellent heat resistance.Measure the naphthenic acid that uses with GC (gas-chromatography)/MS (mass analysis), the result is that carbonatoms is the mixture of 10～30 compound, and carbonatoms is that the content of 17 composition is maximum.Wherein, the amount of naphthenic acid is calculated by molecular-weight average.

[embodiment 3]

(caproic acid+octylame)

Under the condition of embodiment 1, do not use docosoic acid, making caproic acid is 76mmol (that is, only using caproic acid as (B) carboxylic acid), in addition, is conductive ink with the embodiment 1 the same silver-indium of making, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 508.1nm, and volume specific resistance is 12.5 μ Ω cm.The ratio of the indium in the film is 0.1 atom %, center line average roughness Ra is 38.2nm, compare with 2 with above-mentioned embodiment 1, the adaptation and the surface smoothing of film and substrate are poor, but the silver-colored printing ink in the past that forms with using silver-colored monomer is compared, and the adaptation of the surfaceness of the film that is obtained and film and substrate improves.

[embodiment 4]

(caproic acid+octadecanoic acid+octylame)

Under the condition of embodiment 1, use octadecanoic acid at (B) carboxylic acid central replacement docosoic acid, in addition, be conductive ink with the embodiment 1 the same silver-indium of making, film forming on alkali-free glass substrate.The ratio of the indium in the film is 0.1 atom %.The adaptation of film and substrate is poorer than above-mentioned embodiment 1 and 2, but compares with the silver-colored printing ink in the past that uses silver-colored monomer to form, and the adaptation of the surfaceness of the film that is obtained and film and substrate improves.

[embodiment 5]

(docosoic acid+octylame)

Under the condition of embodiment 1, do not use caproic acid, making docosoic acid is 76mmol (that is, only using docosoic acid as (B) carboxylic acid), in addition, equally with embodiment 1 carry out the making that silver-indium is a conductive ink, at room temperature, above-mentioned metal can not fully be dissolved in the solvent, in addition, remain on 60 ℃, similarly make, generated condensation product as can be known.Therefore, under these conditions,, but compare with embodiment 1 even can access adaptation and improve effect with compare in the past, the adaptation of film and substrate to improve effect still poor.

[embodiment 6]

(naphthenic acid+octylame)

Under the condition of embodiment 2, do not use caproic acid, use naphthenic acid (molecular-weight average=about 270) 20.25g (being equivalent to about 75mmol) (promptly, only used naphthenic acid as (B) carboxylic acid), in addition, with the embodiment 2 the same silver-indiums of making is conductive ink, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 286nm, and volume specific resistance is 11.8 μ Ω cm.The adaptation of film and substrate is good, has passed through belt stripping test.The ratio of the indium in the film is 0.8 atom %.Center line average roughness Ra is 3.7nm, is level and smooth film.But, at N ₂Under the gas atmosphere, after 300 ℃ keep 60 minutes down, on the film surface, sporadicly generate the particle of hundreds of nm, compare with the above embodiments 1,2, poor heat resistance, but the silver-colored printing ink in the past that forms with using silver-colored monomer compares, and the surfaceness of the film that is obtained improves.

[embodiment 7]

(caproic acid+tetradecanoic acid+octylame)

Under the condition of embodiment 1,0.3mmol makes 0.4mmol into indium acetate, and uses tetradecanoic acid 8.0mmol at (B) carboxylic acid central replacement docosoic acid 8.0mmol, in addition, with the embodiment 1 the same silver-indium of making is conductive ink, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 422nm, and volume specific resistance is 10.2 μ Ω cm.The adaptation of film and substrate is good, has passed through belt stripping test.The ratio of the indium in the film is 0.3%.The medullary ray surface roughness Ra is 2.7nm, is level and smooth film.

[embodiment 8]

(caproic acid+pentadecylic acid+octylame)

Under the condition of embodiment 1,0.3mmol makes 0.4mmol into indium acetate, and uses pentadecylic acid 8.0mmol at (B) carboxylic acid central replacement docosoic acid 8.0mmol, in addition, with the embodiment 1 the same silver-indium of making is conductive ink, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 384nm, and volume specific resistance is 10.4 μ Ω cm.The adaptation of film and substrate is good, has passed through belt stripping test.The ratio of the indium in the film is 0.4 atom %.Center line average roughness Ra is 1.6nm, is level and smooth film.

[embodiment 9]

(caproic acid+hexadecanoic acid+octylame)

Under the condition of embodiment 1,0.3mmol makes 0.4mmol into indium acetate, and uses hexadecanoic acid 8.0mmol at (B) carboxylic acid central replacement docosoic acid 8.0mmol, in addition, with the embodiment 1 the same silver-indium of making is conductive ink, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 450nm, and volume specific resistance is 10.4 μ Ω cm.The adaptation of film and substrate is good, has passed through belt stripping test.The ratio of the indium in the film is 0.3 atom %.The medullary ray surface roughness Ra is 6.5nm, is level and smooth film.

[embodiment 10]

(caproic acid+octadecenoic acid+octylame)

Under the condition of embodiment 1,0.3mmol makes 0.4mmol into indium acetate, and uses octadecenoic acid 8.0mmol at (B) carboxylic acid central replacement docosoic acid 8.0mmol, in addition, with the embodiment 1 the same silver-indium of making is conductive ink, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 450nm, and volume specific resistance is 10.4 μ Ω cm.The adaptation of film and substrate is good, has passed through belt stripping test.The ratio of the indium in the film is 0.3 atom %.The medullary ray surface roughness Ra is 6.5nm, is level and smooth film.

[embodiment 11]

(caproic acid+octadecadienoic acid+octylame)

Under the condition of embodiment 1,0.3mmol makes 0.4mmol into indium acetate, and uses octadecadienoic acid 8.0mmol at (B) carboxylic acid central replacement docosoic acid 8.0mmol, in addition, with the embodiment 1 the same silver-indium of making is conductive ink, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 329nm, and volume specific resistance is 5.35 μ Ω cm.The adaptation of film and substrate is good, has passed through belt stripping test.The ratio of the indium in the film is 0.2 atom %.The medullary ray surface roughness Ra is 3.9nm, is level and smooth film.

[embodiment 12]

In addition, change the kind of protective colloid, under 300 ℃, 30～90 minutes firing condition of firing time, measure and have or not the result of particle growth as shown in table 1.Although confirm to have particle growth above 50nm, to compare with the monomeric situation of silver, surfaceness is improved to be designated as " △ ", particle suppression being designated as below 50nm " zero ".

Table 1

Protective colloid	Have or not particle growth	Estimate
			Caproic acid, naphthenic acid, octylame	Do not have	○
Caproic acid, octylame	Have	△
			Naphthenic acid, octylame	Have	△
Naphthenic acid, n-Laurylamine	Have	△
			Dodecylic acid, n-Laurylamine	Have	△
Dodecylic acid, octylame	Have	△
			Sad, octylame	Have	△

As mentioned above; according to the present invention; above-mentioned conductive ink composition contains following solid matter; promptly; this solid matter is to cover the surface of the metal particle that is made of the multiple metal that contains noble metal at least and form with the protective colloid that is made of two kinds of organic compound at least; therefore compare as the situation of metal particle with using silver-colored monomer, the particle growth that can form metal is suppressed and surface smoothing is excellent and with the adaptation of coating object with compared more improved film (metallic membrane) in the past.In addition,, except containing amine, also contain the above-mentioned high-molecular weight carboxylic acid and the protective colloid of low-molecular-weight carboxylic acid simultaneously, can significantly improve the effect of the particle growth that suppresses above-mentioned metal by using as protective colloid.

[embodiment 13]

Under the condition of embodiment 1,0.3mmol makes 0.4mmol into indium acetate, and uses octadecadienoic acid 8.0mmol at (B) carboxylic acid central replacement docosoic acid 8.0mmol, in addition, with the embodiment 1 the same silver-indium of making is conductive ink, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 300nm, and volume specific resistance is 4.38 μ Ω cm.Though the indium in the detection membrane, its ratio is less than 0.1 atom %.The medullary ray surface roughness Ra is 2.1nm, is level and smooth film.

Studied the reflection characteristic of this film, the result as shown in figure 29." In 0.1at% " is to use caproic acid and octadecadienoic acid is the coated film (burning till film) of conductive ink as the above-mentioned silver-indium of carboxylic acid, and near the zone of reflection characteristic 400nm reduces, but roughly demonstrates good reflection characteristic in the visible region.

In addition, similarly, studied the reflection characteristic of " In 0.3at% ", " In 0.6at% ", " In 0.8at% ", " Al (sputtered film) " and " In 0.1% (vapor-deposited film) ".Summarized results as shown in figure 29.Here, shown in embodiment 2, " In 0.3at% ", " In 0.6at% ", " In0.8at% " are to be the film forming reflectivity Characteristics of burning of conductive ink formation by the silver-indium that uses caproic acid and naphthenic acid as carboxylic acid, the situation the when ratio of representing indium in the film respectively is 0.3 atom %, 0.6 atom %, 0.8 atom %.In addition, " Al (sputtered film) " expression is based on the film forming Al film of splash." In 0.1% (vapor-deposited film) " is evaporation silver-indium alloy and the vapor-deposited film (not containing protective colloid) that forms, and the ratio of indium is the situation of 0.1 atom % in the expression film.The ratio (In concentration) of indium and the used protective colloid of conductive ink (conductive ink composition) that uses in the film forming of metallic membrane are summarized in the table 2 in the film of each film (metallic membrane) as shown in figure 29.Wherein, the mensuration of above-mentioned reflection characteristic is to use " the spectrophotometer U-4100 of Hitachi " (spectrophotometer of Hitachi Co., Ltd's system) to carry out.

Table 2

	Protective colloid	In concentration
			In 0.1at％	Octadecadienoic acid caproic acid octylame	0.1 atom %
In 0.3at％	Naphthenic acid caproic acid octylame	0.3 atom %
			In 0.6at％	Naphthenic acid caproic acid octylame	0.6 atom %
In 0.8at％	Naphthenic acid caproic acid octylame	0.8 atom %
			In 0.1% (vapor-deposited film)	-	0.1 atom %
Al (sputtered film)	-	-

By result shown in Figure 29 as can be known, the content of indium has a significant impact reflectivity.In addition, the big more reflectivity of the ratio of indium is low more in the film, so in order to obtain good reflection characteristic, be necessary to reduce the indium amount in the film as far as possible.

On the other hand; by embodiment 3,4 as can be known; minimizing along with the ratio of the indium in the film; adaptation to substrate has the trend that weakens; but In concentration is made various changes to be studied; found that; the film that in protective colloid, uses octadecadienoic acid, caproic acid, octylame and form; even if under the extremely low situation of indium content (In concentration); above-mentioned adaptation excellence; in " In 0.1at% " in Figure 29,, also can keep good adaptation even the indium ratio in the film is lower than 0.1 atom %.

And then; shown in " In 0.1at% "; the film that in protective colloid, uses octadecadienoic acid, caproic acid, octylame and form; the particle growth that under the effect of indium and protective colloid, suppresses silver; even if, be suitable for reflector as can be known so after 300 ℃ thermal treatment, also do not see silver-colored distinctive particle growth.About this reflection characteristic with the film of " In 0.1at% " expression, reflectivity is 80% at wavelength 400nm place, lower than " Al (sputtered film) ", but in long wavelength one side longer than wavelength 450nm, surpass reflectivity on the contrary, can obtain and " In 0.1% (vapor-deposited film) " approaching reflection characteristic based on the film forming Al film of splash.

In addition, can infer: should " In 0.1at% " hang down the reason of wavelength one lateral reflection rate not as " In 0.1% (vapor-deposited film) ", may be relevant with the organic composition in residuing in above-mentioned ink film.Therefore, can infer that the reason that the big more reflectivity of In concentration reduces more is not only relevant with In concentration, also relevant with the organic composition that contains.

[embodiment 14]

(silver is conductive ink composition)

Under the condition of embodiment 1, do not use indium acetate, in the middle of (B) carboxylic acid, replace docosoic acid 8.0mmol and use octadecadienoic acid 8.0mmol, in addition, making similarly to Example 1 and using silver-colored monomer is conductive ink (silver is conductive ink composition) as the silver of above-mentioned metal particle, film forming on alkali-free glass substrate.The film forming thickness of the burning that obtains is 298nm, and volume specific resistance is 3.11 μ Ω cm.The adaptation of film and substrate is good, has passed through belt stripping test.The medullary ray surface roughness Ra is 16.3nm, is level and smooth film.According to present embodiment, although use silver-colored monomer,, to compare with using the monomeric silver-colored printing ink in the past of silver by octadecadienoic acid, caproic acid, octylame are used as protective colloid as metal, the surfaceness of the film that obtains improves.

The carbonatoms or the average carbon atom number summary sheet of (B) carboxylic acid that uses in the various embodiments described above are shown in table 3.

Table 3

	(B) carbonatoms of carboxylic acid or average carbon atom number	(B) carboxylic acid
			Embodiment
1	7.68	Caproic acid, docosoic acid
			Embodiment
2	7.16	Caproic acid, naphthenic acid
			Embodiment
3	6.00	Caproic acid
			Embodiment
4	7.26	Caproic acid, octadecanoic acid
			Embodiment
5	22.00	Docosoic acid
			Embodiment
6	17.00	Naphthenic acid
			Embodiment
7	6.84	Caproic acid, tetradecanoic acid
			Embodiment 8	6.95	Caproic acid, pentadecylic acid
Embodiment
	9	7.05	Caproic acid, hexadecanoic acid
Embodiment 10				7.26	Caproic acid, octadecenoic acid
	Embodiment
11		7.26	Caproic acid, octadecadienoic acid
	Embodiment
12		7.16	Caproic acid, naphthenic acid
				6.00	Caproic acid
		17.00	Naphthenic acid
				12.00	Dodecylic acid
		8.00	Sad
	Embodiment
13		7.26	Caproic acid, octadecadienoic acid
	Embodiment
14		7.26	Caproic acid, octadecadienoic acid

From the above; conductive ink composition of the present invention contains following solid matter; promptly; this solid matter is for example to be formed by the metal particle surface that the alloy that contains noble metal at least constitutes with the surface that the protective colloid that is made of two kinds of organic compound at least covers by at least a metal particle that constitutes for the multiple metal of noble metal; therefore compare as the situation of the conductive ink in the past of metal particle with the noble metal monomer as silver-colored printing ink with use, the particle growth that can form metal is suppressed; surface smoothing excellent and with the adaptation of coating object or reflection efficiency with compared improved film (metallic membrane) in the past.Above-mentioned conductive ink composition can be the solid matter that is made of following metal particle and the following protective colloid that surrounds this metal particle; be above-mentioned metal particle by at least a for the multiple metal of noble metal constitutes, and above-mentioned protective colloid is made of two kinds of organic compound at least.For this solid matter, by surrounding (covering) above-mentioned metal particle with protective colloid, it can be dispersed in the organic solvent, thereby can disperse then to use in organic solvent.In addition, above-mentioned conductive ink composition can be the fluent meterial that itself contains organic solvent.That is, above-mentioned conductive ink composition can be to contain above-mentioned metal particle, surround the protective colloid that is made of two kinds of organic compound at least of this metal particle and the fluent meterial of organic solvent.

That is, as mentioned above, the formation of conductive ink composition of the present invention can be: contain that the useful protective colloid that is made of two kinds of organic compound at least covers the surface of the metal particle that is made of the alloy that contains noble metal at least and the solid matter that forms.

In addition, as mentioned above, above-mentioned conductive ink composition can be a formation as described below: promptly, it is the solid matter that constitutes by following metal particle and the following protective colloid that surrounds this metal particle, be above-mentioned metal particle by at least a for the multiple metal of noble metal constitutes, and above-mentioned protective colloid is made of two kinds of organic compound at least; This conductive ink composition can be dispersed in the organic solvent.

In the scope of ratio more than 60 quality %, below the 95 quality % of the metal particle in the preferred above-mentioned solid matter of these conductive ink compositions; in the scope of the ratio of protective colloid more than 5 quality %, below the 40 quality % (but, both total amounts are 100 quality %).

In addition; as implied above, conductive ink composition of the present invention can be to contain by at least a metal particle that forms for the multiple metal of noble metal, surround the protective colloid that is made of two kinds of organic compound at least of this metal particle and the fluent meterial of organic solvent.

Above-mentioned conductive ink composition preferably contains above-mentioned metal particle, protective colloid and organic solvent with following ratio respectively; wherein; in the scope of the ratio of metal particle more than 15 quality %, below the 95 quality %; in the scope of the ratio of protective colloid more than 1 quality %, below the 50 quality %; in the scope of the ratio of organic solvent more than 1 quality %, below the 60 quality % (but, their total amount is 100 quality %).

Constitute according to above-mentioned each; above-mentioned conductive ink composition; by containing following solid matter; promptly; this solid matter is for example to be formed by the metal particle surface that the alloy that contains noble metal at least constitutes with the surface that the protective colloid that is made of two kinds of organic compound at least covers by at least a metal particle that constitutes for the multiple metal of noble metal; therefore compare as the conductive ink in the past of metal particle with silver-colored monomer as silver-colored printing ink with use, the particle growth that can form metal is suppressed; surface smoothing excellent and with the adaptation of coating object or reflection efficiency with compared improved film (metallic membrane) in the past.

In addition, above-mentioned metal particle preferably contain standard oxidationreduction potential and be-0.45～+ metal in the scope of 1.5V/NHE is as the metal outside the above-mentioned noble metal.

In addition, as the metal except above-mentioned noble metal, above-mentioned metal particle preferably contains at least a metal of selecting from be made of iron, cobalt, nickel, copper, cadmium, indium, tin, thallium, lead, molybdenum and bismuth one group.

Preferred especially above-mentioned metal particle is made of silver and indium.

Constitute according to above-mentioned each, by above-mentioned conductive ink composition being used as wiring material and/or the electrode materials on the circuit substrate, with silver-colored monomer is compared as the situation of above-mentioned metal particle, the particle growth that can suppress metal, the adaptation of insulativity substrates (base material) such as improvement and glass substrate.Thus, constitute, can form the particularly low-resistance distribution of low-resistance metal level and/or low-resistance electrode according to above-mentioned each.In addition, the result that above-mentioned conductive ink composition suppresses the particle growth of metal is, with the reflection efficiency of comparing the reflection part that improves this conductive ink composition of use and form in the past.Thus, according to each above-mentioned formation, can provide to form and compare in the past surface smoothing, adaptation, the conductive ink composition of the improved reflection part of reflection efficiency with the coating object.Above-mentioned metal level is particularly preferred for reflecting electrode etc.

In addition; the compound that above-mentioned protective colloid is preferably obtained by the raw material that contains (A) amine, (B) carboxylic acid and/mixture; the mixture of more preferably above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

In addition, above-mentioned (A) amine preferably carbonatoms be 5～20 alkylamine.

Say that more specifically for example, above-mentioned protective colloid preferably is made of octadecadienoic acid, caproic acid and octylame.In addition, above-mentioned protective colloid for example preferably is made of naphthenic acid, caproic acid and octylame.

And then; above-mentioned protective colloid is preferably compound and/or the mixture that is obtained by following raw material; promptly; this raw material contains more than 40 moles of %, the alkylamine of 79 moles of following scopes of %; at least a carboxylic acid (their total amount is 100 moles of %) that (II) of at least a carboxylic acid of selecting from carbonatoms is 4～9 carboxylic acid with 2 moles more than the %, (I) of 40 moles of following scopes of % and 1 mole more than the %, 20 moles of following scopes of % selects from carbonatoms is 10～30 carboxylic acid.

Above-mentioned protective colloid is very high to the inhibition effect of particle growth, can significantly be suppressed in the film that is made of above-mentioned conductive ink composition of the present invention, and (periphery) compares the particle growth of the metal that produces in the many parts of precious metal amount with on every side.For this reason, according to structure of the present invention, can make surface smoothing extremely excellent, with the adaptation and the high metal level (metallic membrane) of reflection efficiency of insulated substrate (base material) such as glass substrate.

In addition; as mentioned above; conductive ink composition of the present invention is by containing solid matter as follows; even using under the situation of noble metal monomer as above-mentioned metal particle; compare with conductive ink in the past; the particle growth that can form metal is suppressed; the surface smoothing excellence; and adaptation and the improved metal level of reflection efficiency (metallic membrane) compared with the past and the coating object; wherein; described solid matter is to use the amine by (A); (B) protective colloid of carboxylic acid formation; the mixture of wherein above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected and (B) average carbon atom number of carboxylic acid be 5～25 protective colloid, cover the metal particle that constitutes by noble metal and form.Above-mentioned conductive ink composition can be to surround the metal particle that (covering) be made of noble metal and the solid matter that forms with above-mentioned protective colloid, and can be dispersed in the organic solvent, himself can be the fluent meterial that contains organic solvent.

Promptly; as mentioned above; conductive ink composition of the present invention can have following structure; promptly; contain useful protective colloid and cover the metal particle that constitutes by noble metal and the solid matter that forms; above-mentioned protective colloid is made of (A) amine, (B) carboxylic acid; the mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

In addition; as mentioned above; conductive ink composition of the present invention also can have following structure; promptly; this conductive ink composition is to use the protective colloid that is made of (A) amine, (B) carboxylic acid to cover the metal particle that is made of noble metal and the solid matter that forms; can be dispersed in the organic solvent; and the mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) selected from carbonatoms is 10～30 carboxylic acid, and (B) average carbon atom number of carboxylic acid is 5～25.

In these conductive ink compositions; in the scope of the ratio of the metal particle in the preferred above-mentioned solid matter more than 60 quality %, below the 95 quality %, in the scope (wherein both total amounts are 100 quality %) of the ratio of protective colloid more than 5 quality %, below the 40 quality %.

In addition; as mentioned above; conductive ink composition of the present invention also can have following structure; promptly; this conductive ink composition is to contain the metal particle that is made of noble metal; surround the protective colloid of this metal particle; fluent meterial with organic solvent; above-mentioned protective colloid is by (A) amine; (B) carboxylic acid constitutes; the mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

So; when above-mentioned conductive ink composition is when containing the fluent meterial of metal particle, protective colloid and organic solvent; above-mentioned conductive ink composition preferably contains above-mentioned metal particle, protective colloid and organic solvent with ratio as described below; be in the scope of metal particle more than 15 quality %, below the 95 quality %; in the scope of protective colloid more than 1 quality %, below the 50 quality %; in the scope of organic solvent more than 1 quality %, below the 60 quality % (wherein, their total amount is 100 quality %).

In addition, use like this in the conductive ink composition of noble metal monomer as metal particle, above-mentioned amine also preferably carbonatoms be 5～20 alkylamine.

In addition, above-mentioned protective colloid preferably is made of octadecadienoic acid, caproic acid and octylame.In addition, above-mentioned protective colloid preference is as being made of naphthenic acid, caproic acid and octylame.

And then; above-mentioned protective colloid be preferably the compound that obtains by following raw material and/mixture; promptly; this raw material contains more than 40 moles of %, the alkylamine of 79 moles of following scopes of %; at least a carboxylic acid (their total amount is 100 moles of %) that (II) of at least a carboxylic acid of selecting from carbonatoms is 4～9 carboxylic acid with 2 moles more than the %, (I) of 40 moles of following scopes of % and 1 mole more than the %, 20 moles of following scopes of % selects from carbonatoms is 10～30 carboxylic acid.

Above-mentioned protective colloid is very high to the inhibition effect of particle growth; in above-mentioned conductive ink composition of the present invention; even using under the situation of noble metal monomer as above-mentioned metal particle; with with noble metal as metal particle and it is dispersed in the conductive inks in the past such as so-called silver-colored printing ink that form in the middle of the organic solvent compares, can form the particle growth, surface smoothing excellence and the improved metal level of adaptation (metallic membrane) compared with the past and the coating object that suppress metal.Therefore, according to structure of the present invention, can provide the conductive ink composition that can form particularly low-resistance distribution of low-resistance metal level and/or electrode.In addition, above-mentioned conductive ink composition, the repressed result of the particle growth of its metal can form the metal level of reflection efficiency excellence.Thus, constitute according to above-mentioned each, can provide can form surface smoothing, with the conductive ink composition of the reflection part of the adaptation of coating object, reflection efficiency excellence.Above-mentioned metal level is particularly preferred for reflecting electrode etc.

In addition, to be preferably carbonatoms be 10～35 hydro carbons to above-mentioned organic solvent.Wherein, to be preferably the carbonatoms with side chain be 16～30 aliphatic hydrocarbon to above-mentioned organic solvent.

Above-mentioned organic solvent obtains easily, and the dispersion stabilization of the metal particle that covers with above-mentioned protective colloid is good simultaneously, and boiling point is lower in addition, so can easily remove by drying or thermal treatment (for example burning till).

In addition, as mentioned above, the formation of reflection part of the present invention is, above-mentioned conductive ink composition of the present invention is carried out drying or thermal treatment (for example burning till) and forms.

In addition, as mentioned above, the formation of circuit substrate of the present invention is, has the metal level that above-mentioned conductive ink composition of the present invention is carried out drying or thermal treatment (for example burning till) and form.

As above-mentioned metal level, that preferably selects from distribution, electrode and reflection part is at least a.

And then as mentioned above, the formation of electronic installation of the present invention is to possess foregoing circuit substrate of the present invention.

As mentioned above, reflection part of the present invention, circuit substrate and electronic installation have the metal level that above-mentioned conductive ink composition of the present invention is carried out drying or thermal treatment (for example burning till) and form, so can provide that the particle growth of metal is suppressed, surface smoothing excellent and, high reliability circuit substrate improved with the adaptation of comparing and be coated with object in the past and electronic installation.In addition, the metal level that above-mentioned metal level forms with using conductive ink is in the past compared, the particle growth of metal more is suppressed, surface smoothing, more excellent with the adaptation of coating object, so with above-mentioned use in the past conductive ink and the metal level that forms compare, resistance is lower, in addition, reflection efficiency is also more excellent.

Conductive ink composition of the present invention can form particle growth, surface smoothing excellence and adaptation or the improved metal level of reflection efficiency (metallic membrane) compared with the past and the coating object that has suppressed metal, use so be applicable to the manufacturing of various circuit substrates such as the tft array substrate that is used for liquid crystal indicator etc., the electrode base board that is used for PDP, printed wiring board, flexible wiring substrate, be particularly preferred for using the manufacturing of the circuit substrate of ink jet method.In addition, such circuit substrate can be applicable to following electronic installation, be display unit such as liquid crystal indicator, PDP, organic EL panel, inorganic EL panel, and be the image-input devices such as two dimensional image input unit of representative with fingerprint sensor, X ray camera head etc.

The present invention is not limited to each above-mentioned embodiment, can carry out various changes in the scope shown in the technical scheme, will be in different embodiments disclosed respectively technological method combination and the embodiment that obtains is also included within the technical scope of the present invention.

In addition, explaining embodiment or the embodiment that finishes in the object of invention in detail, can make the people thoroughly understand technology contents of the present invention, be not to be limited to these embodiment and the example that carries out narrow sense explanation, in the scope of aim of the present invention and technical scheme, can make various enforcements after changing.

Claims (39)

1, a kind of conductive ink composition is characterized in that,

Comprise with the protective colloid (305) that is made of two kinds of organic compound at least and cover the surface of the metal particle (304) that is made of the alloy that contains noble metal at least and the solid matter that forms, described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

2, a kind of conductive ink composition is characterized in that,

It is solid matter by protective colloid (305) formation of metal particle (304) and this metal particle of encirclement (304); described metal particle is made of for the multiple metal of noble metal at least a; and described protective colloid is made of two kinds of organic compound at least; this conductive ink composition can disperse in organic solvent, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

3, a kind of conductive ink composition is characterized in that,

Contain useful protective colloid (305) and cover the metal particle (304) that constitutes by noble metal and the solid matter that forms,

Above-mentioned protective colloid (305) be by (A) amine and (B) carboxylic acid constitute,

The mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

4, a kind of conductive ink composition is characterized in that,

Be use by (A) amine and (B) protective colloid (305) that constitutes of carboxylic acid cover the metal particle (304) that constitutes by noble metal and the solid matter that forms can disperse in organic solvent,

The mixture of above-mentioned (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

5, as any described conductive ink composition in the claim 1～4, it is characterized in that,

In the scope of the ratio of the metal particle in the described solid matter (304) more than 60 quality %, below the 95 quality %, in the scope of the ratio of protective colloid (305) more than 5 quality %, below the 40 quality %, and both total amounts are 100 quality %.

6, a kind of conductive ink composition is characterized in that,

Be contain by at least a be the metal particle (304) that constitutes of the multiple metal of noble metal, surround this metal particle (304) at least by the fluent meterial of two kinds of protective colloids that organic compound constituted (305) and organic solvent, described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

7, a kind of conductive ink composition is characterized in that,

Be to contain the metal particle (304) that constitutes by noble metal, the protective colloid (305) that surrounds this metal particle (304) and the fluent meterial of organic solvent;

Described protective colloid be by (A) amine and (B) carboxylic acid constitute;

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

8, as claim 6 or 7 described conductive ink compositions, it is characterized in that,

Contain described metal particle (304), protective colloid (305) and organic solvent; wherein; in the scope of metal particle (304) more than 15 quality %, below the 95 quality %; in the scope of protective colloid (305) more than 1 quality %, below the 50 quality %; in the scope of organic solvent more than 1 quality %, below the 60 quality %, and their total amount is 100 quality %.

9, as any described conductive ink composition in the claim 1,2,6, it is characterized in that,

Described metal particle (304) contain standard oxidationreduction potential-0.45～+ metal in the scope of 1.5V/NHE is as the metal beyond the described noble metal.

10, as any described conductive ink composition in the claim 1,2,6, it is characterized in that,

Described metal particle (304) contains at least a metal selected as the metal outside the described noble metal from be made of iron, cobalt, nickel, copper, cadmium, indium, tin, thallium, lead, molybdenum and bismuth one group.

11, as any described conductive ink composition in the claim 1,2,6, it is characterized in that,

Described metal particle (304) is to be made of silver and indium.

12, as any described conductive ink composition in the claim 1,2,6, it is characterized in that,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

13, as any described conductive ink composition in the claim 1,2,6, it is characterized in that,

Described (A) amine is that carbonatoms is 5～20 alkylamine.

14, as any described conductive ink composition in the claim 1,2,6, it is characterized in that,

Described (A) amine is that carbonatoms is 5～20 alkylamine,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

15, as any described conductive ink composition in the claim 3,4,7, it is characterized in that,

Described (A) amine is that carbonatoms is 5～20 alkylamine.

16, as any described conductive ink composition in the claim 1～4,6,7, it is characterized in that,

Described protective colloid (305) is to be made of octadecadienoic acid, caproic acid and octylame.

17, as any described conductive ink composition in the claim 1～4,6,7, it is characterized in that,

Described protective colloid (305) is to be made of naphthenic acid, caproic acid and octylame.

18, as any described conductive ink composition in the claim 1～4,6,7, it is characterized in that,

Described protective colloid (305) is by the compound and/or the mixture that have the following raw material that constitutes (302) to obtain; promptly; described raw material contains above, the 79 moles of alkylamines that the following scope of % is interior of 40 moles of %; at least a carboxylic acid of from carbonatoms is 4～9 carboxylic acid, selecting with (I) in 2 moles more than the %, the 40 moles following scopes of %; at least a carboxylic acid of from carbonatoms is 10～30 carboxylic acid, selecting with (II) in 1 mole more than the %, the 20 moles following scopes of %, and their total amount is 100 moles of %.

19, as claim 6 or 7 described conductive ink compositions, it is characterized in that,

Described organic solvent is that carbonatoms is 10～35 hydro carbons.

20, as claim 6 or 7 described conductive ink compositions, it is characterized in that,

Described organic solvent is that carbonatoms with side chain is 16～30 aliphatic hydrocarbon.

21, a kind of reflection part (24,29) is characterized in that,

Conductive ink composition carried out drying or thermal treatment and form,

Described conductive ink composition comprises with the protective colloid (305) that is made of two kinds of organic compound at least and covers the surface of the metal particle (304) that is made of the alloy that contains noble metal at least and the solid matter that forms, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

22, a kind of reflection part (24,29) is characterized in that,

Conductive ink composition carried out drying or thermal treatment and form,

Described conductive ink composition is by metal particle (304) and surrounds the solid matter of protective colloid (305) formation of this metal particle (304); described metal particle is made of for the multiple metal of noble metal at least a; and described protective colloid is made of two kinds of organic compound at least; this conductive ink composition can disperse in organic solvent, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

23, a kind of reflection part (24,29) is characterized in that,

Conductive ink composition carried out drying or thermal treatment and form,

Described conductive ink composition contains useful protective colloid (305) and covers the metal particle (304) that is made of noble metal and the solid matter that forms,

Described protective colloid (305) be by (A) amine and (B) carboxylic acid constitute,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

24, a kind of reflection part (24,29) is characterized in that,

Conductive ink composition carried out drying or thermal treatment and form,

Described conductive ink composition be use by (A) amine and (B) protective colloid (305) that constitutes of carboxylic acid cover the metal particle (304) that constitutes by noble metal and the solid matter that forms, this conductive ink composition can disperse in organic solvent,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

25, a kind of reflection part (24,29) is characterized in that,

Conductive ink composition carried out drying or thermal treatment and form,

Described conductive ink composition be contain by at least a be the metal particle (304) that constitutes of the multiple metal of noble metal, surround this metal particle (304) at least by the fluent meterial of two kinds of protective colloids that organic compound constituted (305) and organic solvent, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

26, a kind of reflection part (24,29) is characterized in that,

Conductive ink composition carried out drying or thermal treatment and form,

Described conductive ink composition is to contain the metal particle (304) that is made of noble metal, the protective colloid (305) that surrounds this metal particle (304) and the fluent meterial of organic solvent,

Described protective colloid (305) be by (A) amine and (B) carboxylic acid constitute,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

27, a kind of circuit substrate (11) is characterized in that,

Have the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition contains that the useful protective colloid that is made of two kinds of organic compound at least (305) covers the surface of the metal particle (304) that is made of the alloy that contains noble metal at least and the solid matter that forms, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

28, a kind of circuit substrate (11) is characterized in that,

Have the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition is by metal particle (304) and surrounds the solid matter of protective colloid (305) formation of this metal particle (304); described metal particle is made of for the multiple metal of noble metal at least a; and described protective colloid is made of two kinds of organic compound at least; this conductive ink composition can disperse in organic solvent, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

29, a kind of circuit substrate (11) is characterized in that,

Have the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition contains useful protective colloid (305) and covers the metal particle (304) that is made of noble metal and the solid matter that forms,

Described protective colloid (305) be by (A) amine and (B) carboxylic acid constitute,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

30, a kind of circuit substrate (11) is characterized in that,

Have the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition be use by (A) amine and (B) protective colloid (305) that constitutes of carboxylic acid cover the metal particle (304) that constitutes by noble metal and the solid matter that forms can disperse in organic solvent,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

31, a kind of circuit substrate (11) is characterized in that,

Have the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition be contain by at least a metal particle (304) that constitutes for the multiple metal of noble metal, surround this metal particle (304) at least by the fluent meterial of two kinds of protective colloids that organic compound constituted (305) and organic solvent, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

32, a kind of circuit substrate (11) is characterized in that,

Have the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition is to contain the metal particle (304) that is made of noble metal, the protective colloid (305) that surrounds this metal particle (304) and the fluent meterial of organic solvent.

Described protective colloid (305) be by (A) amine and (B) carboxylic acid constitute,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

33, as any described circuit substrate (11) in the claim 27～32, it is characterized in that,

Described metal level is select from distribution, electrode and reflection part at least a.

34, a kind of electronic installation is characterized in that,

Possess circuit substrate (11), wherein said circuit substrate has the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition comprises with the protective colloid (305) that is made of two kinds of organic compound at least and covers the surface of the metal particle (304) that is made of the alloy that contains noble metal at least and the solid matter that forms, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

35, a kind of electronic installation is characterized in that,

Possess circuit substrate (11), wherein said circuit substrate has the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition is by metal particle (304) and surrounds the solid matter of protective colloid (305) formation of this metal particle; described metal particle is made of for the multiple metal of noble metal at least a; and described protective colloid is made of two kinds of organic compound at least; this conductive ink composition can disperse in organic solvent, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

36, a kind of electronic installation is characterized in that,

Possess circuit substrate (11), wherein said circuit substrate has the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition contains useful protective colloid (305) and covers the metal particle (304) that is made of noble metal and the solid matter that forms,

Described protective colloid (305) be by (A) amine and (B) carboxylic acid constitute,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

37, a kind of electronic installation is characterized in that,

Possess circuit substrate (11), wherein said circuit substrate has the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition be use by (A) amine and (B) protective colloid that constitutes of carboxylic acid cover the metal particle (305) that constitutes by noble metal and the solid matter that forms can disperse in organic solvent,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

38, a kind of electronic installation is characterized in that,

Possess circuit substrate (11), wherein said circuit substrate has the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition be contain by at least a metal particle (304) that constitutes for the multiple metal of noble metal, surround this metal particle at least by the fluent meterial of two kinds of formed protective colloids of organic compound (305) and organic solvent, and described protective colloid (305) is by containing (A) amine and (B) compound and/or the mixture that obtain of the raw material of carboxylic acid (302).

39, a kind of electronic installation is characterized in that,

Possess circuit substrate (11), wherein said circuit substrate has the metal level that conductive ink composition is carried out drying or thermal treatment and form,

Described conductive ink composition is to contain the metal particle (304) that is made of noble metal, the protective colloid (305) that surrounds this metal particle (304) and the fluent meterial of organic solvent,

Described protective colloid (305) be by (A) amine and (B) carboxylic acid constitute,

The mixture of described (B) carboxylic acid at least a carboxylic acid that to be (I) select from carbonatoms is 4～9 carboxylic acid and at least a carboxylic acid (II) from carbonatoms is 10～30 carboxylic acid, selected, and (B) average carbon atom number of carboxylic acid is 5～25.

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