JP6530673B2 - Composition for forming phosphorus-doped tin oxide conductive film and phosphorus-doped tin oxide conductive film - Google Patents

Description

  The present invention can suppress the change of the surface resistivity of the phosphorus-doped tin oxide conductive film under high temperature and high humidity and under ultraviolet irradiation, has excellent adhesion to a substrate, and has both good conductivity, transparency and light resistance. The present invention relates to a composition for forming a phosphorus-doped tin oxide conductive film and a phosphorus-doped tin oxide conductive film. In the present specification, phosphorus-doped tin oxide may be referred to as PTO (Phosphorus Tin Oxide).

  A transparent electrode is used in a display device such as an LCD (Liquid Crystal Display), a PDP (Plasma Display Panel), an organic EL (ElectroLuminescence), and a touch panel. The transparent electrode is often made of a transparent conductive material made of ITO (Indium Tin Oxide), PTO or the like. Such a transparent electrode is usually formed into a film shape by sputtering or the like (see, for example, Patent Document 1). However, as the size of the substrate on which the film is formed is increased, the size of the sputtering apparatus is increased, and the cost is increased. In order to solve this point, a method of applying a coating liquid for forming a transparent conductive film or a transparent conductive paste composition on a substrate instead of the sputtering method has been proposed (see, for example, Patent Documents 2 and 3).

  Patent Document 2 discloses a coating liquid for forming a transparent conductive film suitable for forming an ITO transparent conductive film having both transparency and conductivity by a coating method, in particular, an inkjet printing method. The coating solution for forming a transparent conductive film contains indium acetylacetone, an organotin compound, a cellulose derivative, an alkylphenol and / or an alkenylphenol, a dibasic acid ester and / or benzyl acetate, a diethylene glycol derivative, and acetylacetonate indium and an organotin compound The total content is 1 to 30% by weight, and the content of the cellulose derivative is 5% by weight or less.

  Patent Document 3 discloses a transparent conductive paste composition capable of forming a transparent conductive film having good surface properties and having both good conductivity and transparency when applied on a substrate by printing. . The transparent conductive paste composition contains 80 to 99% by weight of the transparent conductive particles, the binder resin, and the organic solvent of the terpene solvent and the ketone solvent in the solid content of the composition.

  However, as in the coating liquid for forming a transparent conductive film described in Patent Document 2, when the coating liquid for forming a transparent conductive film is formed on, for example, a PET film of a base material, the film is It is easy to exfoliate from the material, which has been a cause of lowering the reliability. Moreover, when the transparent conductive film apply | coated by the method of the said patent document 2 and 3 was put on high temperature, high humidity for a long time, there existed a tendency for surface resistivity to rise due to the oxygen and moisture in atmosphere. In order to solve this subject, transparent conductive material such as ITO powder, transparent conductive particles such as ITO powder, silica material and silane coupling agent are disclosed, and transparent conductive material with small change in surface resistivity under the influence of temperature and humidity is disclosed. (See, for example, Patent Document 4). The transparent conductive film formed of the transparent conductive material disclosed in Patent Document 4 can sufficiently suppress the increase in surface resistivity even under high temperature and high humidity.

JP, 2004-315951, A (paragraph [0002]) JP, 2006-28431, A (summary, claim 1, claim 7) JP, 2011-192401, A (summary, claim 1) JP, 2009-135044, A (summary, claim 1) WO 2006/028131 (claim 12, paragraph [0010], paragraph [0012], paragraph [0022], paragraph [0025], paragraphs [0041] to [0046], FIG. 1, FIG. 4 and FIG. 8)

  However, in recent years, the application of the transparent conductive film is further diversified, and for forming a conductive film which can suppress the change of the surface resistivity of the transparent conductive film under high temperature and high humidity even under more severe conditions than before. A composition is sought.

  Furthermore, in recent years, the case where the touch panel is used in a severe environment where it is exposed to direct sunlight for a long time is increasing. In this case, the touch panel may be deteriorated by the influence of ultraviolet rays and the like contained in the sunlight. Specifically, when an ITO conductive film is used for the transparent electrode of the touch panel, the surface resistivity of the ITO conductive film is lowered, which causes a defect in the sensitivity of the touch sensor. In order to solve this problem, a resistive film type touch panel having light resistance capable of preventing deterioration due to ultraviolet rays and exhibiting excellent performance even in relatively severe outdoor use is disclosed (for example, a patent). Reference 5). This resistive film type touch panel is configured by laminating a polarizing plate, an upper planar member, an ITO transparent conductive film, a wiring substrate, a spacer, an ITO transparent conductive film, a lower planar member, and an ultraviolet absorbing material as an upper planar member. And a UV-absorbing adhesive layer containing the above is interposed between two layers made of two siloxane crosslinkable acrylic silicone resin films. According to this touch panel, even if ultraviolet rays are incident on the touch panel by the ultraviolet absorbing adhesive layer, the deterioration due to the ultraviolet rays is prevented. However, in this touch panel, it is necessary to separately provide an ultraviolet light absorbing adhesive layer, so that the number of components increases and the manufacturing process becomes complicated.

  The first object of the present invention is to suppress the increase of the surface resistivity of the PTO conductive film under high temperature and high humidity even under more severe conditions than in the prior art, and it is excellent in adhesion to the substrate, and it is favorable. It is an object of the present invention to provide a composition for forming a PTO conductive film having both conductivity and transparency and a PTO conductive film.

  The second object of the present invention is to preferably suppress the decrease in the surface resistivity of the PTO conductive film without requiring a special ultraviolet absorbing adhesive layer even under a severe environment where ultraviolet rays are irradiated for a long time It is an object of the present invention to provide a composition and a PTO conductive film for forming a PTO conductive film which has excellent properties, adhesion to a substrate, and both good conductivity and transparency.

A first aspect of the present invention is a composition for forming a PTO conductive film, comprising PTO particles, a binder resin, and an organic solvent, wherein the composition contains 3 to 45% by mass of the PTO particles in 100% by mass of the composition. 10 to 52 mass% of components other than the PTO particles in 100 mass% of solid content of the product, and the PTO particles have a specific surface area according to BET method of 75 to 110 m ² / g and an L value of 45 or more and 65 or less The binder resin may include ethyl cellulose and a terpene phenol resin having a softening point of 130 to 160 ° C.

  A second aspect of the present invention is the invention based on the first aspect, wherein PTO conductive film formation in which the mass ratio of the ethyl cellulose to the terpene phenol resin is ethyl cellulose: terpene phenol resin = 10 to 80:90 to 20 Composition.

  A third aspect of the present invention is the invention based on the first or second aspect, wherein the composition for forming a PTO conductive film further comprises a dispersing agent in an amount of 3 to 20 parts by mass with respect to 100 parts by mass of the liquid PTO particles. It is.

  A fourth aspect of the present invention is the invention based on any one of the first to third aspects, which is a composition for forming a PTO conductive film used for a screen printing paste or paint.

  A fifth aspect of the present invention is the invention based on the fourth aspect, wherein when used for the screen printing paste, the organic solvent is 3-methoxy-3-methyl-1-butanol, butyl carbitol It is a composition for PTO conductive film formation which consists of a solvent of acetate or alpha-terpineol.

  A sixth aspect of the present invention is the invention based on the fourth aspect, wherein when used in the paint, the organic solvent is 3-methoxy-3-methyl-1-butanol, 2-butanone, 4- 1 type selected from the group consisting of methyl-2-pentanone, ethanol, 2-propanol, 1-butanol, toluene, methanol, 1-propanol, ethyl acetate, butyl acetate, acetone, 2,4-pentanedione and xylene It is a composition for PTO conductive film formation which consists of two or more sorts of solvents.

  A seventh aspect of the present invention is the invention based on any one of the first to sixth aspects, wherein a phenolic antioxidant or a hindered amine light stabilizer is contained in 0% by mass of the solid content of the composition. It is a composition for PTO conductive film formation which further contains .1-5 mass%.

  An eighth aspect of the present invention is the invention based on any one of the first to seventh aspects, wherein the component other than the PTO particles further comprises an organosilicon compound having a hydrolyzable group and water, The content of the silicon compound is 5 to 52% by mass in 100% of the solid content of the composition, and the content of the water is a methoxy group or a hydrolyzable group contained in the organosilicon compound having the hydrolyzable group. It is a composition for PTO conductive film formation which is an ethoxy group and is 0.05 to 0.7 times the number of moles with respect to the number of moles of this hydrolyzable group.

The ninth aspect of the present invention is the invention according to any one of the first to seventh aspects, wherein PTO particles are coated with a hydrolyzate of organosilicon and PTO coated with the hydrolyzate of said organosilicon. PTO conductivity having a specific surface area of 80 to 115 m ² / g according to the BET method of particles, and a coating amount of the hydrolyzate of the organosilicon of 0.5 to 15 parts by mass with respect to 100 parts by mass of PTO particles before coating It is a composition for film formation.

According to a tenth aspect of the present invention, PTO particles having a BET specific surface area of 75 to 110 m ² / g and L values of 45 to 65 are uniformly contained in a terpene phenol resin having a softening point of 130 to 160 ° C. It is a PTO conductive film which is dispersed and which contains 48 to 90% by mass of the PTO particles and 10 to 52% by mass of components other than the PTO particles in the film.

  An eleventh aspect of the present invention is the invention based on the tenth aspect, wherein the phenolic antioxidant or the hindered amine light stabilizer is contained in an amount of 0.1 to 5% in 100% by mass of the solid content of the composition. % PTO conductive film.

A twelfth aspect of the present invention is the invention based on the tenth aspect, wherein the component other than the PTO particles further comprises an organosilicon compound having a hydrolysable group and water, and the content of the organosilicon compound Is 5 to 52% by mass in 100% of the solid content of the composition, and the content of the water is
The PTO conductive film wherein the hydrolyzable group contained in the organosilicon compound having a hydrolyzable group is a methoxy group or an ethoxy group, and the number of moles is 0.05 to 0.7 times the number of moles of this hydrolyzable group It is.

According to a thirteenth aspect of the present invention, there is provided a BET surface method specific surface area of 80 to 115 m ² / g, wherein PTO particles coated with a hydrolyzate of organosilicon have a softening point of 130 to 160 ° C. in a terpene phenol resin And 70 to 90% by mass of the PTO particles coated with the hydrolyzate of the organosilicon in the film, and the components other than the PTO particles coated with the hydrolyzate of the organosilicon in the film It is a PTO conductive film containing 30 mass% and the coating amount of the hydrolyzate of the said organosilicon being 0.5-15 mass parts with respect to 100 mass parts of said PTO particle | grains before coating.

  A fourteenth aspect of the present invention is the invention based on the thirteenth aspect, wherein a phenolic antioxidant or a hindered amine light stabilizer is contained in components other than the PTO particles coated with the organosilicon hydrolyzate. Further included is a PTO conductive film.

  The composition for forming a PTO conductive film according to the first aspect of the present invention contains 3 to 45% by mass of PTO particles having a predetermined specific surface area and L value, and therefore, when the PTO conductive film is formed, it has good conductivity and It can be transparent. Further, by including a terpene phenol resin having a high softening point of 130 to 160 ° C. as a binder resin, when the composition is applied on a substrate, the adhesion of the PTO conductive film to the substrate is excellent, and PTO A change in surface resistivity under high temperature and high humidity of the conductive film is suppressed. Moreover, when the composition is made into the paste for printing, printability can be improved by containing ethyl cellulose.

  In the composition for forming a PTO conductive film according to the second aspect of the present invention, the adhesive effect of the terpene phenol resin is lower if the mass ratio of ethylcellulose is smaller than that of the terpene phenol resin within the predetermined mass ratio range. Since it is easy to express, there is an effect that adhesion to the substrate is enhanced, and conversely, when ethyl cellulose has a larger mass ratio than terpene phenol resin, thickening of the liquid composition with ethyl cellulose can be achieved This has the effect of facilitating the printing and improving the printability as a screen printing paste.

  In the composition for forming a PTO conductive film according to the third aspect of the present invention, the effect of improving the optical characteristics of the film when it is formed into a coating film by containing a predetermined amount of a dispersing agent, that is, the transparency is improved Has the effect of reducing.

  The composition for forming a PTO conductive film of the fourth aspect of the present invention has an advantage of being used for a screen printing paste or paint.

  When used in the screen printing paste of the fifth aspect of the present invention, when 3-methoxy-3-methyl-1-butanol is used as the organic solvent, it is water-soluble while having a relatively high boiling point (174 ° C.) Because of the presence, PTO particles can be easily dispersed, and the optical properties of the coating can be improved. When high-boiling point solvents such as butyl carbitol acetate (247 ° C.) or α-terpineol (219 ° C.) are used in combination, the problem of rapid drying during screen printing when 3-methoxy-3-methyl-1-butanol is used alone It is possible to prevent variations in surface resistivity of the film even in continuous production.

  When used in the paint of the sixth aspect of the present invention, when 3-methoxy-3-methyl-1-butanol is used as the organic solvent, it is water-soluble while having a relatively high boiling point (174 ° C.) The PTO particles can be easily dispersed, and the optical properties of the coating can be improved. Also, low boiling point solvents 2-butanone, 4-methyl-2-pentanone, ethanol, 2-propanol, 1-butanol, toluene, methanol, 1-propanol, ethyl acetate, butyl acetate, acetone, 2,4-pentanedione When one or more solvents selected from the group consisting of and xylene are used in combination, the drying property can be further improved than when 3-methoxy-3-methyl-1-butanol is used alone.

  In the composition for forming a PTO conductive film according to the seventh aspect of the present invention, the surface resistance of the PTO conductive film made from this composition under high temperature can be obtained by further including a phenolic antioxidant or a hindered amine light stabilizer. The change in rate can be further suppressed.

  In the composition for forming a PTO conductive film according to the eighth aspect of the present invention, the hydrolyzable group reacts with water when the composition is heated by further including the organosilicon compound having a hydrolyzable group and water. And some silanol groups are generated. Since the organosilicon compound in which the silanol group is partially generated has a bonding force between the silanol group and PTO, the PTO conductive film made from this composition is further suppressed in the change in surface resistivity under high temperature and high humidity. Ru.

  In the composition for forming a PTO conductive film according to the ninth aspect of the present invention, when PTO particles having a predetermined specific surface area are coated with a predetermined amount of an organosilicon hydrolyzate layer, when made into a PTO conductive film, In the range which does not impair the conductivity which PTO particles originally have, the radical which arises from PTO particles when ultraviolet rays are irradiated is controlled by the covering layer of the above-mentioned hydrolyzate.

  In the PTO conductive film of the tenth aspect of the present invention, PTO particles having a predetermined specific surface area and L value are uniformly dispersed in terpene phenol resin having a high softening point, and other than predetermined amounts of PTO particles and PTO particles By including the component, it is possible to suppress the change in the surface resistivity under high temperature and high humidity of the PTO conductive film, to be excellent in the adhesion to the substrate, and to have both the good conductivity and the transparency.

  In the PTO conductive film of the eleventh aspect and the fourteenth aspect of the present invention, the change in surface resistivity of the PTO conductive film at high temperatures is further suppressed by further including a phenolic antioxidant or a hindered amine light stabilizer. can do.

  In the PTO conductive film of the twelfth aspect of the present invention, the change in surface resistivity of the PTO conductive film under high temperature and high temperature can be further suppressed by further including the organosilicon compound having a hydrolyzable group and water. .

  In the PTO conductive film according to the thirteenth aspect of the present invention, PTO particles having a predetermined specific surface area are coated with a predetermined amount of an organosilicon hydrolyzate, uniformly dispersed in terpene phenol resin having a high softening point, and By containing a predetermined amount of PTO particles and components other than PTO particles, when ultraviolet light is incident on the PTO conductive film, a decrease in surface resistivity can be suppressed, and light resistance is excellent, and adhesion to a substrate is excellent. It is possible to combine good conductivity and transparency.

  Next, a first embodiment of the present invention will be described.

[PTO particles of the first embodiment]
The PTO particles of the first aspect of the present invention have a BET specific surface area of 75 to 110 m ² / g and an L value of 45 or more and 65 or less. When the specific surface area according to the BET method is less than 75 m ² / g, the haze becomes high when the PTO conductive film having a desired surface resistivity is obtained, and the transparency of the film becomes low. If the content of PTO particles of the first form in the film is reduced to lower the haze, the desired surface resistivity of the film can not be obtained and the conductivity of the film is degraded. Normally, when the BET value is high, the particles become small, and thus it is possible to reduce the transparency and the haze, but when the specific surface area by the BET method exceeds 110 m ² / g, a predetermined dispersant When PTO particles of the first form are mixed with the resin at an addition amount of 1, the dispersion of the PTO particles in the resin becomes insufficient, and there is a problem that the haze of the coating film becomes worse. When the first form of PTO particles exceeding 110 m ² / g is used to reduce the haze so as not to cause this problem, it is necessary to increase the amount of dispersant for dispersing the PTO particles in the resin. It occurs. When the amount of the dispersant is increased, the conductivity of the film is deteriorated, and problems such as the adhesion to the substrate are deteriorated. For this reason, the upper limit value of the specific surface area according to the BET method of the PTO particles of the first embodiment is determined to be 110 m ² / g. When the content of the PTO particles in the film is increased to obtain a desired surface resistivity, when the composition for forming a PTO conductive film of the first embodiment is applied onto a substrate, the PTO conductive film group is obtained. Adhesion to the material is poor. When the L value of the PTO particles of the first embodiment exceeds 65, the reduction of the PTO is insufficient, so the surface resistivity of the film becomes high and the conductivity of the film becomes worse. If the L value is less than 45, the particles become large, so that the haze of the film becomes high and the transparency of the film becomes low.

[Method of producing PTO particles of the first embodiment]
The first form of PTO particles is obtained by coprecipitating phosphorus and tin hydroxides and calcining the same in a method for producing phosphorus-doped tin oxide particles by calcining coprecipitated hydroxides of phosphorus and tin. Be

Specifically, PTO particles of the first form are produced in the following manner. First, a tin salt and a phosphorus salt are weighed and mixed in a predetermined ratio, the mixture is dissolved in pure water to form a mixed solution of a tin salt and a phosphorus salt, and the mixed solution is reacted with an alkali. Phosphorus and tin in the solution precipitate in the presence of alkali to form a coprecipitated hydroxide of phosphorus and tin. Salts of tin include hydrochloride, sulfate or nitrate. For example, divalent tin compound as a tin salt (such as SnCl ₂ · 2H ₂ O), using phosphoric acid _(H 3 PO ₄₎ as the phosphorus salt, the pH of the solution from 4.0 to 9.3, preferably pH 5. The liquid temperature is adjusted to 5 ° C. or higher, preferably to a liquid temperature of 10 ° C. to 80 ° C. Thereby, the coprecipitated hydroxide of phosphorus and tin can be precipitated.

In order to adjust the pH of the reaction to pH 4.0 to 9.3, for example, using a mixed aqueous solution of phosphoric acid (H ₃ PO ₄ ) and tin tetrachloride (SnCl ₄ ), this mixed aqueous solution and an aqueous alkaline solution At the same time, and adjusted to the above pH range. As the alkaline aqueous solution, ammonia water [NH ₃ water], ammonium hydrogencarbonate water [NH ₄ HCO ₃ water], sodium hydroxide water [NaOH water], potassium hydroxide solution [KOH water] or the like may be used.

  After the coprecipitated phosphorus tin hydroxide is formed, the coprecipitate is washed with pure water, and washed until the electric conductivity of the supernatant liquid becomes 500 μS / cm or less, preferably 50 μS / cm or less (hereinafter referred to as “tilting” After washing, the solid solution is separated to recover the coprecipitate. When the electric conductivity of the supernatant is higher than 500 μS / cm, impurities such as chlorine are not sufficiently removed, and it is not possible to obtain highly pure phosphorus-doped tin oxide particles.

The above phosphorus-doped tin hydroxide can be produced in the first form by the following three methods.
(a-1) In the first method, first, the phosphorus tin hydroxide solid-liquid separated is dried at 100 to 120 ° C. overnight in a nitrogen gas atmosphere, and then at 270 to 800 ° C. for 30 minutes to 6 Bake in nitrogen atmosphere for time.
(b) In the second method, first, the phosphorus tin hydroxide solid-liquid separated is dried overnight at 100 to 120 ° C. in the atmosphere, then at 270 to 800 ° C. for 30 minutes to 6 hours. Baking in an atmosphere. Next, the oxide obtained by firing is put into a surface treatment solution of alcohol and impregnated, and then the surface is reformed by heating at 150 to 600 ° C. in a nitrogen gas atmosphere.
(c) In the third method, first, the phosphorus tin hydroxide solid-liquid separated is dried overnight at 100 to 120 ° C. in the atmosphere, then at 270 to 800 ° C. for 30 minutes to 6 hours. Baking in.

The aggregates obtained by the above three methods are all crushed and loosened to form phosphorus-doped tin oxide. The PTO particles of the first embodiment thus obtained have a BET specific surface area of 75 to 110 m ² / g and a pale gray gray color having an L value of 45 or more and 65 or less, a <1, b <0 in the Lab colorimetric system. It has a tinted tint. Since the PTO particles are fine, high transparency can be obtained when they are mixed with a resin to form a film or a sheet.

If the calcination temperature is less than 270 ° C., it remains as a hydroxide and does not form an oxide. When the firing temperature exceeds 800 ° C., the PTO particles are sintered to each other, so the specific surface area becomes less than 75 m ² / g.

[Method of Producing Composition for Forming PTO Conductive Film of First Embodiment]
The PTO particles of the first form obtained by the above method are mixed with a binder resin and an organic solvent to prepare a composition for forming a PTO conductive film of the first form. At this time, a dispersant may be mixed. By mixing the dispersant, the transparency of the coating film is further improved. This composition contains the first form PTO particles in an amount of 3 to 45% by mass, preferably 4 to 40% by mass in 100% by mass of the composition, and the first form in 100% by mass of its solid content And 10 to 52% by mass, preferably 15 to 35% by mass, of components other than PTO particles of If the content of the PTO particles of the first form obtained by the above method is less than 3% by mass, the conductivity of the PTO conductive film of the first form produced from this composition does not increase. When the content exceeds 45% by mass, the stability with the passage of time becomes worse, such as thickening of the composition, the binder resin is relatively deficient, and the adhesion between particles of PTO particles of the first embodiment decreases. The surface resistivity of the PTO conductive film of the embodiment 1 is deteriorated. Further, if the component other than the PTO particles of the first form is less than 10% by mass, the increase in surface resistivity under high temperature and high humidity of the PTO conductive film of the first form can not be suppressed, and the adhesion to the substrate is sufficient. Can not get On the other hand, if it exceeds 52% by mass, the stability with the passage of time becomes worse, for example, the composition becomes thick, and the surface resistivity of the PTO conductive film of the first embodiment becomes worse, making it difficult to obtain conductivity.

  As binder resin of the 1st form which is solid content of this composition, ethyl cellulose and terpene phenol resin which has a softening point of 130-160 degreeC are included. If the softening point of the terpene phenol resin is less than 130 ° C., it becomes difficult to suppress the change in the surface resistivity when the use condition of the PTO conductive film of the first embodiment becomes a high temperature of 60 ° C. or more. In addition, terpene phenol resins exceeding 160 ° C. are difficult to obtain. The mass ratio of ethyl cellulose to terpene phenol resin is preferably ethyl cellulose: terpene phenol resin = 10 to 80:90 to 20, and more preferably 20 to 50:80 to 50. If the mass ratio of ethyl cellulose is less than 10 and the mass ratio of terpene phenol resin exceeds 90, it is difficult to increase the viscosity of the paste during screen printing, and there is a problem that the screen printability is deteriorated. When the mass ratio of the terpene phenol resin is less than 20, the adhesion of the PTO conductive film of the first embodiment to the base material may be reduced. Terpene phenolic resin is Sylvares TP7042 (softening point: 145 ° C.) manufactured by Arizona Chemical Co., Tamanor 803 L (softening point: 140-160 ° C.) manufactured by Arakawa Chemical Industries, Ltd., 901 (softening point: 120-135 ° C.), YS manufactured by Yasuhara Chemical Co., Ltd. Polystar T160 (softening point: 160 ° C), T145 (softening point: 145 ° C), T130 (softening point: 130 ° C), U130 (softening point: 130 ° C), S145 (softening point: 145 ° C), G150 (softening point) 150 ° C., K 140 (softening point: 140 ° C.), TH 130 (softening point: 130 ° C.), and the like.

  The dispersant of the first form contained in the composition for forming a PTO conductive film of the first form is preferably contained in an amount of 3 to 20 parts by mass with respect to 100 parts by mass of the PTO particles of the first form. As an example of the dispersant of the first embodiment, any pigment dispersant can be used as long as the pigment can be stably dispersed in fine particles. Specifically, polyoxyethylene styrenated phenyl ether ammonium sulfate, sodium polyoxyalkylene decyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, polyoxyethylene isodecyl ether ammonium sulfate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene Alkyl ether sulfates such as ammonium lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene oleyl cetyl ether sulfate, polyoxyethylene oleyl cetyl ether sodium sulfate, alkyl sulfate ester salt, alkyl benzene sulfonate, alkyl phthalene sulfonic acid Salt, polyoxyethylene alkyl ether phosphate ester, polycarbonate Alkyl phosphoric acids such as ethylene alkyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene tridecyl ether phosphate, polyoxyethylene styrenated phenyl ether phosphate Ester salts, polyoxyethylene alkyl ether acetates, alkyl ether acetates such as sodium polyoxyethylene lauryl ether acetate, disodium lauryl sulfosuccinate polyoxyethylene alkyl sulfosuccinate disodium, polyoxyethylene sulfosodium dilaurate, sodium polyoxyethylene sulfosuccinate Alkyl succinates such as ethylene alkyl sulfosuccinate, anionic surfactants such as polycarboxylic acid type polymers, amine oxide Cationic surfactants, polyoxyethylene block copolymers, surfactants, such as non-ionic surfactants such as polyoxyethylene alkyl amides. When the content of the dispersant is less than 1 part by mass, the dispersion of the composition for forming a PTO conductive film of the first embodiment is insufficient, and the transparency of the coating film tends to be insufficient. If it exceeds 15 parts by mass, the conductivity of the PTO conductive film of the first embodiment and the adhesion of the coating film are likely to be adversely affected.

  As the organic solvent of the first form contained in the composition for forming a PTO conductive film of the first form, 3-methoxy-3-methyl-1-butanol is used as the organic solvent. Since 3-methoxy-3-methyl-1-butanol is water-soluble while having a relatively high boiling point, it is easy to disperse the PTO particles of the first form, and it is possible to improve the optical properties of the coating. It is possible to However, when the composition for forming a PTO conductive film of the first embodiment is a paste for screen printing, if the 3-methoxy-3-methyl-1-butanol alone is used, the drying speed is fast, so many films are formed. Then, since a problem arises in the uniformity of the surface resistivity of the film, high boiling point solvents such as butyl carbitol acetate or α-terpineol are used in combination. In the case where the composition for forming a PTO conductive film of the first embodiment is a paint, quick drying is required, so 2-butanone, 4-methyl-2-pentanone, ethanol, 2-propanol, 1-butanol having a low boiling point. Toluene, methanol, 1-propanol, ethyl acetate, butyl acetate, acetone, 2,4-pentanedione, xylene etc. and 3-methoxy-3-methyl-1-butanol are used in combination.

  The amount of the organic solvent added is preferably 50 to 95% by mass in 100% by mass of the composition. When the amount of the organic solvent added is large, the composition becomes a composition for paint, and when the amount is small, it becomes a composition for paste.

  The composition for forming a PTO conductive film according to the first aspect preferably further comprises a phenolic antioxidant or a hindered amine light stabilizer. As a phenolic antioxidant, ADEKA company, product name AO-20, AO-30, AO-40, AO-60, AO-80 etc. are mentioned. Moreover, as a hindered amine light stabilizer, ADEKA, product name LA-52, LA-57, LA-63, LA-72 etc. are mentioned. By further including a phenolic antioxidant or a hindered amine light stabilizer, it is possible to further suppress the change in surface resistivity of the PTO conductive film made from this composition under high temperature. For this reason, it is preferable that the addition amount of a phenolic antioxidant or a hindered amine light stabilizer is 0.1-5 mass% in 100 mass% of solid content of a composition.

  More preferably, the composition for forming a PTO conductive film according to the first aspect further comprises an organosilicon compound having a hydrolyzable group and water. When an organosilicon compound having a hydrolyzable group is added alone, the change in surface resistivity after a predetermined time in a high temperature and high humidity condition becomes larger, but by adding water, a high temperature and high humidity can be obtained. It is possible to suppress a change in surface resistivity after a predetermined time has elapsed and to further improve the adhesion to the substrate. As an organosilicon compound having a hydrolyzable group, vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name KBM-1003), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., product name KBM-403), 3-Methacryloxypropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., Product Name KBM-503), 3-Mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., Product Name KBM-803), Methyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) , Product name KBE-13) and the like. Moreover, water is added to the organosilicon compound which has a hydrolysable group beforehand, The silane compound (Mitsubishi Materials Electronic Chemicals Co., Ltd. product name SB-10A) etc. which hydrolytically polymerized the organosilicon compound are mentioned.

  In the components other than the PTO particles, by further including an organosilicon compound having a hydrolyzable group and water, the change in surface resistivity of the PTO conductive film made from this composition under high temperature and high humidity is further suppressed Can. For this reason, it is preferable that the addition amount of the organosilicon compound which has a hydrolysable group is 5-52 mass% in 100 mass of solid content of a composition. The amount of water added is, for example, a methoxy group or an ethoxy group and the hydrolyzable group contained in the organosilicon compound having a hydrolyzable group is 0.05 to 0.7 times the molar amount of the hydrolyzable group. Preferably it is a number. If the number is less than 0.05 times the number of moles, hydrolysis is insufficient and it becomes difficult to suppress the temporal change of the surface resistivity. On the other hand, when the number of moles exceeds 0.7, the surface resistivity of the film increases and the haze tends to increase. Also, if an organic solvent incompatible with water is selected to add water, the haze will increase more, so a solvent compatible with water such as 3-methoxy-3-methyl-1-butanol Can be used to reduce the increase in haze.

  In the preparation procedure of the composition for forming a PTO conductive film of the first embodiment, first, the PTO particles of the first embodiment are added to the organic solvent, and the dispersant is used in the organic solvent in which the dispersant is dissolved. PTO particles in the form 1 are added, and the PTO particles are dispersed using a wet bead mill or the like until the particle diameter of the dispersed PTO particles reaches a desired particle diameter to prepare a PTO dispersion. The dispersion concentration is not limited, but is 10 to 75% by mass as PTO. When the content is less than 10% by mass, productivity is poor, and when a resin solution or the like is mixed at the time of paste production in the subsequent step, it becomes impossible to produce a paste of high concentration. Moreover, when it exceeds 75 mass%, it will become difficult to disperse | distribute PTO particle | grains and productivity will worsen. On the other hand, the binder resin is mixed with the organic solvent in which the PTO particles are dispersed or in another organic solvent and mixed, and the organic solvent is heated at a temperature of 40 to 80 ° C. to dissolve the binder resin. Prepare a resin solution. Finally, the resin solution, the PTO dispersion, a phenolic antioxidant, a hindered amine light stabilizer or an organosilicon compound having a hydrolyzable group and an additive such as water are mixed, and this mixture is subjected to a rotation and revolution mixer, 2 bottles The first form is obtained by stirring, kneading, and dispersing in a heated state at a temperature of 40 to 80 ° C. with an apparatus such as a roll, planetary mixer, ball mill, homogenizer, ultrasonic disperser, three-roll, Henschel mixer, etc. A composition for forming a PTO conductive film is obtained.

  Next, a second embodiment of the present invention will be described.

[PTO particles of the second embodiment]
The PTO particles of the second aspect of the present invention are produced by coating the PTO particles of the first aspect described above with a hydrolyzate of organosilicon. Against PTO particles of the first aspect of the present invention as described above have a specific surface area by the BET method of 75~110m ² / g, PTO particles of the second embodiment, 80~115m ² / g Preferably, it has a BET specific surface area of 85 to 110 m ² / g. When the specific surface area by BET method is less than 80 m ² / g, there is a problem that the haze at the time of forming a conductive film becomes high. When the specific surface area by the BET method exceeds 115 m ² / g, there is a problem that the change in surface resistivity can not be improved with respect to ultraviolet irradiation. In the PTO particles of the second embodiment, the coating amount of the hydrolyzate of organosilicon is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the PTO particles before coating. If the coating amount is less than 0.5 parts by mass, photodegradation of the PTO conductive film upon irradiation with ultraviolet light can not be prevented, and if it exceeds 15 parts by mass, the conductivity of the PTO conductive film is lost. The isoelectric point of PTO particles before coating is around pH 7 and the isoelectric point of PTO particles after coating is around pH 2. Moreover, the volume resistivity of PTO particle | grains before coating is 5 ohm-cm or less, and the volume resistivity of PTO particle | grains after coating is 100-50000 ohm-cm.

[Method of producing PTO particles of the second embodiment]
The second form of PTO particles can be produced by the following three methods.
(A-2) The silica sol-gel solution, which is a hydrolyzate of organosilicon, is impregnated with the PTO particles of the first embodiment described above. The PTO particles impregnated in the silica sol-gel solution are dried, and the dried product is crushed to obtain PTO particles coated with an organosilicon hydrolyzate. In this method, the coating amount of the hydrolyzate of organosilicon per 100 parts by mass of PTO particles before coating is adjusted by adjusting the ratio of the mass of silica in the silica sol-gel solution to the mass of PTO particles to be impregnated. Adjusted to parts by mass.
(B-2) While stirring the PTO particles of the first embodiment described above with a dry stirrer, a silica sol-gel solution, which is a hydrolyzate of organosilicon, is sprayed. The PTO particles sprayed with the silica sol-gel solution are dried, and the dried product is crushed to obtain PTO particles coated with an organosilicon hydrolyzate. In this method, the coated amount of the organosilicon hydrolyzate to 100 parts by mass of PTO particles before coating is adjusted by adjusting the ratio of the mass of silica in the silica sol-gel liquid to be sprayed and the mass of PTO particles to be impregnated. Adjusted to 15 parts by mass.
(C-2) The silicon alkoxide is heated to generate a vapor, and the vapor is brought into contact with the PTO particles of the first embodiment described above for a predetermined time. The vapor-contacted PTO particles are dried, and the dried product is pulverized to obtain organosilicon hydrolyzate-coated PTO particles. In this method, the coating amount of the hydrolyzate of organosilicon per 100 parts by mass of PTO particles before coating is controlled by adjusting the temperature at which the silicon alkoxide is heated (the evaporation amount of silicon alkoxide) and the time for contacting the PTO particles. It is adjusted to 0.5 to 15 parts by mass.

  The drying in the methods (a-2) to (c-2) is performed in the air or in a nitrogen atmosphere. When drying is performed in the atmosphere, the drying temperature is set in the range of 150 to 200 ° C. When the temperature exceeds 200 ° C., the PTO particles are oxidized, and when the PTO conductive film is formed, the conductive film becomes yellowish, which is not preferable. When the temperature is less than 150 ° C., the light resistance of the PTO conductive film when the PTO conductive film is formed is deteriorated. When drying is performed under a nitrogen atmosphere, the drying temperature is set in the range of 150 to 700 ° C. When the temperature exceeds 700 ° C., the haze of the conductive film becomes high when the PTO conductive film is formed, and the transparency of the conductive film is inferior. When the temperature is less than 150 ° C., the light resistance of the PTO conductive film when the PTO conductive film is formed is deteriorated.

  The hydrolyzate of organosilicon used in the above methods (a-2) and (b-2) can be produced by using an alcohol solution such as tetramethoxysilane or tetraethoxysilane, tetrabutoxysilane, silicon alkoxide such as tetraacetoxysilane, etc. The mixture is prepared by adding a mixture of nitric acid and, if necessary, an organic solvent of glycol ether, heating and stirring. Tetramethoxysilane or tetraethoxysilane, tetrabutoxysilane, tetraacetoxysilane or the like is preferable because when it is used as a conductive film, the resistance change of the conductive film with respect to ultraviolet light is small. Specifically, the hydrolyzate of this organosilicon is, first, ethanol or isopropanol in an amount of 1.0 to 100.0 parts by mass with respect to 1 part by mass of tetramethoxysilane or tetraethoxysilane as a silicon alkoxide. An organic solvent such as (IPA) or propylene glycol monomethyl ether (PGME) is added, and the first solution is prepared by stirring for preferably 5 to 20 minutes at a temperature of 30 to 40 ° C. On the other hand, separately from this first solution, 0.5 to 5.0 parts by mass of water and 0.005 to 1.0 parts by mass of nitric acid are added to 1 part by mass of the silicon alkoxide, The second solution is prepared by stirring for 5 to 20 minutes at a temperature of -40 ° C. Next, the above prepared first solution is maintained at a temperature of preferably 30 to 80 ° C. using a water bath or the like, and then the second solution is added to the first solution, and preferably the above temperature is maintained. Stir for 30 to 180 minutes. Thereby, the hydrolyzate of the said silicon alkoxide is prepared.

[Method of producing composition for forming PTO conductive film of second embodiment]
The PTO particles of the second aspect obtained by the above method are mixed with the binder resin of the first aspect and the organic solvent of the first aspect to prepare a composition for forming a PTO conductive film of the second aspect. . This preparation method is the same as the preparation method of the composition for forming a PTO conductive film of the first embodiment except that the PTO particles of the second embodiment are used, and therefore the repeated description is omitted.

[Method of forming PTO conductive film]
The PTO conductive film can be obtained by, for example, screen printing the composition for forming a PTO conductive film of the first form or the second form obtained above on a film such as polyethylene terephthalate (PET) as a base material, a bar It forms by making it dry at the temperature of 80-130 degreeC, after apply | coating by a coating method, the die-coating method, a doctor blade, a spin method, etc.

  Next, an example of the present invention will be described in detail along with a comparative example.

[Production of PTO particles of five types of the first form]
A phosphoric acid aqueous solution and tin tetrachloride are mixed, and this mixed aqueous solution and an ammonia aqueous solution are simultaneously added dropwise to water to adjust the pH for reaction. The formed precipitate was repeatedly subjected to inclined washing with ion exchange water. When the electric conductivity of the supernatant liquid became 20 μS / cm or less, the precipitate (P / Sn coprecipitated hydroxide) was separated by filtration to obtain coprecipitated phosphorus tin hydroxide. The solid-liquid separated phosphorus tin hydroxide is surface-modified by the above-described first to third methods, and as shown in Table 1, the first of five types (No. 1 to No. 5) Formed PTO particles were obtained.

For example, No. 1 PTO particles were produced by the following method. First, 100 mL of a phosphoric acid (H ₃ PO ₄ ) aqueous solution (containing 0.7 g of P) as a raw material and 55 g of tin tetrachloride (SnCl ₄ ) as a raw material are mixed, this mixed aqueous solution and an aqueous solution of sodium hydroxide (NaOH) The solution was simultaneously added dropwise to 1000 ml, adjusted to pH 7, and reacted at a liquid temperature of 50 ° C. for 30 minutes. Then, the formed precipitate was repeatedly subjected to inclined washing with ion exchange water. When the electric conductivity of the supernatant liquid became 50 μS / cm or less, the precipitate (P / Sn coprecipitated hydroxide) was separated by filtration to obtain coprecipitated phosphorus tin hydroxide. The solid-liquid separated phosphorus tin hydroxide was dried at 110 ° C. overnight, and then baked in nitrogen at 780 ° C. for 3 hours, and the aggregate was crushed and loosened to obtain about 25 g of PTO particles.

  According to the method for producing No. 1 PTO particles, PTO particles of No. 2 to No. 5 are obtained by changing the raw material, the pH at the time of reaction, the temperature at the time of reaction, and the temperature which is the firing conditions. The The specific surface area and L value of the five types of PTO particles of No. 1 to No. 5 obtained were measured by the BET method.

  The specific surface area of five types of PTO particles of the first form No. 1 to No. 5 according to the BET method is measured using an apparatus (SA-1100) manufactured by Shibata Scientific Co., Ltd. L value is a color of Suga Test Instruments It measured using the computer (SM-T). These measurement results are also shown in Table 1.

Preparation of 9 Types of First Forms of PTO Dispersion
As shown in Table 2, any one of the five types of PTO particles of the first form of No. 1 to No. 5 and a dispersant consisting of polyoxyethylene alkyl ether phosphate were added to three kinds of organic solvents. The resultant was dispersed by a wet bead mill to prepare nine PTO dispersions of A to I. In Table 2, MMB means 3-methoxy-3-methyl-1-butanol.

Preparation of Resin Solutions of Eight Different First Forms
As shown in Table 3, three types of organic solvents are prepared, and ethyl cellulose and terpene phenol resin as binder resins are respectively added to the above organic solvents and mixed, and this is heated at a temperature of 60 ° C. to obtain a binder The resin was dissolved to prepare eight first-form resin solutions. Terpene phenol resin used the thing of the product number made by Yashara Chemical Co., Ltd. mentioned above. In Table 3, MMB means 3-methoxy-3-methyl-1-butanol, BCA means butyl carbitol acetate, and α-T means α-terpineol.

Preparation of Composition for Forming PTO Conductive Film of First Embodiment of Examples 1 to 8 and Comparative Examples 1 to 5
As shown in Table 4, after diluting each of the eight types of resin solutions of the first form with a diluting solution to make a 25% by mass resin solution, a predetermined resin solution is selected from among them, and nine types of resin solutions are selected. A predetermined PTO dispersion is selected from among the PTO dispersions, and the selected resin solution and the selected PTO dispersion consist of a phenolic antioxidant, a hindered amine light stabilizer, an organosilicon compound having a hydrolysable group, and water The additive was mixed and stirred and dispersed by a rotation revolution mixer to prepare a composition for forming a PTO conductive film of the first embodiment of Examples 1 to 8 and Comparative Examples 1 to 5. "BCA" shown in Table 4 is butyl carbitol acetate and "EtOH" is ethanol. Moreover, in Table 4, Examples 7 and 8 are respectively shown as an example of the composition for PTO conductive film formation containing the organosilicon compound which has a hydrolysable group. The "molar ratio" shown in Table 4 represents the ratio of the number of moles of water to the number of moles of hydrolyzable groups contained in the organosilicon compound as a molar ratio.

[Percentage of Solid Content of First Form in Composition of Example and Comparative Example, Percentage of Non-PTO Particles and PTO Particles]
The ratio of the solid content of the first form in the composition of Examples 1 to 8 and Comparative Examples 1 to 5 from Table 4 and the ratio other than PTO particles and PTO particles are summarized. These percentages are shown in Table 5.

[Proportion of PTO particles and PTO particles other than PTO particles in composition of Examples and Comparative Examples, Physical properties of PTO particles, Ratio of binder resin, and dispersant]
From Table 4, the proportions other than PTO particles and PTO particles in the composition of Examples 1 to 8 and Comparative Examples 1 to 5, the physical properties of PTO particles, the proportions of the binder resin and the dispersant were summarized. These percentages are shown in Table 6.

[Formation of PTO conductive film of the first embodiment and evaluation of printability]
The PTO conductive film of the first form was formed on the substrate for each composition from the 13 compositions of the PTO conductive film formation of the first form obtained in Examples 1 to 8 and Comparative Examples 1 to 5 . Specifically, using a screen printer (Mitani Micronix Co., Ltd., Model No. MEC-2400), these compositions are 40 mm × 40 mm on a film substrate of polyethylene terephthalate (PET) and on a glass of 1 mm thickness Each printed on the size of. After printing, 13 kinds of PTO conductive films were obtained by drying at 130 ° C. for 5 minutes in the air atmosphere. The printability at this time was evaluated. The evaluation of the printability was visually judged by the above-mentioned screen printing machine, the degree of bleeding after printing and the degree of clogging of the screen when printing. Those that did not cause bleeding after printing and clogging of the screen were regarded as “good”, those causing bleeding after printing were regarded as “slightly poor”, and those causing clogging of the screen were considered “defective”. The results are shown in Table 7.

[Evaluation of PTO conductive film of the first embodiment]
The evaluation test of the following items was done about the PTO conductive film of 13 types of 1st forms formed by the said method.

(1) Adhesion to substrate The adhesion to the substrate was examined for the PTO conductive film on the film substrate by the cross-cut method (in accordance with JIS K5600-5-6). In the adhesion test, among the 100 grids, the number of squares remaining without peeling after the test is shown as a molecule, and the adhesion is evaluated. Specifically, when 100 squares are all left, it is represented by 100/100, and when 20 squares are peeled off and 80 squares are left, it is represented by 80/100. These results are shown in Table 7.

(2) Transparency The film formed on the glass substrate was measured for total light transmittance and haze using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model number HZ-2), and the transparency of the PTO conductive film was measured. In addition, the total light transmittance described in the table is a numerical value including the base material, the total light transmittance of the base material alone is 89%, and the same haze is 0.03%. These results are shown in Table 7.

(3) Conductivity and change in surface resistivity under high temperature and high humidity The surface resistivity of the PTO conductive film immediately after being prepared on a glass substrate using Hiresta made by Mitsubishi Chemical Analytech (model: MCP-HT450) Resistivity was measured to evaluate the conductivity. Then, after storing in a room adjusted to 85 ° C. for 24 hours as a heat resistance test, the rate of change of surface resistivity at the same place as the place where the initial resistivity was measured was determined based on the following equation.
Rate of change (%) = [(surface resistivity after heating-initial surface resistivity) / initial surface resistivity] × 100
After storing for 24 hours in a room adjusted to a temperature of 60 ° C and a relative humidity of 90% as a humidity resistance test, the surface resistivity of the same place as the place where the initial resistivity was measured is measured, and the change rate is expressed by the following equation It asked based on.
Rate of change (%) = [(Surface resistivity after humidification-initial surface resistivity) / initial surface resistivity] × 100
The results are shown in Table 8.

(4) Composition analysis of PTO conductive film The composition of the PTO conductive film was analyzed by preparing a paint of the component except PTO, forming a paint on glass, and measuring it by FT-IR made by Horiba, Ltd. First, a solution from which PTO was removed was prepared from the composition of Example 1, and the FT-IR of this solution was measured. Next, this solution was formed into a film on glass by screen printing, and FT-IR of the film from which the solvent was removed was measured. It was confirmed that the peak ratio of ethyl cellulose and terpene phenol resin of the solution and the film was the same, and it could be confirmed that the composition of the feed and the composition of the film were the same.

  As is clear from Tables 7 and 8, in Comparative Example 1, the adhesion to the substrate of the PTO conductive film was very poor because it did not contain the terpene phenol resin. Since the concentration of the PTO dispersion was as low as 2% by mass, the screen printability of the composition was inferior. In addition, since the ratio of PTO to PTO particles in the PTO dispersion was 40% by mass, the initial surface resistivity of the PTO conductive film was very large and inferior in conductivity.

  In Comparative Example 2, the solid content concentration was 25%, but the PTO concentration in the solid content was 50% and the ratio of PTO was low, so the initial surface resistivity was very large and the conductivity was inferior. Moreover, since it did not contain ethyl cellulose, it was inferior in screen printability.

  In Comparative Example 3, since the softening point of the terpene phenol resin is 110 ° C. lower, the change in the surface resistivity after the heat resistance test is worse than the other ones. In addition, the surface resistivity was poor because the amount of dispersant was large relative to PTO particles.

In Comparative Examples 4 and 5, since the specific surface area of the PTO particles was as low as 70 m ² / g, the haze of the PTO conductive film was a little large and the transparency was inferior.

On the other hand, the compositions of Examples 1 to 8 are screen compositions because they are compositions comprising ethyl cellulose capable of increasing the viscosity and a high boiling point solvent of butyl carbitol acetate or α-terpineol. Excellent. Furthermore, in 100% by mass of the paste composition, 3 to 45% by mass of PTO particles are contained, and 10 to 52 parts by mass of components other than the PTO particles with respect to 100 parts by mass of solid content of the composition BET specific surface area of 75 to 110 m ² / g and L value of 45 to 65, and the binder resin comprises a terpene phenol resin having a softening point of 130 to 160 ° C., and the ethyl cellulose and the terpene phenol resin The mass ratio is ethyl cellulose: terpene phenol resin = 10 to 80: 90 to 20, and the dispersing agent is filled in 3 to 20 parts by mass with respect to 100 parts by mass of the liquid PTO particles, the substrate of the PTO conductive film Adhesion to the film, transparency, conductivity, heat and moisture resistance was excellent. In particular, the composition of Example 6 was able to improve the heat resistance by containing the phenolic antioxidant. Moreover, the composition of Examples 7-8 was able to aim at the further improvement of moisture resistance and adhesiveness because the organosilicon compound containing a hydrolyzable group and water were included.

[Production of Six Different Second Forms of PTO Particles]
PTO particles (hereinafter referred to as coated PTO particles) coated with hydrolysates of six types of organosilicons were all produced by the method of (a-2) described above (No. 6 to No. 11).

Coated PTO particles of No. 6: 1.7 g of tetraethoxysilane (0.5 parts by mass relative to PTO particles in terms of SiO ₂ equivalent) and 130 g of ethanol were stirred and mixed at 25 ° C., 0.1 g of nitric acid, water 3. A liquid obtained by stirring and mixing 4 g at 25 ° C. was added and the mixture was heated and stirred at a temperature of 60 ° C. for 1 hour. To the above solution cooled to room temperature, 100 g of PTO particles were added, and after stirring and mixing for 1 hour, the liquid in the slurry was heated and evaporated. This gave No. 6 coated PTO particles.

No. 7 coated PTO particles: 7.6 g of tetramethoxysilane (3.0 parts by mass relative to PTO particles in terms of SiO ₂ equivalent), 50 g of ethanol are stirred and mixed at 25 ° C., 0.1 g of nitric acid, water 7. A liquid obtained by stirring and mixing 6 g at 25 ° C. was added and the mixture was heated and stirred at a temperature of 60 ° C. for 1 hour. While stirring 100 g of PTO particles with a stirrer, the whole amount of the above solution was added while being dropped little by little. After recovery, the liquid was heated and evaporated. This gave No. 7 coated PTO particles.

No. 8 coated PTO particles: 37.4 g (7.0 parts by mass relative to PTO particles in terms of SiO ₂ equivalent) of tetrabutoxysilane, 120 g of ethanol, 3.0 g of nitric acid, and 15.0 parts of water The coated PTO particles of No. 8 were obtained in the same manner as in the method of preparing the coated PTO particles of 17.

No. 9 coated PTO particles: 34.7 g of tetraethoxysilane (10.0 parts by mass relative to PTO particles in terms of SiO ₂ equivalent), 150 g of ethanol, 3.0 g of nitric acid, 18.0 parts of water, No. The coated PTO particles of No. 9 were obtained in the same manner as in the method of preparing the coated PTO particles of 17.

Coated PTO particles of No. 10: 29.4 g (15.0 parts by mass relative to PTO particles in terms of SiO ₂ equivalent) of 3- to 5-mer of tetraethoxysilane, 150 g of ethanol, 3.0 g of nitric acid, water 18. At 0, a coated PTO particle of No. 10 was obtained in the same manner as in the method of producing a coated PTO particle of No. 17.

No. 11 coated PTO particles: 39.2 g (20.0 parts by mass relative to PTO particles in terms of SiO ₂ equivalent) of 3- to 5-mer of tetraethoxysilane, 150 g of ethanol, 3.0 g of nitric acid, water 18. At 0, the coated PTO particles of No. 11 were obtained in the same manner as in the method of preparing the coated PTO particles of No. 17.

  The coated PTO particles of No. 6 to No. 11 obtained by the above method were dried for 4 hours under the atmosphere and temperature shown in Table 9 respectively. The specific surface area of the obtained coated PTO particles by BET method was measured using an apparatus (SA-1100) manufactured by Shibata Scientific Co., Ltd. The measurement results are shown in Table 9. Moreover, the amount of Si in the obtained coated PTO particles was measured by ICP, and it was confirmed that it was the same as the preparation value.

Preparation of PTO Dispersions of Six Second Forms
As shown in Table 10, the organic solvent 3-methoxy-3-methyl-1-butanol (MMB) and any one of the coated second form PTO particles of the above-mentioned No. 6 to No. 11 and poly A dispersant consisting of oxyethylene alkyl ether phosphate was added and dispersed by a wet bead mill to prepare six PTO dispersions of J to O.

[Preparation of PTO conductive film forming compositions of the second embodiment of Examples 9 to 14 and Comparative Example 6]
The resin solution d of the first embodiment, the dispersion liquid of the above six types of the second embodiment, and butyl carbitol acetate (BCA) as a dilution medium are mixed in the proportions shown in Table 11, and the mixture is stirred by an autorotational revolution mixer. By dispersing, the compositions for forming a PTO conductive film of the second forms of Examples 9 to 14 and Comparative Example 6 were prepared. In Example 14, a product name AO-20 manufactured by ADEKA Co., Ltd. of a phenolic antioxidant as an additive was added at a ratio shown in Table 11.

[Percentage of Solid Content of Second Form in Composition of Example and Comparative Example, Ratio Other Than PTO Particles and PTO Particles]
The ratio of the solid content of the second form in the composition of Examples 9 to 14 and Comparative Example 6, and the ratio other than PTO particles and PTO particles were summarized. These percentages are shown in Table 12.

[Proportion of PTO particles and PTO particles other than PTO particles in composition of Examples and Comparative Examples, Physical properties of PTO particles, Ratio of binder resin, and dispersant]
The proportions other than PTO particles and PTO particles in the composition of Examples 9 to 14 and Comparative Example 6, the physical properties of PTO particles, the proportions of the binder resin and the dispersant were summarized. These ratios are shown in Table 13.

[Formation of PTO conductive film of second form and printability of composition and evaluation of PTO conductive film of second form]
From the compositions for forming a PTO conductive film of the six types of the second embodiment obtained in Examples 9 to 14 and Comparative Example 6, the PTO conductive film of the second embodiment for each composition is the same method as the first embodiment. Formed on a substrate, printability of the composition as in the first embodiment, adhesion to the substrate of the PTO conductive film of the second embodiment, transparency, conductivity, and surface under high temperature and high humidity The change in resistivity was evaluated. The rate of change of the surface resistivity under high temperature was determined in the same manner as in the first embodiment after storage for 72 hours in a room adjusted to 85 ° C. The rate of change in surface resistivity under high humidity was determined in the same manner as in the first embodiment after storage for 72 hours in a room adjusted to a temperature of 60 ° C. and a relative humidity of 90%. The evaluation method of the other items is the same as the evaluation method of the first embodiment. The results are shown in Tables 14 and 15.

[Evaluation of light resistance of second form PTO conductive film]
The light resistance of the six types of PTO conductive films of the second form formed by the above method was evaluated. Specifically, the PTO conductive film formed on the substrate is placed in a room adjusted to a temperature of 63 ° C. at a relative humidity of 50%, and the PTO conductive film is irradiated with ultraviolet light (Iwasaki Electric, Eye Super UV Tester SUV Ultraviolet rays with an illuminance of 0.15 W / cm ² and an integrated light amount of 270 J / cm ² were irradiated for 30 minutes using -W16). The initial surface resistivity before irradiation and the surface resistivity after irradiation were measured, and the rate of change was determined based on the following equation.
Rate of change (%) = [(surface resistivity after UV irradiation-initial surface resistivity) / initial surface resistivity] × 100
The results are shown in Table 16.

As apparent from Tables 9 to 16, in Comparative Example 6, a PTO dispersion was prepared using PTO particles of No. 11 of 20.0 parts by mass (Table 9) for the coated amount of the hydrolyzate of organosilicon. Since the specific surface area of the PTO particles is 122 m ² / g (Table 9), the total light transmittance is 85.0% (Table 14), which is the transparency evaluation of the PTO conductive film obtained by the dispersion. ) And the haze was as high as 3.0%. In addition, the initial surface resistivity exceeds the measurement range of Hiresta (Table 16) and is described as "Over". ) Could not express conductivity.

On the other hand, the compositions of Examples 9 to 14 have a screen property because they are a composition containing ethyl cellulose which can increase the viscosity, and a high boiling point solvent of butyl carbitol acetate or α-terpineol. It was excellent. Furthermore, in 100% by mass of the paste composition, 14.0 to 31.5% by mass of PTO particles is contained, and in 100% by mass of the solid content of the composition, 10.0 to 30% by mass of components other than the PTO particles are contained. The PTO particles have a BET specific surface area of 80 to 115 m ² / g, and the binder resin includes a terpene phenol resin having a softening point of 160 ° C., and a mass ratio of the ethyl cellulose to the terpene phenol resin is ethyl cellulose : PTO conductivity made from the composition of Examples 35 to 40, since the terpene phenol resin = 30: 70 or 20: 80, and the dispersing agent is 5 parts by mass with respect to 100 parts by mass of the liquid PTO particles. The film was excellent in adhesion to the substrate, transparency, conductivity and heat and moisture resistance. In particular, the change ratio of the PTO conductive film made from the composition of these Examples 9 to 14 before and after the ultraviolet irradiation was within -10%, and the light resistance was excellent.

Claims (14)

In a composition for forming a phosphorus-doped tin oxide conductive film, comprising phosphorus-doped tin oxide particles, a binder resin, and an organic solvent,
The composition contains 3 to 45% by mass of the phosphorus-doped tin oxide particles in 100% by mass of the composition, and 10 to 52% by mass of components other than the phosphorus-doped tin oxide particles in 100% by mass of the solid content of the composition.
The phosphorus-doped tin oxide particles have a BET specific surface area of 75 to 110 m ² / g and an L value of 45 or more and 65 or less,
The composition for forming a phosphorus-doped tin oxide conductive film, wherein the binder resin comprises ethyl cellulose and a terpene phenol resin having a softening point of 130 to 160 ° C.   The composition for forming a phosphorus-doped tin oxide conductive film according to claim 1, wherein a mass ratio of the ethyl cellulose to the terpene phenol resin is ethyl cellulose: terpene phenol resin = 10 to 80: 90-20.   The composition for forming a phosphorus-doped tin oxide conductive film according to claim 1 or 2, further comprising 3 to 20 parts by mass of a dispersant based on 100 parts by mass of the phosphorus-doped tin oxide particles.   The composition for forming a phosphorus-doped tin oxide conductive film according to any one of claims 1 to 3, which is used for a paste or paint for screen printing.   The phosphorus-doped tin oxide conductive film according to claim 4, wherein the organic solvent comprises 3-methoxy-3-methyl-1-butanol and a solvent of butyl carbitol acetate or α-terpineol when used in the screen printing paste. Composition for formation.   When used in the paint, the organic solvent is 3-methoxy-3-methyl-1-butanol, 2-butanone, 4-methyl 2-pentanone, ethanol, 2-propanol, 1-butanol, toluene, methanol, 1 5. The composition for forming a phosphorus-doped tin oxide conductive film according to claim 4, comprising one or more solvents selected from the group consisting of: -propanol, ethyl acetate, butyl acetate, acetone, 2,4-pentanedione and xylene object.   The phosphorus-doped tin oxide conductive film according to any one of claims 1 to 6, further comprising 0.1 to 5% by mass of a phenolic antioxidant or hindered amine light stabilizer in 100% by mass of the solid content of the composition. Composition for formation.   It further contains an organosilicon compound having a hydrolyzable group and water, and the content of the organosilicon compound is 5 to 52% by mass in 100 mass of the solid content of the composition, and the content of the water is the hydrolysis The hydrolyzable group contained in the organosilicon compound having a decomposable group is a methoxy group or an ethoxy group, and the number of moles is 0.05 to 0.7 times the number of moles of this hydrolyzable group. A composition for forming a phosphorus-doped tin oxide conductive film according to any one of the above. The phosphorus-doped tin oxide particles are coated with a hydrolyzate of organosilicon, and the specific surface area according to the BET method of the phosphorus-doped tin oxide particles coated with the hydrolyzate of organosilicon is 80 to 115 m ² / g, the organosilicon The coating amount of the hydrolyzate of the present invention is 0.5 to 15 parts by mass with respect to 100 parts by mass of the phosphorus-doped tin oxide particles before the coating, for forming a phosphorus-doped tin oxide conductive film according to any one of claims 1 to 7. Composition. Phosphorus-doped tin oxide particles having a specific surface area according to a BET method of 75 to 110 m ² / g and an L value of 45 to 65 are uniformly dispersed in a terpene phenol resin having a softening point of 130 to 160 ° C. A phosphorus-doped tin oxide conductive film comprising 48 to 90% by mass of the phosphorus-doped tin oxide particles and 10 to 52% by mass of components other than the phosphorus-doped tin oxide particles.   The phosphorus-doped oxide according to claim 10, further comprising 0.1 to 5% by mass of a phenolic antioxidant or a hindered amine-based light stabilizer in 100% by mass of the composition in components other than the phosphorus-doped tin oxide particles. Tin conductive film.   The component other than the phosphorus-doped tin oxide particles further contains an organosilicon compound having a hydrolyzable group and water, and the content of the organosilicon compound is 5 to 52% by mass in 100 mass of the solid content of the composition The content of the water is such that the hydrolyzable group contained in the organosilicon compound having the hydrolyzable group is a methoxy group or an ethoxy group, and 0.05 to 0.7 with respect to the number of moles of the hydrolyzable group. The composition for forming a phosphorus-doped tin oxide conductive film according to claim 10, which has a mole number that is double. A phosphorus-doped tin oxide particle coated with an organosilicon hydrolyzate and having a BET specific surface area of 80 to 115 m ² / g uniformly dispersed in a terpene phenol resin having a softening point of 130 to 160 ° C. And 70 to 90% by mass of the phosphorus-doped tin oxide particles coated with the hydrolyzate of the organosilicon in the film, and 10 to 30% by mass of components other than the phosphorus-doped tin oxide particles coated with the hydrolyzate of the organosilicon A PTO conductive film, wherein the coated amount of the organosilicon hydrolyzate is 0.5 to 15 parts by mass with respect to 100 parts by mass of the phosphorus-doped tin oxide particles before the covering.   The phosphorus-doped tin oxide conductive film according to claim 13, further comprising a phenolic antioxidant or a hindered amine light stabilizer among the components other than the phosphorus-doped tin oxide particles coated with the organosilicon hydrolyzate.