JP2007206677A - Toner for electronic printing and method for producing glass plate having conductor pattern - Google Patents

Abstract

[PROBLEMS] To produce a glass plate having a conductor pattern excellent in adhesion to a glass plate surface, which does not require a screen plate for each type, can be easily adjusted to desired electrothermal performance and antenna performance. And provision of toner for electronic printing therefor.
A toner base particle including conductive fine particles, a heat decomposable binder resin, and glass frit, and a heat decomposable organic resin fine particle attached to a surface of the toner base particle, the heat decomposable organic resin fine particles. A toner for electronic printing, characterized in that the thermal decomposition temperature of the organic resin is lower than the thermal decomposition temperature of the thermally decomposable binder resin. Using the toner for electronic printing, forming a pattern made of the toner on the surface of the glass plate by an electronic printing method, and then heating the glass plate to a predetermined temperature, thereby firing the toner pattern and converting it into a conductor pattern; A method of forming a conductor pattern on a glass plate surface.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a glass plate having a toner for electronic printing and a conductor pattern, and in particular, forming a conductor pattern having excellent adhesion to a glass plate surface used for windows of automobiles and the like. The present invention relates to a toner for electronic printing and a method for producing a glass plate having a conductor pattern.

  A glass plate used for an automobile window is provided with a conductive wire as a heater wire for removing fog and an antenna wire for receiving television, radio, or the like. Such conductive wires are mainly provided in the rear window and the rear window of the automobile. The conductive wire is mainly composed of a fired body of paste containing silver. Specifically, a paste containing silver and glass frit contained in a resin solution is printed on a glass plate surface in a predetermined pattern by screen printing, and the glass plate is heated to decompose the resin component. After fixing silver on the glass plate surface, the silver is fired to form a conductive wire on the glass plate surface.

  Since there is a restriction on the voltage of the electric system used in the automobile, it is necessary to set the resistance value of the heater wire to a predetermined resistance value in order to obtain a desired heat generation amount. In addition, in order to receive radio waves with a predetermined antenna pattern, it is necessary to set the resistance value of the antenna line to a predetermined resistance value. The resistance value of the conductive line depends on the line width and line thickness.

  On the other hand, it is necessary to devise an arrangement pattern of heater wires and antenna wires in order to sufficiently remove fogging over the entire area of the window and to receive radio waves with a desired sensitivity. How much haze can be removed by these patterns, or how much antenna performance can be obtained, can be predicted to some extent by computer simulation. In addition, a conductive tape is simply attached to a glass plate surface, and each performance is preliminarily measured (for example, see Patent Document 1). However, it is necessary to measure each performance by actually providing a conductive wire to determine whether the defogging or antenna performance to be finally obtained is achieved.

  Therefore, the arrangement pattern of the conductive lines may be changed even after the screen plate is manufactured and the glass plate having the conductive lines is manufactured in anticipation of the almost final stage. In this case, the screen version must be corrected according to the corrected arrangement pattern.

  Since automobiles are mass-produced products, glass plates for windows used in automobiles are also mass-produced products. Therefore, once the pattern of the conductive line is determined, it is required to sequentially print the conductive paste on a large number of glass plates according to the determined pattern. For such mass production, screen printing of a conductive paste using a screen plate is suitable. However, as described above, even if a screen plate having a substantially fixed pattern is prepared, it is necessary to correct the screen plate to a pattern that finally makes the heat generation performance and antenna performance desired. And when using a glass plate for a motor vehicle window etc., the shape of a glass plate, the pattern shape of a conductive wire, etc. differ according to the model of a motor vehicle. Therefore, screen plates must be prepared according to the type of automobile, and many screen plates must be stocked. For this reason, development of the manufacturing method of the glass plate which has a conductive wire which does not require correction of a screen plate, and the electroconductive composition for it is calculated | required.

  On the other hand, recently, a toner (ink) containing conductive fine particles made of a metal such as silver and a thermoplastic resin is printed on an inorganic substrate by an electronic printing method and baked to form a conductive wiring pattern. Various electronic printing toners have been proposed. As a typical example, for example, an electronic printing toner (Patent Document 2) in which conductive fine particles are encapsulated with a thermoplastic resin and glass frit or the like is added thereto has been proposed. However, since a thermoplastic resin such as a styrene-acrylate copolymer resin is used in the toner for electronic printing, the resin remains as a carbide in the conductive wire during firing. As a result, the sintering of the conductive fine particles was hindered, and the electrical characteristics (resistance value) of the obtained conductive wires were not sufficient as a wiring pattern. Further, the adhesion between the conductive wire after firing and the inorganic substrate was not good.

  On the other hand, when printing color toner on paper by electronic printing, the surface of the toner base particles is made of an inorganic material such as silica or titanium oxide for the purpose of improving the fluidity of the toner to improve the resolution and obtaining an excellent image. It is known to coat an external additive composed of spherical fine particles (see, for example, Patent Document 3). However, as a result of intensive studies by the present inventors, when an external additive composed of inorganic spherical fine particles is present on the surface of the toner base particles, the binder (resin) in the toner base particles and the glass plate surface during thermal transfer to the glass plate surface. It has been found that there is a problem in that the adhesion rate is hindered and the transfer rate is remarkably deteriorated. In addition, when a toner using an external additive composed of inorganic spherical fine particles is electronically printed on the glass plate surface, the inorganic spherical fine particles remain in the conductive wire even after firing. There was also a problem of significantly inhibiting the value). Furthermore, when inorganic spherical fine particles are used as an external additive for toner base particles containing glass frit, the adhesion between the conductive fine particles and the glass plate surface is present because the inorganic spherical fine particles are present in the glass frit melted by heating. As a result, the adhesion strength between the conductive wire after firing and the glass plate surface may be impaired. Therefore, development of an electronic printing toner capable of transferring a conductive wire to a glass plate surface with a high image quality and a high transfer rate by an electronic printing method, and an external additive therefor is demanded.

JP 2003-188622 A (Claims) JP 2002-244337 A (Claims) Japanese Patent Laying-Open No. 2005-99878 (Claims and Examples)

  TECHNICAL FIELD The present invention relates to a method for producing a toner for electronic printing and a glass plate having a conductor pattern. In particular, the pattern of a conductor excellent in adhesion to a glass plate surface used for a window of an automobile or the like is high in image quality and high. It is an object of the present invention to provide a method for producing a glass plate having a toner and a conductive pattern that can be formed at a transfer rate.

  This invention provides the manufacturing method of the glass plate which has a toner for electronic printing as described in following (1)-(8) and a conductor pattern as described in following (9)-(11).

  (1) A toner mother particle containing conductive fine particles, a heat decomposable binder resin and glass frit, and a heat decomposable organic resin fine particle attached to the surface of the toner mother particle. A toner for electronic printing, wherein the thermal decomposition temperature of the resin is lower than the thermal decomposition temperature of the thermally decomposable binder resin.

  (2) The toner for electronic printing according to (1), wherein the toner base particles have an average particle size of 10 to 35 μm.

  (3) The toner for electronic printing according to (1) or (2), wherein an average particle size of the thermally decomposable organic resin fine particles is 10 to 800 nm.

  (4) The toner base particles are 59.8 to 94.8 parts by weight of conductive fine particles, 5 to 40 parts by weight of thermally decomposable binder resin, and 100% by weight of the total solid content of the toner base particles. The toner for electronic printing according to any one of (1) to (3), wherein 0.2 to 5 parts by mass of the toner is contained.

  (5) The toner for electronic printing according to any one of (1) to (4), wherein the amount of the thermally decomposable organic resin fine particles is 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner base particles.

  (6) The toner for electronic printing according to any one of (1) to (5), wherein the glass frit has a melting temperature of 450 to 500 ° C.

(7) a _{T 100} is four hundred and twenty-five to four hundred and fifty ° C. of the heat decomposable binder resin, _{T 100} of the organic resin in the heat decomposable organic resin fine particles are two hundred fifty to four hundred and twenty ° C., one of (1) to (6) The toner for electronic printing according to any one of the above.

Here, T ₁₀₀ indicates a temperature at which the weight change disappears when the temperature is increased from room temperature at a temperature increase rate of 10 ° C./min using a thermogravimetric analyzer (TG).

  (8) The toner for electronic printing according to any one of (1) to (7), wherein the thermally decomposable binder resin is a thermally decomposable resin having an acidic group having an acid value of 5 to 100.

  (9) The toner for electronic printing according to any one of (1) to (7), wherein the thermally decomposable binder resin is a thermally decomposable resin having an acid value of 20 to 100.

  (1)-using the toner according to any one of (9), forming a pattern of the toner on the glass plate surface by an electronic printing method, and heating the glass plate on which the toner pattern is formed A step of converting the toner pattern into a conductor pattern by heating to a temperature at which the decomposable binder resin and the thermally decomposable organic resin fine particles disappear and the glass frit melts. The manufacturing method of the glass plate which has a body pattern.

  (11) The manufacturing method of the glass plate which has a conductor pattern as described in (10) whose temperature which heats the said glass plate is 600-740 degreeC.

  (12) The glass plate having the conductor pattern according to (10) or (11), wherein the glass plate is heated to convert the toner pattern into a conductor pattern, and the heated glass plate is thermally processed. Manufacturing method.

  According to the present invention, since a predetermined conductor pattern is formed using electronic printing, it is not necessary to prepare a screen plate for each pattern. Further, the toner of the present invention for use in this electronic printing can form a conductor pattern having excellent adhesion to the glass plate surface. In particular, the toner of the present invention has a high transfer rate and can form a conductor pattern with excellent electrical characteristics (specific resistance value), thereby easily forming a conductor pattern having desired heat generation performance and antenna performance. Is possible.

  In the present invention, electronic printing refers to xerographic printing. In the xerographic method, a photosensitive drum having an electrostatic charge is exposed to form an electrostatic latent image, and the latent image is developed with toner to form a toner pattern on the surface of the photosensitive drum. Basically, the image is transferred from the surface of the photosensitive drum to the surface of the substrate (in the case of the present invention, the surface of a glass plate, etc.) The present invention is an invention of a toner suitable for this electronic printing.

  When the toner of the present invention is heated to a predetermined temperature, the thermally decomposable binder resin and thermally decomposable organic resin fine particles in the toner disappear and the glass frit starts to melt. Furthermore, it is considered that by increasing the temperature, the conductive fine particles are sintered and bonded, and the molten glass fills the gaps between the sintered conductive fine particles. Thereafter, when the molten glass is solidified by cooling, it is considered that a conductor composed of the combined conductive fine particles and the solidified glass filling the particle gap is generated. Therefore, the pattern formed by the toner of the present invention is heated to the predetermined temperature and then cooled to be converted into a conductor pattern. Heating to a temperature at which the thermally decomposable binder resin and the thermally decomposable organic resin fine particles disappear and the glass frit melts is also referred to as firing, and the temperature is also referred to as firing temperature. The toner of the present invention is an invention of a toner suitable for use in which a toner pattern formed by electronic printing is converted into a conductor pattern by baking.

  The substrate on which the conductor pattern is formed on the surface using the toner of the present invention may be a substrate made of a material that can withstand the predetermined temperature. As a board | substrate in this invention, a glass plate is preferable and especially the glass plate used for the window of a motor vehicle is preferable. The present invention also provides a method for producing a glass plate having a conductor pattern, which comprises using the toner to form a conductor pattern on the surface of the glass plate.

  The conductor pattern in the present invention may be a pattern made of a linear conductor, a pattern made of a strip-like conductor, or a pattern in which a linear conductor and a strip-like conductor are combined. May be. For example, as shown in FIG. 3, the defogger and the antenna are usually configured with a pattern made of a linear conductor, and the bus bar is configured with a pattern made of a strip-shaped conductor.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a side conceptual view showing an example of a series of steps for producing a glass plate having a conductor pattern of the present invention. The glass plate G is conveyed to a printing process through steps (ST1) such as cutting, chamfering, and washing into a predetermined shape. In the printing step ST2, the toner of the present invention is printed in a predetermined pattern on the surface of the glass plate G by the electronic printing apparatus 10. The glass plate G on which toner is printed in a predetermined pattern is conveyed into the heating furnace 30. When the glass plate G is heated to a predetermined temperature in the heating furnace 30, the toner is baked on the surface of the glass plate G to be converted into a conductor, and a glass plate having a predetermined conductor pattern is manufactured. The formed conductor pattern is conveyed to an inspection process (ST4; not shown), and the resistance value is inspected. The inspection result in the inspection process ST4 is transmitted to the computer C, and after determining whether the desired electrothermal performance or antenna performance is obtained, the determination information is converted into pattern adjustment information such as the shape of the pattern and the line width, This is used for printing pattern control in the printing process ST2.

  In the step ST1, a rectangular glass plate is cut into a predetermined shape, and the cut surface is chamfered. Thereafter, the glass plate is washed, preheated as necessary, and conveyed to the printing process ST2 by the conveying roll 20.

  In the printing process ST2, after the photosensitive drum 13 is neutralized by the static eliminator 14 while rotating the photosensitive drum 13, the photosensitive drum 13 is charged by the charger 12, and exposed to exposure light from the light source 15 to be exposed in a predetermined pattern. The drum 13 is exposed. Next, the exposure surface of the photosensitive drum 13 is rotated to the toner supply unit 11, and toner is given to the photosensitive drum 13, whereby a toner layer having a predetermined pattern is formed on the surface of the photosensitive drum 13. The toner layer having a predetermined pattern on the surface of the photosensitive drum 13 is transferred to the surface of the glass plate G that has been conveyed along with the rotation of the photosensitive drum 13. Thus, a toner layer having a predetermined pattern is formed on the glass plate G surface. At this time, a secondary transfer plate such as an intermediate transfer belt may be interposed between the photosensitive drum 13 and the glass plate G surface.

  The computer C stores pattern information for exposing with a predetermined pattern by irradiating exposure light. Therefore, the exposure light is emitted from the light source 15 in a predetermined pattern according to a command from the computer C. When the glass plate G is used for an automobile window, the shape of the glass plate, the shape of the conductor pattern, and the like differ depending on the model of the automobile. Therefore, by changing the command signal based on these data corresponding to the model of the automobile, it is possible to easily change from the production of one type of glass plate to the production of another type of glass plate.

  The glass plate G having a toner layer of a predetermined pattern is conveyed into the heating furnace 30 and heated to a predetermined temperature, usually about 600 to 740 ° C. Thus, the toner is baked on the surface of the glass plate G, and a conductor having a predetermined pattern is formed on the glass plate. Since glass plates for automobile windows are usually curved, when a glass plate having a conductor pattern manufactured as described above is used for an automobile window, it is heated in the firing step ST3 and strengthened through bending. Processing is performed. In some cases, not the tempering treatment but the slow cooling treatment is performed (bending of a glass plate for laminated glass). The thermal processing of the glass plate means that the glass plate is heated to bend or strengthen. In addition, the temperature when heat-processing a glass plate is hereafter called heat processing temperature.

  The lower limit of the firing temperature is the lowest temperature at which the binder resin disappears and the glass frit melts (preferably further sintering of the conductive fine particles occurs), and the upper limit of the firing temperature is the temperature at which the conductive fine particles normally melt. Or it is the temperature lower than the temperature at which the molten glass disappears. Since the heat processing temperature is usually a temperature equal to or higher than the lower limit of the baking temperature, the toner is baked in the heating process by heating the glass plate to the heat processing temperature.

  When the toner is baked, a composition of conductive fine particles and molten glass frit is formed. Furthermore, it is preferable that the conductive fine particles are in a sintered state (the fine particles are combined with each other while maintaining the fine particle shape). In that case, the molten glass frit is considered to fill the gaps between the sintered conductive fine particles. It is also conceivable to form a conductor without sintering the conductive fine particles. In this case, the conductive fine particles are kept in contact with each other, and a gap between the conductive fine particles is filled with a molten glass frit to conduct the conductive. It is considered that the fine particles are bound to each other. Thereafter, when the glass plate is cooled, the melted glass is solidified to obtain a conductor composed of the conductive fine particles and the solidified glass.

  The toner for electronic printing of the present invention (hereinafter referred to as the present toner) is a toner base particle (hereinafter referred to as the present toner base particle) containing conductive fine particles, a thermally decomposable binder resin (hereinafter referred to as the present binder resin) and glass frit. And thermally decomposable organic resin fine particles adhering to the surface of the toner base particles. The thermally decomposable organic resin fine particles have a function of maintaining high fluidity of the toner powder until it is supplied to the photosensitive drum. This binder resin functions as a binder that combines the conductive fine particles and the glass frit as a single mother particle, and also transfers the toner pattern on the photosensitive drum or the like to the substrate and before the glass frit is melted. It is a component that functions as a binder for fixing conductive fine particles and glass frit to a substrate.

  After the pattern of the toner is formed on the glass plate, in the heating process, the organic resin constituting the thermally decomposable organic resin fine particles is first decomposed and volatilized so that the fine particles disappear, and then in the toner base particles. This binder resin decomposes. The decomposed binder resin volatilizes and disappears from the glass plate by heating. After most of the binder resin is volatilized, the glass frit starts to melt and the conductive fine particles in the toner base particles are fixed on the glass plate surface mainly by the adhesiveness of the glass frit. In these processes, by completely decomposing and volatilizing the binder resin until the glass frit is completely melted, the amount of residual resin in the conductor after firing can be reduced. Finally, when the glass plate is heated to a temperature exceeding 600 ° C., the conductive fine particles are sintered to form a conductor.

The lower limit of the firing temperature is approximately equal to or higher than the melting temperature Ts of the glass frit, and T _{100 of the} binder resin (substantially the disappearance temperature of the binder resin) is approximately equal to or lower than Ts. Preferably it is temperature. If based on this Ts, there is a possibility that T ₁₀₀ of the binder resin is decomposed product of the binder resin in too high conductor than Ts remains. Further, a possibility that T ₁₀₀ of the binder resin is too too low than the Ts, the binder resin before the glass frit is melted completely decomposed, it can not be a conductor on the glass plate surface is sufficiently secured There is. Therefore, it is preferable to select a resin having an appropriate T ₁₀₀ according Ts of the glass frit as the binder resin.

Further, the binder resin _is preferably is _{0.1~15 ℃ (T 100 -T 90)} . Since (T ₁₀₀ -T ₉₀ ) is 0.1 ° C. or higher, a small amount of the binder resin remains even when the glass frit starts to melt, so that the conductor is made of resin and glass frit in the vicinity of Ts. Both adhesiveness can fix to a glass plate surface, and can improve the adhesiveness of a glass plate surface and a conductor. On the other hand, when (T ₁₀₀ -T ₉₀ ) is 15 ° C. or less, the binder resin can be sufficiently decomposed until the glass frit is completely melted. It becomes difficult to remain, and it is hard to produce the sintering defect of electroconductive fine particles. In particular, (T ₁₀₀ -T ₉₀ ) is preferably 5 to 15 ° C.

The T ₁₀₀ indicates a temperature at which the weight change disappears when the temperature is increased from room temperature at a temperature increase rate of 10 ° C./min using a thermogravimetric analyzer (TG). The T ₉₀ is a value obtained when the decrease in the binder resin is 90% by weight when the temperature is increased from room temperature at a temperature increase rate of 10 ° C./min using a thermogravimetric analyzer (TG). Indicates temperature.

  Examples of the conductive fine particles include metal fine particles and conductive oxide fine particles. As the metal fine particles, fine particles of gold, platinum, silver or copper are preferable. The conductive oxide fine particles are preferably ITO (indium doped tin oxide) or ATO (antimony doped tin oxide) fine particles. When a glass plate on which a linear conductor pattern is formed is used for an automobile window, the line width of the linear conductor is made too large because it is necessary to prevent the provided linear conductor pattern from obstructing the field of view. It is not possible. Therefore, in order to obtain a desired resistance value with a narrow line width, it is particularly preferable to select silver fine particles as the conductive fine particles.

  The content of the conductive fine particles is preferably 59.8 to 94.8 parts by mass with respect to 100 parts by mass of the total solid content of the toner base particles. Since the content of the conductive fine particles is 59.8 parts by mass or more, the conductivity of the conductor can be sufficiently maintained, and the volume shrinkage at the time of cooling of the conductor formed by firing can be suppressed. Separation from the plate surface and generation of cracks can be prevented. Further, when the amount is 94.8 parts by mass or less, a stable charge amount as a toner can be expressed. The content of conductive fine particles is particularly preferably 69.8 to 89.8 parts by mass.

  The conductive fine particles preferably have an average particle size of 0.2 to 20 μm. When the average particle size is 0.2 μm or more, volume shrinkage of the obtained conductor is suppressed, and peeling from the glass plate surface can be prevented. On the other hand, when the average particle size is 20 μm or less, the print quality of the obtained conductor pattern can be improved. The average particle size of the conductive fine particles is particularly preferably from 0.5 to 10 μm. In the present specification, the average particle diameter of fine particles refers to the average diameter based on the number of particles. An average particle diameter can be measured by a well-known method, for example, can be measured using particle size distribution analyzers, such as a flow type, a laser diffraction and scattering type, and a dynamic light scattering type. Among these, a flow-type particle size distribution meter is particularly preferable because it can accurately measure the distribution of infrequent particles and can also measure the particle shape at the same time as the average particle size.

Any glass frit can be used regardless of whether it is lead-based or lead-free, but lead-free bismuth-silica glass frit is preferable from the viewpoint of the environment. The melting temperature Ts of the glass frit is preferably 400 to 550 ° C, and particularly preferably 450 to 500 ° C. By melting temperature Ts of the glass frit is 400 to 550 ° C., it becomes easy to select a binder resin having a _{T 100} of the relationship between the _{T 100} of the Ts and the binder resin are met, in particular 450 to 550 ° C. By doing so, it becomes easy to employ a binder resin having good decomposition characteristics. If the Ts of the glass frit exceeds 550 ° C., it is too close to the lower limit 600 ° C. of the normal processing temperature of the glass plate, and the glass frit may not be sufficiently melted when the glass plate is thermally processed.

  The binder resin is a thermally decomposable resin having the above functions, and the type of the resin is not limited as long as it has an appropriate thermal decomposition temperature and a function as a binder. However, toner aggregation or the like hardly occurs until it is supplied to the photosensitive drum, the toner adheres to the photosensitive drum with an appropriate adhesion force, and the toner pattern on the photosensitive drum is well transferred to the substrate. The binder resin is preferably a thermally decomposable resin having a functional group in order to exhibit functions such as good fixability of the toner pattern transferred to the surface. Furthermore, the functional group is preferably an acidic group such as a carboxy group.

  The binder resin is preferably a thermally decomposable resin mainly composed of an acid-modified thermoplastic resin having an acid value of 5 or more because it has good fixability to the glass plate surface and good decomposability during heat treatment. . Here, the acid value refers to the number of mg of potassium hydroxide required to neutralize acidic groups present in 1 g of resin. Although the reason why the fixability is improved by adopting a heat-decomposable resin mainly composed of an acid-modified thermoplastic resin having an acid value of 5 or more has not been elucidated, the acidic group in the binder resin is not present on the surface of the glass plate. It is thought to interact with the silanol group. Here, the binder resin may be composed of an acid-modified thermoplastic resin alone, or from a combination of an acid-modified thermoplastic resin and another thermally decomposable resin (for example, a thermoplastic resin having no acidic group). It may be. In the latter case, the proportion of the thermally decomposable resin other than the acid-modified thermoplastic resin is preferably a relatively small amount relative to the acid-modified thermoplastic resin, and the proportion is 30 with respect to the total resin amount of the binder resin. It is preferably not more than 10% by weight, particularly not more than 10% by weight. The polymer of the main chain of the acid-modified thermoplastic resin and the polymer of the main chain of another thermally decomposable resin are preferably polymers obtained by vinyl polymerization. Both main chain skeletons may be the same or different. Even when other thermally decomposable resins are contained, the acid value of this binder resin is 5 or more, and the acid value of all resins including other thermally decomposable resins having no acidic group is 5 or more. Preferably there is. Moreover, a commercially available thing can be used as an acid-modified thermoplastic resin and other thermally decomposable resin in this binder resin.

  The acid value of the binder resin is preferably 5 to 100. The acid value of the present binder resin is more preferably 20-100. As a result, when the present toner is electronically printed on the glass plate surface, a pattern with better fixability can be formed. When the acid value is 5 or more, particularly 20 or more, the number of acidic groups can be secured, so that the fixability of the pattern is stabilized, and after firing, poor adhesion of the conductive body is less likely to occur. On the other hand, when the acid value is 100 or less, the melt viscosity of the binder resin does not become too high, and the toner can be sufficiently fixed on the substrate surface when electronic printing is performed, and there is a defect such as offset on the photosensitive drum. It becomes difficult to get up. The acid value is more preferably 30 to 70.

  The acid-modified thermoplastic resin is a polymer having an acidic group, and the acidic group in the present invention refers to a carboxy group and a carboxylic anhydride group. The acid-modified thermoplastic resin is a thermoplastic resin having either or both of a carboxy group and a carboxylic anhydride group. The acid-modified thermoplastic resin is preferably a polymer obtained by copolymerizing a monomer having an acidic group or a polymer obtained by reacting a compound having an acidic group with a thermoplastic resin. Moreover, an acidic group containing polymer can also be obtained by hydrolyzing a polymer obtained by copolymerizing an unsaturated carboxylic acid ester monomer. The acid-modified thermoplastic resin in the present invention is particularly preferably an acid-modified thermoplastic resin obtained by reacting a pre-manufactured thermoplastic resin with a compound having an acidic group.

  The main monomers constituting the acid-modified thermoplastic resin include aromatic vinyl monomers such as olefins and styrene, (meth) acrylate monomers such as acrylic esters and methacrylic esters, and unsaturated alcohol ester monomers such as vinyl acetate. And diene monomers such as butadiene. In particular, a thermoplastic resin obtained using an olefin having 6 or less carbon atoms such as ethylene or propylene as a main monomer is preferable.

  As the compound having an acidic group (hereinafter referred to as an acid modifier), an unsaturated carboxylic acid or an unsaturated polycarboxylic acid anhydride is preferable. In particular, unsaturated dicarboxylic acid and unsaturated dicarboxylic acid anhydride are preferable. Specific examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, and citraconic anhydride. In particular, maleic anhydride is preferred as the acid modifier. Accordingly, the acid-modified thermoplastic resin is preferably an acid-modified thermoplastic resin obtained by reacting an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride with a thermoplastic resin, and particularly preferably a maleic anhydride-modified thermoplastic resin.

  As the acid-modified thermoplastic resin, an acid-modified polyolefin obtained by reacting a polyolefin-containing compound with an acidic group is preferable. Examples of the polyolefin include polyethylene, polypropylene, and ethylene-propylene copolymer. Among them, polypropylene is preferable because it is easy to ensure a stable charge amount as a toner. As a method of reacting an acid modifier with a polyolefin, a method in which an acid modifier and a radical generator (peroxide, etc.) are mixed in the polyolefin and heated, a low molecular weight obtained by partial thermal decomposition of the polyolefin in advance. A method in which an acid modifier is mixed and reacted with polyolefin (having a reactive site such as an unsaturated group) can be employed. As the acid-modified polyolefin, maleic anhydride-modified polyolefin obtained by these methods using maleic anhydride as an acid-modifying agent, particularly maleic anhydride-modified polypropylene, has a large charge amount, a rapid charge rise, and stable charge. From the viewpoint of sex. The weight average molecular weight of the acid-modified polyolefin is not particularly limited, but is preferably 3000 to 150,000, and particularly preferably 5000 to 80,000.

As for the thermal decomposability of the binder resin, it is preferable to have an appropriate T ₁₀₀ according to the melting temperature Ts of the glass frit as described above. Therefore, it is preferable to select a thermally decomposable resin having an appropriate T ₁₀₀ according to the value of Ts of the glass frit used. The difference (Ts−T ₁₀₀ ) between the melting temperature Ts of the glass frit and the T _{100 of the} binder resin is preferably 0 to 20 ° C. When (Ts−T ₁₀₀ ) is 0 to 20 ° C., melting of the glass frit can be started before the binder resin is decomposed and completely volatilized, and adhesion between the glass plate surface and the conductor is improved. Can be enhanced. In addition to the above, the difference (Ts−T ₉₀ ) between Ts and T _{90 of the} binder resin is preferably 0 to 80 ° C. Since (Ts−T ₉₀ ) is 0 ° C. or more, a small amount of the binder resin remains even when the glass frit starts to melt, and thus the adhesive properties of both the binder resin and the glass frit in the vicinity of Ts. Thus, it is considered that the conductor can be fixed to the glass plate surface and the conductor can be sufficiently adhered to the glass plate surface. On the other hand, when (Ts−T ₉₀ ) is 80 ° C. or less, the binder resin can be sufficiently decomposed until the glass frit is completely melted, so that the binder resin remains as a carbide in the conductor. This is considered to be difficult to cause sintering failure between the conductive fine particles and to improve the adhesion of the conductor to the glass plate surface. More preferably _{(Ts-T 90)} is 0.1 to 50 ° C..

As will be described later, the melting temperature Ts of the glass frit is preferably 450 to 500 ° C. In that case, _{T 100} of the binder resin is preferably 420-450 ° C.. In this case, by T ₁₀₀ is 420 ° C. or higher, before the glass frit is melted, the binder resin can be prevented from being completely decomposed, that conductor on the glass plate surface is sufficiently secured it can. On the other hand, when T ₁₀₀ is 450 ° C. or lower, when the toner is baked, the binder resin is rapidly decomposed and volatilized, so that there is almost no residual carbon remaining in the conductor. In addition to being able to obtain a conductor excellent in conductivity without interfering with each other, it is possible to obtain a conductor excellent in adhesion to the glass plate surface.

  The content of the binder resin is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the total solid content of the toner base particles. When the content is 5 parts by mass or more, when the toner is electronically printed, the fixing property with the substrate can be sufficiently secured. When the content is 40 parts by mass or less, the binder resin is less likely to remain in the fired conductor, so that defects such as cracks and voids are less likely to occur in the conductor. The content of the binder resin is particularly preferably 10 to 30 parts by mass.

  The glass frit content is preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the toner base particles. When the content of the glass frit is 0.2 parts by mass or more, the adhesion of the conductor to the substrate surface can be sufficiently ensured. On the other hand, when the content is 5 parts by mass or less, the glass against the conductive fine particles is obtained. An increase in the specific resistance of the conductor pattern due to an increase in the amount of the frit component can be suppressed. The glass frit is preferably a powder having an average particle size of 0.1 to 5 μm. When the glass frit has an average particle size of 0.1 μm or more, sufficient adhesion to the substrate surface can be secured, and when the average particle size is 5 μm or less, the glass frit is exposed on the surface of the toner particles. This can be prevented, and the fixability is hardly lowered when printed on the surface of the substrate by the electronic printing method. The glass frit particularly preferably has an average particle size of 0.5 to 3 μm.

  The toner base particles optionally contain inorganic pigments such as black iron oxide, cobalt blue, and brown, as well as charge control agents such as azo-based metal-containing dyes, salicylic acid-based metal-containing dyes, and quaternary ammonium salts. can do.

  The toner base particles are produced, for example, by mixing the binder resin, conductive fine particles, glass frit and the like, kneading and cooling to produce pellets, and then pulverizing and classifying. The heating temperature is preferably 150 to 200 ° C. By setting the heating temperature to 150 ° C. or higher, the present binder resin, conductive fine particles, glass frit and the like can be mixed uniformly. On the other hand, decomposition of this binder resin can be prevented because heating temperature is 200 degrees C or less. The toner base particles preferably have an average particle size of 10 to 35 μm. When the average particle size is 10 μm or more, the conductive fine particles in the toner base particles are prevented from being exposed on the surface and the charge amount of the toner can be secured. Occurrence of pattern defects such as ground fogging due to the shortage can be suppressed. On the other hand, when the average particle size is 35 μm or less, high-definition pattern quality is easily obtained.

The thermally decomposable organic resin fine particles in the toner are dispersed and adhered to the surface of the toner base particles, so that the toner in the toner feeder 11 and the like is not impaired without impairing the transfer rate from the photosensitive drum 13 or the like to the glass plate surface. It has the function of improving the fluidity of Further, the charge amount distribution of the toner can be controlled by using thermally decomposable organic resin fine particles. As an organic resin constituting the thermally decomposable organic resin fine particles (hereinafter referred to as the present organic resin), it is essential to use a resin having a decomposition temperature lower than that of the present binder resin constituting the present toner base particles. . To _{T 100} of the binder resin, _{T 100} of the present organic resin is suitable to be 5 ° C. or more lower, it is preferable 20 ° C. or more lower. In particular, it is preferably 40 ° C. or lower. The lower limit of the _{T 100} of the present organic resin is preferably from 200 ° C., particularly 250 ° C. are preferred. To the organic resin and T ₁₀₀ of the present organic resin is less than 200 ° C. stickiness tends to occur, when the ambient temperature of the toner supply machine is increased the fluidity of the toner may deteriorate. Specifically, if the _{T 100} of the binder resin is 425~450 ℃, _{T 100} of the present organic resin is preferably from 250 to 420 ° C.. As the organic resin, it is preferable to use a thermoplastic resin that decomposes and volatilizes rapidly upon heating, and examples thereof include one or more selected from the group consisting of polyethylene, polypropylene, polystyrene, acrylic resin, and styrene acrylic resin. Among these, an acrylic resin and / or a styrene acrylic resin are preferable in that the charging characteristics of the toner can be improved.

  In the present toner, the particle size of the thermally decomposable organic resin fine particles is preferably 10 to 800 nm. By setting the particle size to 10 nm or more, it is easy to obtain the effect of improving the fluidity of the toner and improving the transfer rate and image quality. On the other hand, by setting the particle size to 800 nm or less, the thermally decomposable organic resin fine particles are uniformly dispersed on the surface of the toner base particles, and the fluidity of the toner can be improved. Before the binder resin begins to decompose, the thermally decomposable organic resin fine particles decompose and volatilize, and do not hinder the fixing property between the toner base particles and the substrate surface. At this time, the ratio between the particle size of the thermally decomposable organic resin fine particles and the particle size of the toner base particles is [particle size of fine particles] / [particle size of the toner base particles] = 0.003 to 0.05. When the value is within the range, the effect of improving the fluidity of the present toner is easily obtained, which is particularly preferable.

  The content of the thermally decomposable organic resin fine particles is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner base particles. When the content is 0.1 part by mass or more, the fluidity of the toner is improved, and the effect of improving the transfer rate and the image quality is easily obtained. On the other hand, by setting the content of the thermally decomposable organic resin fine particles to 5 parts by mass or less, the fine particles decompose and volatilize before the binder resin in the toner base particles starts to be decomposed by heating. And does not hinder the fixing property between the glass plate surface. The content of the thermally decomposable organic resin fine particles is particularly preferably 1 to 3 parts by mass with respect to 100 parts by mass of the toner base particles.

  The toner base particles obtained as described above are subjected to the above-mentioned thermally decomposable organic resin fine particles by using a particle compounding device represented by a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mixer such as a Henschel mixer or a pass mixer This toner can be obtained by adhering. The conductive material can be formed by printing the toner on the substrate surface by an electronic printing method and then baking the toner. When the substrate is a glass plate, the firing temperature is preferably 600 to 740 ° C. When the firing temperature is 600 ° C. or higher, the conductive fine particles are sufficiently sintered. On the other hand, when the firing temperature is 740 ° C. or lower, deformation of the glass plate can be prevented. In the present invention, soda lime glass, non-alkali glass, quartz glass and the like can be used as the glass plate.

  The conductor formed according to the present invention preferably has a specific resistance of 20 μΩ · cm or less. This is preferable because it can be used as a conductor for various purposes such as wiring. Moreover, it is preferable that the film thickness of a conductor is 5-30 micrometers. When the film thickness is 5 μm or more, a stable specific resistance can be easily obtained, and when the film thickness is 30 μm or less, a desired film thickness can be easily obtained even by one-time electronic printing, and the handling is excellent.

  FIG. 2 is a conceptual diagram illustrating a control process according to a preferred embodiment of the present invention. The glass plate pretreated in ST1 is printed with a toner in a predetermined pattern in the printing step ST2, heated in the firing step ST3, and the toner is baked to produce a glass plate having a conductor pattern. After the firing step ST3, the resistance value of the conductor fired in the inspection step ST4 is measured. The measured resistance value data is sent to the computer C which controls the toner pattern in the printing process. If necessary, temperature data in the firing step ST3 is also sent to the computer C. The data sent to the computer C is used as data for determining whether desired electric heat performance and antenna performance can be obtained. When it is determined that the desired performance is not obtained, the line width of the toner printed or the print pattern itself is adjusted by the calculation of the computer C so as to obtain the desired performance. The adjusted toner line width and printing pattern are fed back to the printing step ST2, and a conductor is provided on the next glass plate.

  When desired electrothermal performance and antenna performance are obtained by such feedback, control data can be fixed and a large number of glass plates having a conductor pattern can be manufactured.

  Further, when the glass plate G is used for an automobile window, the computer C can store and accumulate glass plate shape data, conductor pattern shape data, and the like corresponding to the type of the vehicle. This makes it easy to change from one type to another by sending a command based on data on the pattern shape of the conductor corresponding to that type to the electronic printer when manufacturing a glass plate for that type. Printing according to each model can be performed. Furthermore, by sending a command based on the shape data of the glass plate among the data relating to the model to the cutting and chamfering step (ST1) of the glass plate, it is possible to easily change from one type to another type according to each type. Cutting and chamfering can be performed.

  In the printing step ST2, not only the main toner but also colored toner can be printed on the glass plate surface. For example, the rear window of the automobile illustrated in FIG. 3 is provided with a conductor (defogger 1, antenna wire 2, bus bar 3) in the central region of the glass plate G, and a dark ceramic fired body 4 in the peripheral region. By printing colored toner having a pigment in a predetermined pattern on the photosensitive drum shown in FIG. 1, the colored toner can be printed on the glass plate surface together with the toner. Similar to the conductor, conventionally, the dark ceramic fired body is also printed by screen printing. Thus, by performing electronic printing of the colored toner together with the present toner, a manufacturing method suitable for mass production can be obtained. In addition, two electronic printing apparatuses are provided, and a toner pattern is formed by electronic printing using the present toner and a toner pattern is formed by electronic printing using the colored toner on one glass plate sequentially. It is also possible to produce a glass plate having a pattern of a conductor and a dark ceramic fired body.

Examples 1 to 4 (Examples) and Examples 5 to 7 (Comparative Examples) are shown below. Here, in Examples 1 to 7, the decomposition temperature was from room temperature to 700 ° C. using a thermogravimetric analyzer (manufactured by Shimadzu Corporation, model: DTG-50) at a heating rate of 10 ° C./min. perform the measurement, the temperature T ₁₀₀ of weight change of the resin is eliminated, reducing the amount of the resin was determined and the temperature T ₉₀ at the time point when 90%.

The average particle diameter of the particles is 50 in a cumulative particle size distribution curve based on the number of equivalent circle diameters measured using a flow type particle image analyzer (trade name: FPIA-3000, manufactured by Sysmex Corporation). %.
In addition, the average molecular weight of the resin used in Examples 1 to 7 refers to the weight average molecular weight.

[Example 1]
Maleic anhydride-modified polypropylene (manufactured by Sanyo Kasei Co., Ltd., trade name: Yumex 1010, average molecular weight 30000, acid value 52, T ₁₀₀ = 430 ° C., T ₉₀ = 420 ° C.) 20 parts by mass, silver powder (average particle size 2 μm) 79 parts by mass 1 part by weight of glass frit (bismuth-silica lead-free glass frit, melting temperature Ts = 450 ° C., average particle size 2 μm), kneaded at 170 ° C. using a kneader, cooled to room temperature and solid Got. The solid was pulverized with a jet mill and classified to obtain particles (toner mother particles) having an average particle size of 20 μm.

With respect to 99 parts by mass of the particles obtained above, spherical fine particles made of an acrylic resin as thermally decomposable organic resin fine particles (manufactured by Soken Chemical Co., Ltd., trade name: MP-2200, average particle size 350 nm, T ₁₀₀ = 330 ° C.) 1 part by mass was added, and spherical fine particles made of an acrylic resin were adhered to the toner base particles using a hybridization system (manufactured by Nara Machinery Co., Ltd.) to obtain an electronic printing toner having an average particle diameter of 20 μm.

  Using this electronic printing toner, a fine line pattern having a line width of 1 mm and a length of 80 mm is printed on a secondary transfer belt maintained at 180 ° C. using an electronic printing machine (manufactured by Mitsubishi Heavy Industries, Ltd.). The pattern was transferred from the transfer belt onto soda lime glass (length 30 cm, width 30 cm, thickness 3.5 mm) kept at room temperature, and then baked at 700 ° C. for 4 minutes to form conductive lines. The following evaluation was performed on this conductive wire. The evaluation results are shown in Table 1. Hereinafter, evaluation was similarly performed in Examples 2 to 7.

[Transfer rate]
The transfer rate was calculated from the ratio of the area of the pattern transferred onto the glass plate surface / the area of the pattern printed on the belt.

[Specific resistance evaluation]
The resistance value of the conductor pattern was measured with a resistance measuring instrument (trade name: Nanovolt / Microohmmeter 34420A manufactured by Agilent), and the film thickness was measured with a stylus type surface shape measuring instrument (trade name: Dektak 8 manufactured by ULVAC). ). The specific resistance value was calculated from the resistance value and the film thickness value.

[Example 2]
Except using spherical fine particles (made by Soken Chemical Co., Ltd., trade name: MP-1451, average particle size 150 nm, T ₁₀₀ = 353 ° C.) as the thermally decomposable organic resin fine particles, the same as Example 1 was used. Operation was performed to obtain an electronic printing toner having an average particle size of 20 μm.

[Example 3]
Except using spherical fine particles (manufactured by Soken Chemical Co., Ltd., trade name: MP-4009, average particle size 600 nm, T ₁₀₀ = 388 ° C.) as the thermally decomposable organic resin fine particles, the same as Example 1. Thus, an electronic printing toner having an average particle size of 20 μm was obtained.

[Example 4]
Except using spherical fine particles (made by Soken Chemical Co., Ltd., trade name: MP-5000, average particle size 400 nm, T ₁₀₀ = 418 ° C.) as the thermally decomposable organic resin fine particles, the same as Example 1 was used. Thus, an electronic printing toner having an average particle diameter of 20 μm was obtained.

[Example 5 (comparative example)]
The same operation as in Example 1 was performed except that spherical silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: R972, average particle diameter of 16 nm, not decomposed at 700 ° C.) were used as fine particles to be adhered to the toner base particles. A toner for electronic printing having an average particle size of 20 μm was obtained.

[Example 6 (comparative example)]
The operation was carried out in the same manner as in Example 1 except that spherical silica fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: RY200, average particle size 12 nm, not decomposed at 700 ° C.) were used as fine particles to be adhered to the toner base particles. A toner for electronic printing having an average particle size of 20 μm was obtained.

[Example 7 (comparative example)]
The operation was performed in the same manner as in Example 1 except that spherical titania fine particles (manufactured by Nippon Aerosil Co., Ltd., trade name: T805, average particle size 21 nm, not decomposed at 700 ° C.) were used as fine particles to be adhered to the toner base particles. A toner for electronic printing having an average particle size of 20 μm was obtained.

  From the results of Table 1, it was found that in Examples (Examples 1 to 4) using thermally decomposable organic resin fine particles, a glass plate with conductive wires having a good transfer rate and a low specific resistance value was obtained. Recognize.

  The present invention relates to a method of providing a conductor on the surface of a glass plate and a toner for electronic printing therefor, and is particularly suitable for a method of manufacturing a glass plate having a conductor pattern for an automobile window.

It is a side surface conceptual diagram which shows an example of a series of processes which manufacture the glass plate which has a conductor pattern of this invention. It is a conceptual diagram explaining the control process which concerns on the preferable form of this invention. It is a front view which shows an example of a motor vehicle rear window.

Explanation of symbols

1: Defogger 2: Antenna wire 3: Bus bar 4: Dark ceramic fired body 10: Electronic printing device 11: Toner feeder 12: Charging machine 13: Photoconductive drum 14: Electric remover 15: Light source 20: Conveying roll 30: Heating furnace G : Glass plate C: Computer ST1: Chamfering process ST2: Printing process ST3: Firing process ST4: Inspection process

Claims (12)

  A toner base particle containing conductive fine particles, a thermally decomposable binder resin and glass frit, and a thermally decomposable organic resin fine particle attached to the surface of the toner base particle, and heat of the organic resin in the thermally decomposable organic resin fine particles A toner for electronic printing, wherein a decomposition temperature is lower than a heat decomposition temperature of the heat-decomposable binder resin.   The toner for electronic printing according to claim 1, wherein the toner base particles have an average particle size of 10 to 35 μm.   The toner for electronic printing according to claim 1, wherein an average particle size of the thermally decomposable organic resin fine particles is 10 to 800 nm.   The toner base particles are 59.8 to 94.8 parts by weight of conductive fine particles, 5 to 40 parts by weight of thermally decomposable binder resin, and 0. 0 to glass frit with respect to 100 parts by weight of the total solid content of the toner base particles. The toner for electronic printing according to any one of claims 1 to 3, comprising 2 to 5 parts by mass.   The toner for electronic printing according to claim 1, wherein the amount of the thermally decomposable organic resin fine particles is 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner base particles.   The toner for electronic printing according to any one of claims 1 to 5, wherein the glass frit has a melting temperature of 450 to 500C. _{T 100} of the heat decomposable binder resin is a four hundred twenty-five to four hundred fifty ° C., a _{T 100} of the organic resin 250-420 ° C. in the heat decomposable organic resin fine particles, electrons according to claim 1 Toner for printing.
Here, T ₁₀₀ indicates a temperature at which the weight change disappears when the temperature is increased from room temperature at a temperature increase rate of 10 ° C./min using a thermogravimetric analyzer (TG).   The toner for electronic printing according to any one of claims 1 to 7, wherein the thermally decomposable binder resin is a thermally decomposable resin having an acidic group having an acid value of 5 to 100.   The toner for electronic printing according to any one of claims 1 to 7, wherein the thermally decomposable binder resin is a thermally decomposable resin having an acid value of 20 to 100.   A step of forming the toner pattern on a glass plate surface by an electronic printing method using the toner according to any one of claims 1 to 9, and the thermal decomposition of the glass plate on which the toner pattern is formed. A step of converting the toner pattern into a conductor pattern by heating to a temperature at which the binder resin and the thermally decomposable organic resin fine particles disappear and the glass frit melts. The manufacturing method of the glass plate which has this.   The manufacturing method of the glass plate which has a conductor pattern of Claim 10 whose temperature which heats the said glass plate is 600-740 degreeC.   The method for producing a glass plate having a conductor pattern according to claim 10 or 11, wherein the glass plate is heated to convert the toner pattern into a conductor pattern, and the heated glass plate is thermally processed.

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