JP2009175399A - Photosensitive composition for forming insulating layer of electron emission device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition which has good dispersibility, enables uniform film formation even in the case of a thin film, and fulfills an adequate function as an insulating layer with a fine pattern. <P>SOLUTION: The photosensitive composition for forming an insulating layer of an electron emission device comprises a photosensitive organic component, a dispersant and an inorganic powder, wherein the number of aggregates having a particle diameter of ≥20 μm in 100 g of the composition is <50. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive composition used for forming an insulating layer of an electron-emitting device, a method for producing the photosensitive composition, and an electron-emitting device using the same.

  As an image display device replacing a cathode ray tube, an image display device using an electron-emitting device which is a self-luminous discharge type display has been proposed. Compared to liquid crystal displays and plasma displays, this image display device has a bright and dark contrast, low power consumption, excellent video performance, and can meet the demands for high definition. The needs are growing. Moreover, the use as a fluorescent light-emitting device used as a light source instead of an image display device has been proposed and developed. Among such electron emission type flat image display devices and fluorescent light emitting devices, a CNT-field emission display (FED) using carbon nanotubes (CNT) as an electron emission element is easy to increase electron emission characteristics and area. There is active development for some reason.

  Such an electron emission type flat image display device and a fluorescent light emitting device include a front glass substrate and a back glass substrate having respective functions. The back glass substrate is provided with a plurality of electron-emitting devices and matrix wiring for connecting these devices. These wirings are installed in the X direction and the Y direction, and intersect at the electrode portion of the electron-emitting device. In order to insulate both at the intersecting portion, a patterned insulating layer is necessary.

  Regarding the production of this insulating layer, a method of forming a silicon oxide film by vacuum deposition, printing, sputtering, etc., a method of forming a pattern by ultraviolet exposure after applying a photosensitive composition over the entire surface by screen printing, etc. are disclosed. (For example, refer to Patent Document 1).

  On the other hand, as a photosensitive composition forming a member such as an insulating layer for a display, a photosensitive composition comprising a photosensitive organic component containing a photosensitive monomer, a binder polymer and a photopolymerization initiator, and an inorganic component (for example, Various proposals such as a photosensitive composition comprising an alkali-soluble polyorganosiloxane resin composition and an acid generator, and an inorganic component (see, for example, Patent Document 3) have been proposed. Among these, a photosensitive composition comprising a photosensitive organic component and an inorganic component containing a photosensitive monomer and a photopolymerization initiator is preferably used because of many variations in material selection and easy control of its performance. .

In order to obtain a member such as an insulating layer of an image display device and a fluorescent light-emitting device from such a photosensitive composition, the photosensitive composition is applied as a thin film on a substrate, a pattern is formed by photolithography, and then Firing is performed. In order to apply a thin film, a photosensitive composition having excellent dispersibility is required. As a composition having excellent dispersibility, a glass paste in which the number of aggregates is a certain value or less is known (see, for example, Patent Document 4). A method for obtaining a conductive paste with good dispersibility is also known (see, for example, Patent Document 5). However, none of the compositions was used as an insulating layer for image display devices and fluorescent light emitting devices.
JP 2002-245928 A (paragraph 29-30) JP-A-11-185601 (Claim 4) JP-A-2005-300633 (Claims 1 and 11) JP-A-2005-97084 (Claim 1) JP-A-2006-351348 (Claim 1)

  In order to further reduce the driving voltage of the electron-emitting device to achieve lower power consumption, it is required to reduce the coating film thickness and facilitate electron emission in the coating process. For this purpose, a composition with good dispersibility that can be applied to a further thin film is required. However, a conventionally known composition is not sufficient, and defects and irregularities are generated, and pattern workability is insufficient. Further, since it is photosensitive, there is a problem that the amount of the photosensitive organic component is large and poor dispersion and aggregation are likely to occur.

  The present invention relates to a photosensitive composition for forming an insulating layer of an electron-emitting device, has good dispersibility, can form a uniform film even if it is a thin film, and is sufficient as an insulating layer having a fine pattern. It aims at providing the photosensitive composition which expresses a function.

    The present invention is a photosensitive composition for forming an insulating layer of an electron-emitting device comprising a photosensitive organic component, a dispersant, and an inorganic powder, and the number of aggregates having a particle size of 20 μm or more in 100 g of the composition is 50. It is a photosensitive composition characterized by being less than one.

  The photosensitive composition of the present invention is free from defects and can form a thin film insulating layer having good fine pattern / insulating properties. Moreover, the electron-emitting device obtained by using the photosensitive composition of the present invention can emit a low driving voltage and uniform electrons.

  The photosensitive composition of the present invention is a photosensitive composition for forming an insulating layer of an electron-emitting device comprising a photosensitive organic component, a dispersant, and an inorganic powder, and has a particle size of 20 μm or more in 100 g of the composition. The number of aggregates is less than 50. If the particle size of the aggregate is 20 μm or more, it becomes larger than the coating thickness of the photosensitive composition, causing defects and irregularities. If it is less than 20 micrometers, it will become smaller than the coating film thickness of a photosensitive composition, and since it will become a possibility of causing a defect and an unevenness | corrugation, it will not become a problem. In the present invention, it is important that the number of aggregates having a particle size of 20 μm or more is less than 50 in 100 g of the composition. Preferably it is less than 40, more preferably less than 35. If it is less than 50, even if an aggregate having a particle size of 20 μm or more is contained, there is no problem because the possibility of causing defects and irregularities is reduced. The agglomerate here means that each primary particle such as an inorganic powder or filler existing in a dispersed state in the photosensitive composition passes through water, an organic solvent or the like, or the van der Waals force of the particle itself, ion It is a consolidated structure composed of a plurality of primary particles that are firmly bonded by a decrease in cohesive energy caused by attractive force due to the sharing of atomic force and valence electrons. Depending on the magnitude of the bonding force, it can be easily crushed, and in some cases, considerable energy is required to crush. Even if such an aggregate is recognized as one structure by the naked eye, each particle can be observed with the interface clearly distinguished by a microscope or the like, and acts between the particles. It behaves as one particle by the above binding force. These are sometimes referred to as aggregates, coagulums, aggregates and the like. In many cases, the aggregates are not spherical, and the particle diameter of the aggregates herein is defined as the major axis of the aggregates observed with an optical microscope or the like.

In the present invention, the number of aggregates is calculated by the following method. First, the photosensitive composition of the present invention was applied to a substrate on which a ITO cathode electrode (thickness 150 nm) was formed on a 200 mm × 200 mm × 1.8 mm soda lime glass substrate with a spinner at 1500 rpm for 30 seconds and dried. A coating film was formed. The same operation is repeated, and 10 coated substrates are prepared, and then the aggregates are observed with respect to any 20 cm ² of the surface of the coating film using a microscope. Among the aggregates observed in the observation range, the number of aggregates whose major axis is 20 μm or more is counted. The same operation is repeated 10 times randomly on one substrate, and the average number of aggregates is calculated. Thereafter, the same operation is performed on 10 substrates, and after calculating the average number of aggregates of the photosensitive composition, the specific gravity of the composition or the average weight of the composition per substrate is converted to 100 g of the composition. To do.

  The photosensitive composition of the present invention can be prepared as follows. First, a dispersant is added to inorganic powder to obtain a primary mixture (mixing step). Next, the primary mixture is subjected to high shear stress of 100 MPa or more and kneaded (primary dispersion step). Thereafter, a photosensitive organic component is added to obtain a secondary mixture (secondary mixing step), and the secondary mixture is dispersed by a roll mill or the like (secondary dispersion step). Finally, an organic solvent is added to adjust the viscosity (viscosity adjustment step). Since only the dispersant is added to the inorganic powder, there is little organic matter contained in the primary mixture state, and since this is subjected to a high shear stress of 100 MPa or more, the aggregate is stressed, and the primary mixture is easily obtained. It can be crushed and dispersed into particles. After the pulverization, the dispersing agent effectively adheres to the primary particles, whereby reaggregation can be suppressed. The shear stress is preferably 100 MPa or more, more preferably 200 MPa or more, and still more preferably 500 MPa or more. In addition, after performing a primary dispersion step in which a high shear stress of 100 MPa or more is applied and kneaded, a secondary dispersion step in which a photosensitive organic component is added, dissolved and diluted, and mixed and dispersed, and then dispersed by a roll mill or the like. Since the tertiary dispersion step is performed, the adsorption of the organic binder to the inorganic powder can be facilitated. For this reason, the photosensitive composition which was further excellent in the dispersibility is obtained. In the photosensitive composition thus obtained, the number of aggregates having a particle size of 20 μm or more can be less than 50 in 100 g of the composition.

  The apparatus used in the primary dispersion step is not particularly limited as long as it can apply a high shear stress of 100 MPa or more, but an automatic mortar, a kneader, and a planetary mixer are preferable. The viscosity in the primary dispersion step is preferably 10,000 Pa · s (Pascal · second) or more. Within this viscosity range, the inorganic powder can be sufficiently crushed and dispersed. In the primary dispersion step and the secondary dispersion step, it is preferable to use the same disperser. However, different dispersers are used in consideration of the viscosity of the mixture to be dispersed, the productivity of the disperser, and the characteristics. Also good.

  Further, various ball mills and the like can be appropriately selected and used as an apparatus used in the tertiary dispersion step. Here, the ball mill includes not only a so-called narrow ball mill that functions to dissociate the agglomerated particles by rolling ceramic balls or the like in a container, but also includes a vibrating ball mill, a medium planetary mill, and the like. In addition, a roll mill or the like can be used, and a three-roll mill or its application device can be used.

  The viscosity adjustment of the photosensitive composition is appropriately adjusted depending on the addition ratio of the inorganic component, the thickener, the organic solvent, the plasticizer, the precipitation inhibitor, and the like, and the range is preferably 0.5 to 200 Pa · s. For example, when applying to a glass substrate by a spin coat method, 0.5-5 Pa.s is preferable. In order to obtain a film thickness of 10 to 20 μm by applying it once by the screen printing method, 50 to 200 Pa · s is preferable. In the case of using a blade coater method or a die coater method, 2 to 20 Pa · s is preferable.

  Examples of the organic solvent used for adjusting the viscosity of the solution include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, and 3-methoxy-3-methyl-1. -Butanol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, terpineol, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid and the like, and an organic solvent mixture containing one or more of these Used.

  In addition, since the photosensitive composition of the present invention is used in a state where the solvent is volatilized, hereinafter, when it is simply referred to as “photosensitive composition”, it is assumed that the solvent is not included unless otherwise specified. When the content in the inside is calculated, the content with respect to the whole solid excluding the solvent is shown.

  Moreover, the photosensitive composition of this invention contains a dispersing agent. Examples of the dispersant include a dispersant having an acid group such as phosphoric acid, carboxylic acid, fatty acid, and esters thereof. In particular, a compound having a phosphate ester skeleton is preferably used. In addition, addition of nonionic, cationic, anionic surfactants, wetting agents such as polyvalent carboxylic acids, amphoteric substances, and resins having highly sterically hindered substituents can be mentioned. Moreover, the polarity of the system at the time of dispersion or after dispersion can be controlled by addition of a solvent. The content of the dispersant is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 10% by weight, still more preferably from 1 to 5% by weight, based on the inorganic powder. If it is in this range, it adheres to the surface of the inorganic powder and can effectively exert the dispersion effect.

  Examples of the inorganic powder used in the present invention include glass powder, ceramic powder, glass / ceramic powder, metal powder such as silver, copper, palladium, tungsten, etc., but the insulating layer forming application includes glass powder, ceramic powder, glass / ceramic. Powder is preferable, and glass powder is more preferable because it can be fired at a low temperature. Moreover, it is preferable that the inorganic powder contains particles having an average refractive index of 1.8 or more. More preferably, it is 1.9 or more and 2.2 or less. More preferably, it is 2.0 or more and 2.2 or less. Within this range, the pattern can be finely processed.

  The average particle size of the inorganic powder used in the present invention is preferably 0.01 μm to 5 μm. The average particle diameter of the inorganic powder can be determined by measuring the specific surface area by laser diffraction method or BET method, and then converting the particle assuming a sphere. When the particles are nano-sized, it is difficult to measure accurately, and therefore the BET method equivalent value is used in the present invention.

  The content of the inorganic powder in the photosensitive composition is preferably 10 to 95% by weight, more preferably 50 to 90% by weight, and further preferably 70 to 88% by weight. By making it 10% by weight or more, the pattern shape at the time of firing can be made preferable, while by making it 90% by weight or less, good photosensitive characteristics can be obtained. Moreover, as volume content, 20-70 volume% is preferable, 30-65 volume% is more preferable, and 40-60 volume% is further more preferable. The pattern shape at the time of baking can be made preferable by setting it as 20 volume% or more, and a favorable photosensitive characteristic is acquired by setting it as 70 volume% or less.

  The refractive index of the inorganic powder is measured using a Becke method, a V block method, an ellipsometer, or the like. Measuring the refractive index at the exposure wavelength is accurate in confirming the effect. In particular, it is preferable to measure with light in the wavelength range of 350 to 650 nm. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable. In the present invention, it is a value measured by an ellipsometer.

The components of the glass powder used in the present invention, it is desirable _{to Bi} 2 _{O 3} comprises in the range of 70 to 91 wt%, more preferably 73 to 85 wt%. If Bi ₂ O ₃ is less than 70% by weight, the thermal softening point is increased, which is not preferable. If Bi ₂ O ₃ exceeds 91% by weight, the heat resistant temperature of the glass is lowered, which is not preferable in terms of baking onto a glass substrate.

SiO2 is preferably ₃ to 15% by weight. When it is less than 3% by weight, vitrification becomes difficult. On the other hand, if it exceeds 15% by weight, the heat softening point becomes high, and baking on the glass substrate becomes difficult.

B ₂ O ₃ is preferably 5 to 20 wt%. More preferably, it is 7 to 15% by weight. By including B ₂ O ₃ , electrical, mechanical and thermal characteristics such as electrical insulation, strength, thermal expansion coefficient, and denseness can be adjusted. If it exceeds 20% by weight, the stability of the glass with respect to acid and water decreases.

ZrO ₂ is preferably contained in the range of 0 to 5% by weight, more preferably 0.01 to 2.5% by weight, and still more preferably 0.01 to 1% by weight. ZrO ₂ improves the acid resistance of the glass material, but if it exceeds 5% by weight, the glass becomes non-uniform.

  ZnO is preferably 1 to 10% by weight, more preferably 2 to 5% by weight. If it is less than 1% by weight, the effect of improving the density is small, and if it exceeds 20% by weight, the baking temperature becomes low and it becomes difficult to control, and the insulation resistance also becomes low.

As raw materials for glass powder, for example, as SiO ₂ , potassium feldspar, soda feldspar, kaolin, silica sand, etc., Al ₂ O ₃ as alumina, aluminum hydroxide, potassium feldspar, soda feldspar, kaolin, etc., B _{As 2} O ₃ , boric acid or borax can be used, and as ZnO, zinc white or the like can be used. These raw materials, Bi ₂ O ₃ , ZrO _2, and the like are mixed so as to have a predetermined composition, melted at 900 to 1200 ° C., rapidly cooled, glass frit, and then pulverized into a fine powder. As a method for pulverizing glass, there are a ball mill, a bead mill, an attractor, a sand mill, and the like. Of these, a ball mill and a bead mill are preferably used.

In addition to the glass powder, a filler may be added as the inorganic powder of the photosensitive composition when used for forming the insulating layer of the electron-emitting device. Specific examples of the filler include ceramic powders such as SiO ₂ , Al ₂ O ₃ , ZrO ₂ , mullite, spinel, magnesia, ZnO, and titanium oxide. These may be used alone or in combination. Also good. The amount of filler added is preferably less than 10% by volume with respect to the total volume of the photosensitive composition. If it is more than that, cracks may occur during sintering. The filler is preferably one that does not melt during sintering.

  The average particle size of the glass powder contained in the inorganic powder used for forming the insulating layer of the electron-emitting device is preferably 0.1 to 5 μm, more preferably 0.1 to 2 μm, and more preferably 0.1. ˜1 μm. By using a glass powder having an average particle diameter of 0.1 μm or more, a photosensitive composition that hardly causes aggregation is obtained. By using a glass powder having an average particle diameter of 5 μm or less, processing by fine photolithography in a thin film can be performed. It becomes possible. The average particle size of the filler contained in the inorganic powder used for forming the insulating layer of the electron-emitting device is preferably 0.01 μm to 0.5 μm, and more preferably 0.01 to 0.05 μm. . The strength of the fired member can be improved by adding a filler of 0.01 μm or more, and good photosensitive characteristics can be obtained by using a filler of 0.5 μm or less.

  When the insulating layer is not directly formed on the substrate, for example, when the insulating layer is formed separately from the substrate and then laminated, it is preferable to include ceramic powder. Furthermore, in order to reduce the melting point and enable firing at a low temperature, the following modes are preferably used for the inorganic powder, for example. 30 to 70% by weight of a glass component, and at least one ceramic component 30 to 30 selected from the group consisting of alumina, zirconia, magnesia, beryllia, mullite, spinel, forsterite, anosart, serdian, cordierite, and aluminum nitride It is a mixture with 70% by weight. The heat softening temperature of the glass component contained in the inorganic powder is preferably 500 ° C to 700 ° C. When the insulating layer is not directly formed on the substrate, the average particle size of the ceramic component contained in the inorganic powder is preferably 0.01 to 5 μm, more preferably 0.03 to 0.2 μm. Within this range, processing by fine photolithography is possible.

In addition to the use for forming an insulating layer of an electron-emitting device, it is preferably used for, for example, an insulating layer of a semiconductor circuit and an insulating layer of a ceramic multilayer substrate, but is not limited thereto.
In the present invention, the photosensitive organic component may be a negative type that is cured by light or a positive type that is solubilized by light.

  In the present invention, the photosensitive organic component is one or more selected from the group consisting of a) an ethylenically unsaturated group-containing compound and a photopolymerization initiator, b) a glycidyl ether compound, an alicyclic epoxy compound, and an oxetane compound. Any one or more of a cationically polymerizable compound and a photocationic polymerization initiator, and c) one or more compounds selected from the group consisting of a quinonediazide compound, a diazonium compound and an azide compound are preferably used.

  The content of the ethylenically unsaturated group-containing compound is preferably 50 to 99.95% by weight, more preferably 60 to 90% by weight, based on the entire component a). By making it 50% by weight or more, fine pattern processing becomes possible, and by making it 99.95% by weight or less, the pattern shape after firing can be kept good.

  Moreover, it is preferable to use what has a sensitivity also to visible light with a wavelength of 400-450 nm as a photoinitiator among components a). In the present invention, one or more of these can be used. The photopolymerization initiator is preferably in the range of 0.05 to 50% by weight, more preferably 1 to 35% by weight, based on the entire component a). Within this range, the sensitivity is good and the remaining ratio of the exposed portion can be increased.

  The proportion of one or more cationically polymerizable compounds selected from the group consisting of glycidyl ether compounds, alicyclic epoxy compounds and oxetane compounds in the total component b) is preferably 50 to 99.99% by weight. Is 60 to 90% by weight. By making it within this range, the pattern shape can be kept good.

  The blending amount of the cationic photopolymerization initiator is preferably in the range of 0.01 to 50% by weight of the total component b). In addition, 9,10-dimethoxy-2-ethyl-anthracene, 9,10-diethoxyanthracene, 2,4-diethylthioxanthone, etc. are preferably added as a photocationic polymerization accelerator.

  The proportion of the quinonediazide compound in the total component c) is preferably 1% by weight or more and 90% by weight or less, more preferably 3% by weight or more and 80% by weight or less. If the quinonediazide compound is less than 1% by weight, the change in solvent solubility due to the quinonediazide compound during exposure is reduced, resulting in poor pattern formation. On the other hand, if it is more than 90% by weight, the dispersibility of the photosensitive composition is reduced. May cause problems.

  The proportion of the diazonium compound in the total component c) is preferably 5 to 80% by weight, more preferably 10 to 50% by weight. If the amount of the diazonium compound is too small, curing may be insufficient. Conversely, if the amount is too large, a problem may occur in the storage stability of the composition.

  The proportion of the azide compound in the total component c) is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. When the amount of the azide compound is too small, curing of the photosensitive component may be insufficient, and when the amount is too large, the stability of the composition may be adversely affected.

  As the photosensitive organic component as described above, an ethylenically unsaturated group-containing compound and a photo-radical polymerization initiator as component a) are preferred because of the wide variation in material selection and the ease of controlling the performance based thereon.

  The content of the compound selected from components a) to c) is preferably 5 to 98% by weight with respect to the photosensitive organic component. More preferably, it is 10 to 70% by weight. By making it the range of 5-98 weight%, pattern workability can be maintained favorable.

  The refractive index of the photosensitive organic component is generally in the range of 1.4 to 1.7. The average refractive index of the photosensitive organic component is determined by the following method. First, the refractive index at a desired wavelength is measured for each component by the V-block method. Next, it is obtained by adding the respective refractive indexes according to the weight% of the photosensitive organic component. For example, a certain photosensitive organic component is composed of A (50 wt%) and B (50 wt%), the refractive index of component A at a certain wavelength is 1.46, and the refractive index of component B is 1.58. In this case, the average refractive index of the photosensitive organic component is (1.46 × 0.5) + (1.58 × 0.5) = 0.73 + 0.79 = 1.52. Alternatively, the photosensitive organic component is applied on glass and dried, and then directly measured using an ellipsometer. The refractive index is measured accurately at the wavelength used when exposing the photosensitive composition in order to confirm the effect. Since light in a wavelength range of 350 to 650 nm is usually used for exposure, it is preferable to measure in this range. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable.

  Generally, in a photosensitive composition containing a photosensitive organic component and glass powder, it is preferable that the average refractive index of the photosensitive organic component and the average refractive index of the glass powder are as close as possible. When the refractive index is close, light scattering at the interface between the photosensitive organic component and the glass powder hardly occurs, and fine pattern processing becomes possible when pattern formation is performed using photolithography.

  However, the bismuth glass preferably used in the present invention has advantages such as low firing temperature and high acid resistance and alkali resistance, but has a large refractive index and it is difficult to make the average refractive index less than 1.8. . Therefore, the refractive index difference between the photosensitive organic component and the glass powder is as large as 0.1 to 1.3. When the refractive index difference is large, light does not reach the inside of the photosensitive composition sufficiently due to light scattering at the interface between the photosensitive organic component and the glass powder, and the portion far from the exposure surface is difficult to cure.

  Therefore, in this invention, it is preferable to contain the compound (henceforth a compound (A)) which absorbs light and emits a light of a longer wavelength than this absorbed light in a photosensitive organic component. When such a compound is contained, even when the refractive index difference between the photosensitive organic component and the glass powder is large, it is possible to cure a portion far from the exposure surface. The compound (A) absorbs light having a wavelength used for exposure, emits light having a longer wavelength than the absorbed light, and the emitted light cures or solubilizes the photosensitive organic component. Since the compound (A) absorbs ultraviolet rays to suppress scattering and emits long-wavelength fluorescence that is more transmissive than ultraviolet rays, a portion far from the exposure surface can be cured.

  The absorption wavelength range of the compound (A) is preferably a wavelength range of 320 to 410 nm, more preferably 350 nm to 380 nm, still more preferably 360 nm to 375 nm. In particular, the maximum absorption wavelength is more preferably in the range of 350 nm to 380 nm. In addition, the fluorescence emission wavelength region of the compound (A) when measured in a 3-methoxy-3-methyl-1-butanol solution is preferably 400 to 500 nm, more preferably 400 to 450 nm. More preferably, it is 430 nm-445 nm. In particular, the maximum emission wavelength is more preferably in the range of 400 nm to 450 nm. If the absorption wavelength region and the emission wavelength region are within this range, it effectively absorbs ultraviolet rays at the time of exposure, suppresses scattering, and emits fluorescence in a wavelength region that is more transmissive than ultraviolet rays to irradiate, That is, the photosensitive organic component can be cured or solubilized to a portion far from the exposure surface.

  In the range of the content of the compound (A), the molar extinction coefficient of the compound (A) is preferably 20000 or more. The molar extinction coefficient is preferably 60000 or less. Within this range, ultraviolet rays can be absorbed effectively, scattering of ultraviolet rays during exposure can be suppressed, and the photosensitive organic component can be cured or solubilized to a deeper portion.

  The absorption wavelength of ultraviolet rays, the emission wavelength of fluorescence, and the molar extinction coefficient were measured with a spectrofluorometer (F-2500, manufactured by Hitachi, Ltd.), and an ultraviolet-visible spectrophotometer (MultiSpec 1500, manufactured by Shimadzu Corporation). Can be measured.

  Examples of the compound (A) used in the present invention include fluorescent whitening agents such as coumarin fluorescent whitening agents, oxazole fluorescent whitening agents, stilbene fluorescent whitening agents, imidazole fluorescent whitening agents, and triazole fluorescent whitening agents. Preferably, fluorescent whitening agents such as imidazolones, imidazolones, methines, pyridines, anthrapyridazines, and carbostyrils are used. A coumarin-based fluorescent brightener or an oxazole-based fluorescent brightener is more preferably used because of its good compatibility with the compounds selected from a) to c) contained in the photosensitive organic component and a binder polymer. In particular, a coumarin-based optical brightener is preferable because of its high solubility in polar solvents. The solubility of the compound (A) in the polar solvent is preferably 2 g / 100 g solvent or more, more preferably 50 g / 100 g solvent or more. From the viewpoint of solubility, a coumarin fluorescent whitening agent is particularly preferable. These may be used alone or in combination. The coumarin fluorescent whitening agent has a coumarin structure in the molecule. Specific examples of the coumarin fluorescent brightener include 7-diethyldiamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7-dimethylamino-4- Examples thereof include methylcoumarin and 7-amino-4-methylcoumarin. The oxazole fluorescent whitening agent has an oxazole ring in the molecule. The stilbene fluorescent whitening agent has a stilbene structure in the molecule. Specific examples of the stilbene fluorescent brightener include s-triazine ring substitution of 4,4'-diaminostilbene-2,2'-disulfonic acid, stilbene triazole, imidazole, and oxazole substitution. The imidazole fluorescent whitening agent has an imidazole structure in the molecule. The triazole fluorescent whitening agent has a hetero 5-membered ring composed of 3 nitrogen atoms and 2 carbon atoms in the molecule. Specific examples of the 5-membered ring include the following rings.

  The content of the compound (A) in the present invention is preferably 0.1 to 30% by weight with respect to the photosensitive organic component. Particularly for field emission members and fluorescent light emitting device applications, the content is preferably 2 to 20% by weight, more preferably 5 to 15% by weight. Within this range, fine pattern processing is possible.

  In the present invention, the photosensitive organic component may further contain a cage silsesquioxane. The cage silsesquioxane may be added to the photosensitive composition as it is, or may be added after previously reacting with another compound. In the case of reacting with another compound in advance, it is preferable to react with a compound constituting the photosensitive organic component from the viewpoint of increasing the compatibility.

  In the present invention, the photosensitive organic component preferably further has a binder polymer, and contains additives such as an ultraviolet absorber, a sensitizer, a polymerization inhibitor, a plasticizer, a dispersant, and an antioxidant. be able to.

  As the binder polymer, various polymers such as acrylic resin, epoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, silicone resin, melamine resin, phenol resin, cellulose derivative, and polyvinyl alcohol can be used. Methacrylate, polyvinyl butyral, polyvinyl alcohol, ethyl cellulose, (meth) acrylic acid ester copolymer and the like are preferable. Furthermore, from the viewpoint of dispersibility and developability of the inorganic powder, in addition, from the viewpoint of pattern formation by photosensitivity, the binder polymer has a reactive functional group such as a carboxyl group, a hydroxyl group, and an ethylenically unsaturated double bond. It is preferable.

  A preferable binder polymer when the component a) is used as the photosensitive organic component is a reactive functional group of the binder polymer obtained by copolymerization of the ethylenically unsaturated double bond-containing compound as described above or by copolymerization. It can be obtained by adding an ethylenically unsaturated group-containing compound having a reactive functional group to a part of the group.

  The content of the binder polymer in the photosensitive organic component is preferably 1 to 70% by weight with respect to the photosensitive organic component. More preferably, it is 5 to 50% by weight. By setting the content in the range of 1 to 70% by weight, it is possible to achieve both pattern processability and characteristics such as shrinkage during firing.

  It is also effective to contain an ultraviolet absorber in the photosensitive composition of the present invention. By containing the ultraviolet absorber, light scattering in the exposure process is further suppressed, and a pattern with a high aspect ratio, high definition and high resolution can be formed. As the ultraviolet absorber, an organic dye, particularly an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Even when an organic dye is added as an ultraviolet absorber, it is preferable because it does not remain in the glass film after firing and the deterioration of the insulating film characteristics due to the ultraviolet absorber can be reduced. As such a compound, an azo dye or a benzophenone dye is preferable because the absorption wavelength can be easily controlled in a desired wavelength region. The content of the ultraviolet absorber in the photosensitive organic component is preferably 0.05 to 5% by weight with respect to the photosensitive organic component. More preferably, it is 0.1 to 1 weight%. If it is less than 0.05% by weight, the effect of adding an ultraviolet absorber is reduced, and if it exceeds 5% by weight, the properties of the insulating film after firing are deteriorated.

  A sensitizer is added in order to improve sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, Examples include 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone and Michler's ketone. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When it contains a sensitizer, its content is preferably 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, based on the photosensitive organic component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

  Furthermore, it is preferable to contain a polymerization inhibitor. Specific examples of the polymerization inhibitor include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, and pyrogallol. When a polymerization inhibitor is contained, the content thereof is preferably 0.001 to 1% by weight with respect to the entire photosensitive composition.

  Moreover, you may contain a plasticizer or antioxidant. Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like. Specific examples of antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol, 2,2-methylene-bis (4 -Methyl-6-t-butylphenol), and the like. When it contains a plasticizer, its content is preferably 0.5 to 10% by weight with respect to the entire photosensitive composition. When adding an antioxidant, the content is preferably 0.001 to 1% by weight with respect to the entire photosensitive composition.

  The photosensitive composition of the present invention is preferably used for various insulating layer members of electron-emitting devices, but is particularly preferably used as a field emission member typified by an insulating layer of a field emission display. Field emission refers to field electron emission. Field electron emission refers to a cathode made of a conductor such as a semiconductor or metal in a vacuum. When an anode is placed near the surface, electrons are emitted from the cathode surface toward the anode. A physical phenomenon that is released into a vacuum. In the present invention, the field emission member refers to a member utilizing such field electron emission. Specific examples include, but are not limited to, field emission displays, backlights for liquid crystal displays, field emission lamps, electron beam sources for scanning electron microscopes, and micro vacuum tubes.

  The thickness of the insulating layer of the electron-emitting device is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and further preferably 1 to 10 μm. When the thickness is 0.1 μm or more, the function as an insulating layer can be achieved, and when the thickness is 20 μm or less, the electron emission characteristics can be kept good. When producing a field emission member using the photosensitive composition of the present invention, a glass substrate is preferably used as the substrate. As the glass substrate, soda lime glass or heat resistant glass (PD200 manufactured by Asahi Glass Co., Ltd., PP8 manufactured by Nippon Electric Glass Co., Ltd., CS25 manufactured by Saint-Gobain Co., Ltd., CP600V manufactured by Central Glass Co., Ltd.) can be preferably used. It is more preferable to use soda lime glass from the viewpoint of low cost. Moreover, a ceramic substrate, a metal substrate, a semiconductor substrate (AlN, CuW, CuMo, SiC substrate, etc.), and various plastic films can also be used. On these substrates, if necessary, one or more insulators, semiconductors, and conductors, or a combination thereof may be formed.

  Next, as an example, a method for manufacturing a field emission member will be described with reference to a method for manufacturing an insulating layer of a field emission display.

  As a substrate, the photosensitive composition of the present invention is applied to the whole or a part of a glass substrate on which an ITO cathode electrode is formed. As a coating method, general methods such as screen printing, bar coater, roll coater, and slit die coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the photosensitive composition, but considering the shrinkage due to drying or baking, the thickness after drying is 5 to 100 μm, preferably 5 to 60 μm, More preferably, it is preferably applied so as to be 5 to 40 μm.

  When the photosensitive composition is applied a plurality of times, the first and second and subsequent photosensitive compositions may be the same photosensitive composition or different photosensitive compositions. . Moreover, when apply | coating a photosensitive composition in multiple times, it is preferable to dry after the photosensitive composition application of the 1st time and before the photosensitive composition application of the 2nd time or later. If it does so, the reduction | decrease of the thickness of the coating film at the time of the 2nd photosensitive composition application | coating can be prevented. Although the drying temperature and time vary depending on the composition of the photosensitive composition to be constituted, it is preferably applied at 50 to 100 ° C. for about 5 to 30 minutes. Further, it is desirable that drying be performed in a convection drying furnace or an IR drying furnace.

  Moreover, the organic solvent residual amount in the photosensitive composition before subjecting to exposure is 3 weight% or less, Preferably, it is 1 weight% or less. When it exceeds 3% by weight, tackiness is deteriorated, and adhesion of the composition to the photomask becomes a problem.

  After forming a film of the photosensitive composition on the substrate as described above, a pattern can be formed by exposure and development. The shape of the pattern varies depending on the field emission member. In the case of the insulating layer of the field emission display, a pattern including a circular hole having a diameter of 3 to 100 μm or a square having a side of 3 to 100 μm is formed. It is preferable to do. One side of the circle or quadrangle is more preferably 3 to 50 μm, still more preferably 3 to 20 μm. If it exists in this range, the effect of the photosensitive composition can fully be exhibited.

  For exposure, a mask exposure method using a photomask and a direct drawing exposure method using a laser beam or the like can be used. However, exposure using a photomask can shorten the exposure time. As an exposure apparatus in this case, a stepper exposure machine, a proximity exposure machine, or the like can be used.

Examples of the active light source used include visible light, near ultraviolet light, ultraviolet light, near infrared light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable, and as the light source, for example, Low pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, halogen lamp, germicidal lamp, etc. can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, exposure is performed for 0.5 to 30 minutes using an ultrahigh pressure mercury lamp with an output of 0.5 to 1000 W / m ² . In particular, it is preferable to perform exposure with an exposure amount of about 0.05 to 1 J / cm ² . The wavelength of light used for exposure is preferably 300 to 650 nm, more preferably 350 to 650 nm, still more preferably 350 to 500 nm, and most preferably 350 nm to 450 nm.

  Thereafter, development is performed using a developing solution. In this case, the immersion method, the spray method, the shower method, and the brush method are used. Among these, the shower method is preferable in that uniform development can be realized. As the developer, an organic solvent or an aqueous solution in which an organic component in the photosensitive composition can be dissolved or dispersed is used. An aqueous solution containing an organic solvent may be used. When the photosensitive composition contains a compound having a functional group such as a carboxyl group, a phenolic hydroxyl group, or a silanol group, it can be developed even in an alkaline aqueous solution. A metal alkali aqueous solution such as sodium hydroxide, calcium hydroxide, sodium carbonate aqueous solution or the like can be used as the alkali aqueous solution. However, it is preferable to use an organic alkali aqueous solution because an alkaline component can be easily removed during firing. As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine. The concentration of the alkali component in the aqueous alkali solution is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight. If the alkali concentration is too low, the unexposed portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the exposed portion may be corroded. It is preferable in terms of process control that the temperature of the developer during development is 20 to 50 ° C.

  In addition, it is preferable to add a surfactant to the developer in order to improve the wettability of the photosensitive composition to the coating film, the uniformity of development, and the reduction of residues. As the surfactant, nonionic, anionic, cationic and amphoteric surfactants can be used. Moreover, it is preferable to perform ultrasonic treatment in a developing solution at the time of development. Furthermore, the frequency modulation type ultrasonic treatment, in which the frequency modulation type ultrasonic treatment is modulated in a wavelength range between 20 and 50 KHz, is preferable. By such ultrasonic treatment, a great effect can be obtained in forming a fine and uniform pattern and reducing the residue.

  By the method as described above, a pattern containing a circular hole having a thickness of 5 to 100 μm and a diameter of 3 to 100 μm or a side of 3 to 100 μm can be formed on the substrate from the photosensitive composition of the present invention.

  Thereafter, the patterned substrate is baked in a baking furnace to burn out organic components, and at the same time, the glass powder is sintered to form an insulating layer. The firing atmosphere, temperature, and time can be appropriately selected depending on the type of the photosensitive composition and the substrate, and firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. Baking is preferably performed by holding at a temperature of 400 to 600 ° C. for 10 to 60 minutes. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. Moreover, you may heat at 50-300 degreeC in the above each process for the purpose of drying and a preliminary reaction.

  Through the above steps, an insulating layer for a field emission display having a pattern including a circular hole having a thickness of 5 to 100 μm and a diameter of 3 to 100 μm or a square of 3 to 100 μm on one side formed on the substrate is obtained. In order to reduce the voltage of the field emission display, it is necessary to make the distance between the gate electrode portion and the electron emission source closer. Therefore, the thickness of the insulating layer is preferably 20 μm or less. Further, in order to achieve high resolution and uniform luminance, the holes formed in the insulating layer are preferably 40 μm or less.

  For example, the gate electrode is formed by the following method. After forming an electrode film by sputtering or vapor deposition on the insulating layer in which holes having a desired pattern are formed, a method of etching the electrode film of the hole part or a process of covering the hole part first, The electrode film is formed by a sputtering method or a vapor deposition method and the cover is removed. The method of forming the electron emission source differs depending on the electron emission source. When the electron emission source is a Spindt type metal chip (or microchip), a vapor deposition method is used. When a carbon nanotube (CNT) is used, a photosensitive paste is used. Or a direct growth method using a plasma CVD method. A back electrode of a field emission display can be obtained by forming a gate electrode on the insulating layer with the hole pattern obtained in this way, and creating an electron emission source inside the hole pattern. Then, the back plate and the front plate having the anode electrode are bonded to each other with a spacer glass sandwiched between them, vacuum exhausted and sealed with an exhaust pipe connected to the container, and then wiring is mounted, resulting in high brightness and high contrast. A triode type field emission display can be obtained. In order to confirm the electron emission state, by supplying a voltage of 1 to 5 kV to the anode electrode, electrons are emitted from the electron emission source, and phosphor emission can be obtained.

Below, it demonstrates concretely using an Example. However, the present invention is not limited to this.
<Measurement method>
The weight average molecular weight of the binder polymer was measured by size exclusion chromatography using tetrahydrofuran as a mobile phase. The column was Shodex KF-803, and the weight average molecular weight was calculated in terms of polystyrene.

  The acid value of the binder polymer was determined by dissolving 1 g of the binder polymer in 100 mL of ethanol and then titrating with a 0.1N potassium hydroxide aqueous solution.

  The viscosity of the binder polymer was measured with a rotational viscometer (RVDVII +, manufactured by Brookfield) at a temperature of 25 ± 0.1 ° C., a rotation speed of 10 rpm, and a viscosity after 5 minutes from the start of measurement.

  The thermal decomposition temperature of the binder polymer is set with an about 20 mg sample with a TG measuring device (TGA-50, manufactured by Shimadzu Corporation), in an air atmosphere with a flow rate of 20 ml / min, at a heating rate of 10 ° C./min. The temperature is raised to 700 ° C. A chart in which the relationship between temperature (vertical axis) and weight change (horizontal axis) was plotted was printed, the tangent line between the part before decomposition and the part during decomposition was drawn, and the temperature at the intersection was taken as the thermal decomposition temperature.

  The glass transition point (Tg) of the binder polymer was measured using a DSC-50 type measuring device manufactured by Shimadzu Corporation with a sample weight of 10 mg at a heating rate of 20 ° C./min under a nitrogen stream, The temperature at which the initiation starts was defined as Tg.

  The thermal softening temperature of glass powder is put into a platinum cell, and differential thermal analysis is performed at a temperature increase rate of 20 ° C./min from room temperature to 700 ° C. using a differential thermal analyzer (TG8120, manufactured by Rigaku Corporation). The temperature at which the endotherm ends through the minimum point of the endothermic portion that appears first is defined as the softening point (Ts).

  The average particle diameter of the glass powder was measured by a laser diffraction scattering measurement device (Microtrac particle size distribution analyzer HRA, manufactured by Nikkiso Co., Ltd.) and the BET method, that is, the specific surface area was measured by adsorbing an inert gas such as nitrogen gas. Later, assuming that the particles are spheres, the particle diameter was determined from the specific surface area, and the average particle diameter was calculated as the number average. The specific gravity was measured by processing the glass into a size of about 5 × 5 × 5 mm and using the Archimedes method.

  The viscosity at the time of primary dispersion was measured with a rotational viscometer (RVDVII +, manufactured by Brookfield) at a temperature of 25 ± 0.1 ° C., a rotational speed of 0.3 rpm, and a viscosity after 5 minutes from the start of measurement.

The number of agglomerates was obtained by applying the photosensitive composition to a substrate having an ITO cathode electrode (thickness 150 nm) formed on a 200 mm × 200 mm × 1.8 mm soda lime glass substrate with a spinner at 1500 rpm for 30 seconds and drying. Then, a coating film was formed. After repeating the same operation and preparing 10 coated substrates, the surface of the coating film was observed visually and using a microscope, and the aggregates having a major axis of 20 μm or more were observed in an observation area of 20 cm ² . The number of aggregates obtained is counted, and the same operation is randomly repeated 10 times for one substrate to calculate the average number of aggregates. Thereafter, the same operation was performed on 10 substrates, the average number of aggregates of the photosensitive composition was calculated, and then converted per 100 g of paste.

<Binder polymer I>
Weight average obtained by addition reaction of 0.4 equivalent of glycidyl methacrylate (GMA) to a carboxyl group of a copolymer composed of 40 parts by weight of methyl methacrylate, 20 parts by weight of ethyl acrylate, and 40 parts by weight of methacrylic acid It is a polymer having a molecular weight of 16000, an acid value of 105 mgKOH / g, a double bond density of 2.5 mmol / g, and a viscosity of 11.2 Pa · s. The thermal decomposition temperature was 430 ° C. and Tg was 74 ° C.

<Glass powder I>
The glass powder is Bi ₂ O ₃ (77.2 wt%), SiO ₂ (6.9 wt%), B ₂ O ₃ (10.2 wt%), ZrO ₂ (0 wt%) in terms of oxides, A glass powder having a composition of ZnO (2.5 wt%) and Al ₂ O ₃ (2.7 wt%) was used. The glass powder had a heat softening temperature of 493 ° C., an average particle diameter of 0.5 μm, a specific gravity of 6.1 g / cm ³ , and a refractive index ( _ng ) of 2.21.

<Glass powder II>
The glass powder is Bi ₂ O ₃ (67 wt%), SiO ₂ (7.6 wt%), B ₂ O ₃ (13.7 wt%), ZrO ₂ (0 wt%), ZnO (in terms of oxide) Glass powder having a composition of 8.0 wt%) and Al ₂ O ₃ (3.2 wt%). This glass powder had a heat softening temperature of 534 ° C., an average particle size of 1.4 μm, a specific gravity of 5.4 g / cm ³ , and a refractive index ( _ng ) of 1.98.

<Glass powder III>
The glass powder is composed of PbO (70 wt%), SiO ₂ (13 wt%), Al ₂ O ₃ (3 wt%), B ₂ O ₃ (10 wt%), ZnO (4 wt%) in terms of oxides. Glass powder of composition was used. This glass powder had a heat softening temperature of 590 ° C., an average particle size of 1.2 μm, and a refractive index ( _ng ) of 2.1.

<Glass powder IV>
The glass powder is Bi ₂ O ₃ (77.2 wt%), SiO ₂ (6.9 wt%), B ₂ O ₃ (10.2 wt%), ZrO ₂ (0 wt%) in terms of oxides, A glass powder having a composition of ZnO (2.5 wt%) and Al ₂ O ₃ (2.7 wt%) was used. This glass powder had a heat softening temperature of 493 ° C., an average particle diameter of 0.1 μm, a specific gravity of 6.1 g / cm ³ , and a refractive index ( _ng ) of 2.21.

<Glass powder V>
The glass powder is Bi ₂ O ₃ (77.2 wt%), SiO ₂ (6.9 wt%), B ₂ O ₃ (10.2 wt%), ZrO ₂ (0 wt%) in terms of oxides, A glass powder having a composition of ZnO (2.5 wt%) and Al ₂ O ₃ (2.7 wt%) was used. This glass powder had a heat softening temperature of 493 ° C., an average particle diameter of 6 μm, a specific gravity of 6.1 g / cm ³ , and a refractive index ( _ng ) of 2.21.

<Glass powder VI>
The glass powder is Li ₂ O (8 wt%), SiO ₂ (27 wt%), B ₂ O ₃ (30 wt%), ZnO (15 wt%), Al ₂ O ₃ (5 wt%) in terms of oxide. ), Glass powder having a composition of CaO (15 wt%) was used. The glass powder had a heat softening point of 500 ° C., an average particle diameter of 1.5 μm, a specific gravity of 2.6 g / cm ³ , and a refractive index ( _ng ) of 1.58.

<Glass powder VII>
The glass powder is SiO ₂ (60 wt%), PbO (17.5 wt%), CaO (7.5 wt%), MgO (3 wt%), Na ₂ O (3.2 wt%) in terms of oxides. , K ₂ O (2 wt%) and B ₂ O ₃ (5.8 wt%) were used. This glass powder had a glass softening point of 686 ° C. and an average particle size of 2 μm.

<Filler I>
Silica: Silica particles having an average particle diameter of 12 nm (Nippon Aerosil Co., Ltd., trade name: Aerosil 200), the average particle diameter is determined by measuring the specific surface area by the BET method using nitrogen gas, and assuming that the particles are spheres. The particle diameter was determined from the surface area, and the average particle diameter was determined as the number average.

<Ceramic powder I>
Alumina: Alumina particles having an average particle diameter of 37 nm (trade name Nanotech Al ₂ O ₃ manufactured by C-I Kasei Co., Ltd.) The average particle diameter is assumed to be a sphere after measuring the specific surface area by the BET method using nitrogen gas The particle diameter was determined from the specific surface area, and the average particle diameter was determined as the number average.

<Compound (A) I>
Coumarin derivative (Nippon Kayaku Co., Ltd., trade name Kayight B). The absorption maximum wavelength of ultraviolet light in a 3-methoxy-3-methyl-1-butanol solution was 370 nm, and the maximum emission wavelength of fluorescence was 441 nm.

<Compound (A) II>
Oxazole derivative (Nippon Kayaku Co., Ltd., trade name Kaylight O) The absorption maximum wavelength of ultraviolet light in a 3-methoxy-3-methyl-1-butanol solution was 374 nm, and the maximum emission wavelength of fluorescence was 436 nm.

<Dispersant I>
Phosphate ester dispersant (BIC Chemie Japan Co., Ltd., trade name W9010)
<Dispersant II>
Polymer Comb Dispersing Agent (Nippon Yushi Co., Ltd., trade name Mariarim AKM-053)
<Dispersant III>
Acrylic dispersant (Kyoeisha Chemical Co., Ltd., trade name Floren G-700)
Example 1
As a photosensitive organic component, 7.2 g of acrylic monomer (Nippon Kayaku Co., Ltd. Kayrad (registered trademark) TPA-330) which is an ethylenically unsaturated group-containing compound, 7.2 g of the binder polymer I, a solvent ( 20 g of 3-methyl-3-methoxybutanol), photopolymerization initiator (manufactured by Nippon Kayaku Co., Ltd., 2,4-dimethylthioxanthone and Ciba Specialty Chemicals, Inc., Irgacure (registered trademark) 369, weight of 1: 2 1.4 g of compound (used in ratio), 2.2 g of compound (A) I, 0.1 g of ultraviolet light absorber (Kayaset SF-G: manufactured by Nippon Kayaku Co., Ltd.), polymerization inhibitor (p-methoxyphenol) 0.3g was mixed and melt | dissolved, and it filtered using the membrane filter (pore diameter: 0.2 micrometer). As the inorganic powder, 80 g of the glass powder I and 1.6 g of the dispersant I as a dispersant were mixed, and the primary dispersion step was performed for 1 hour using an automatic mortar. The shear rate at this time was 20000 s ⁻¹ . Moreover, the viscosity at this time was 10000 Pa · s or more which is the measurement limit of the viscometer. The shear stress was given by shear rate × viscosity, and the shear stress at this time was 200 MPa or more. A photosensitive organic component was added thereto, and the mixture was stirred and mixed for 5 minutes to obtain a secondary mixture. Then, the secondary dispersion step was performed by passing the mixture through three rolls 5 times, and a solvent (3-methyl-3-methoxy was added thereto. The viscosity was adjusted by adding 15 g of butanol) and stirring to prepare a photosensitive composition. The photosensitive composition was further filtered using a PTFE filter (pore size: 4 μm). The specific gravity of the photosensitive composition was 2.5 g / cm ³ . The viscosity of the obtained photosensitive composition was 2 Pa · s.

  When the number of aggregates of the photosensitive composition was measured, it was 10 per 100 g of the photosensitive composition.

Thereafter, the layer of the obtained photosensitive composition was subjected to an ultra-high pressure mercury lamp with an output of 0.5 kW from the upper surface using a negative chrome mask having a 15 μm via pattern / 90 μm pitch and a 20 μm via pattern / 110 μm pitch pattern. UV exposure. The exposure amount was 400 mJ / cm ² .

  Next, a 0.1% by weight aqueous solution of sodium carbonate maintained at 25 ° C. was developed for 30 seconds in a shower. Thereafter, it was washed with water using a shower spray, and a portion not photocured was removed to form a via pattern having a hole diameter of about 15 μm and about 20 μm on the glass substrate.

  The board | substrate after pattern formation was observed with the optical microscope, and the ratio by which the via pattern corresponding to each hole diameter was formed among 100 via patterns of a mask was evaluated as a via | veer processing rate (%). As a result, 100 via patterns were formed in both 15 μm and 20 μm, and the via processing rate was 100%. Moreover, when the surface of the pattern formation board | substrate was observed, the crack of the pattern was not seen. The substrate after pattern formation was heated up to the vicinity of the softening point of the glass powder at a temperature rising rate of 10 ° C./min, and held for 10 minutes for firing. The film thickness after firing was 10 μm.

Next, a positive type photoresist (trade name: AZ4620 manufactured by AZ Electronic Materials Co., Ltd.) was applied to the baked pattern forming substrate by a spin coater method, and then baked at 100 ° C. for 2 minutes. The film thickness of the photoresist was 10 μm. The obtained patterned substrate with a resist film was exposed to ultraviolet rays from an upper surface with an ultra-high pressure mercury lamp having an output of 0.5 kW using a negative chrome mask having a 35 μm via pattern / 90 μm pitch and a 50 μm via pattern / 110 μm pitch. The exposure amount was 100 mJ / cm ² . Next, the resist developer (trade name AZ400K manufactured by AZ Electronic Materials Co., Ltd., diluted by a factor of 5) maintained at 25 ° C. was immersed for 90 seconds and rocked for development. Thereafter, the resist pattern was obtained by washing with pure water for 30 seconds and performing post-baking at 120 ° C. for 2 minutes. Thereafter, a chromium film having a thickness of 150 nm was formed by sputtering.

  Subsequently, the resist film and the chromium film formed thereon were peeled off by immersing and shaking for 30 seconds in a resist stripping solution (trade name: AZ Remover 700, manufactured by AZ Electronic Materials Co., Ltd.) maintained at 25 ° C. Thereafter, the substrate was washed with pure water for 30 seconds to obtain a pattern formation substrate on which a gate electrode was formed.

  The electrical resistance of the pattern-formed substrate on which the obtained gate electrode was formed was measured using a tester to evaluate the electrical insulation. Those having a resistance value of 1 MΩ or more were judged good (（), those having a resistance value of 1 kΩ or more and less than 1 MΩ were judged as good (◯), and those having a resistance value of less than 1 kΩ were judged as bad (×). The evaluation result of electrical insulation was good (◎).

Examples 2-19
In the same manner as in Example 1, after preparing photosensitive compositions having the composition ratios shown in Tables 1 and 2, the number of aggregates was measured. Moreover, pattern formation was performed on the glass substrate in which the cathode electrode was formed, and the via processing rate and the electrical insulation after forming the gate electrode were evaluated. The results are shown in Tables 1-2. In Tables 1 and 2, the “photosensitive organic component” does not contain a solvent. Further, “amount (% by weight)” indicates the content with respect to the entire solid excluding the solvent.

Comparative Example 1
A photosensitive organic component was prepared in the same manner as in Example 1, mixed with inorganic powder and a dispersant, and then subjected to primary dispersion by passing it through three rolls five times, followed by solvent (3-methyl-3- Viscosity was adjusted by adding 15 g of methoxybutanol) and stirring and mixing to prepare a photosensitive composition. The shear rate during the primary dispersion was 20000 s ⁻¹ . Further, the viscosity at this time was 100 Pa · s or more. The shear stress at this time was 2 MPa. When this photosensitive composition was further filtered using a PTFE filter (pore diameter: 4 μm), a part was filtered, but the filter was clogged and could not be completely filtered. When the number of aggregates of the photosensitive composition was evaluated, it was 300 per 100 g of the photosensitive composition.

  When the electrical insulating properties of the patterned substrate on which the gate electrode formed in the same procedure as in Example 1 was evaluated, it was in a state where the gate electrode passed through the cathode electrode due to a defect, and it was defective (x). It was.

Comparative Examples 2-5
In the same manner as in Comparative Example 1, a photosensitive composition having a composition ratio shown in Table 3 was prepared, and the number of aggregates was measured. Moreover, pattern formation was performed on the glass substrate in which the cathode electrode was formed, and the via processing rate and the electrical insulation after forming the gate electrode were evaluated. The results are shown in Table 3. In Table 3, “photosensitive organic component” does not contain a solvent. Further, “amount (% by weight)” indicates the content with respect to the whole solid excluding the solvent.

Example 20
In the same manner as in Example 1, a photosensitive composition having a composition ratio shown in Table 4 was prepared, and then applied onto a PET film as a support using a doctor blade method, followed by drying at 85 ° C. for 15 minutes. The obtained sheet was cut into a size of 200 mm × 200 mm. The film thickness of the obtained sheet was 40 μm. After measuring the number of aggregates by the same method, pattern formation was performed and the via processing rate was evaluated. As a result, the via processing rate was 100% for both 15 μm and 20 μm. Next, the sheet was peeled off from the support, and the patterned sheet was heated to 850 ° C. at a temperature rising rate of 10 ° C./min, and held for 10 minutes for firing. The film thickness after firing was 20 μm. A gate electrode was formed on the obtained substrate, and electrical insulation was evaluated. The result was good.

Comparative Example 5
After preparing a photosensitive composition having the composition ratio shown in Table 4 in the same manner as in Example 20, the number of aggregates was measured by the same method, and after forming a gate electrode, the electrical insulation was evaluated. The results are shown in Table 4. In Table 4, “photosensitive organic component” does not contain a solvent. Further, “amount (% by weight)” indicates the content with respect to the whole solid excluding the solvent.

Claims (11)

A photosensitive composition for forming an insulating layer of an electron-emitting device comprising a photosensitive organic component, a dispersant, and an inorganic powder, wherein the number of aggregates having a particle size of 20 μm or more in 100 g of the composition is less than 50 The photosensitive composition characterized by the above-mentioned. A compound that absorbs light and emits light having a longer wavelength than the absorbed light is contained as the photosensitive organic component, and the content of the compound is 0.1 to 30% by weight with respect to the photosensitive organic component. 1. The photosensitive composition according to 1. The compound that absorbs the light and emits light having a longer wavelength than the absorbed light has a maximum absorption in the wavelength range of 350 nm to 380 nm and was measured in a 3-methoxy-3-methyl-1-butanol solution. The photosensitive composition according to claim 2, wherein the maximum emission wavelength of fluorescence is in the range of 400 nm to 450 nm. The photosensitive composition according to claim 2 or 3, wherein the compound that absorbs light and emits light having a longer wavelength than the absorbed light is a coumarin-based fluorescent brightener. The photosensitive composition according to claim 1, wherein the dispersant is a phosphate ester type. The photosensitive composition according to claim 1, wherein the inorganic powder is a glass powder. The glass powder is expressed in terms of oxide, Bi ₂ O ₃ 70 to 91 wt%, SiO _{2 3 to} 15 wt%, B ₂ O ₃ 5 to 20 wt%, ZrO ₂ 0 to 5 wt%, ZnO 1 to 10 wt% %. The photosensitive composition according to claim 6, comprising: The photosensitive composition according to claim 6 or 7, wherein the glass powder has an average particle diameter in terms of BET method of 0.01 to 5 µm. A method for producing a photosensitive composition for forming an insulating layer of an electron-emitting device comprising a photosensitive organic component, a dispersant, and an inorganic powder, wherein the method adds a dispersant to the inorganic powder to obtain a primary mixture. A mixing step, a primary dispersion step of dispersing the primary mixture, a secondary mixing step of adding a photosensitive organic component to the dispersion to obtain a secondary mixture, and a secondary dispersion step of dispersing the secondary mixture; A method for producing a photosensitive composition for forming an insulating layer of an electron-emitting device, comprising: a viscosity adjusting step for adjusting the viscosity of the dispersion, wherein shear stress in the primary dispersing step is 100 MPa or more. The method for producing a photosensitive composition according to claim 9, wherein the viscosity of the primary mixture in the primary dispersion step is 10,000 Pa · s or more. A field electron emission device using the photosensitive composition according to claim 1.