JP2007086761A - Photosensitive paste - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive paste capable of performing a pattern formation by a single exposure even in the case of a thick film of >50 μm, and having sensitivity slightly affected by an increased amount of glass particles added. <P>SOLUTION: The photosensitive paste comprises: (A) glass particles surface-modified with an organic compound; (B) an alkali-soluble resin or a resin which becomes alkali-soluble by the action of an acid; (C) a compound which generates an acid upon irradiation with ionizing radiation; and (D) an organic solvent as essential components, wherein the organic compound which surface-treats the glass particles comprises an organic high molecular compound having an acid group in a molecule. Barrier ribs for a plasma display using the photosensitive paste and a member for a plasma display equipped with the barrier ribs are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive paste.

  In recent years, miniaturization and high definition have progressed in displays, and accordingly, improvement of pattern processing technology is desired. As a pattern processing technique, for example, a photosensitive paste method is known, which is used for forming a partition wall of a back plate that is a member of a plasma display.

  As a method of forming the partition wall of the back plate of the plasma display, for example, a photosensitive paste containing an alkali-soluble polyorganosiloxane resin and glass particles is applied on the substrate, exposed and developed to form a partition pattern. And the method of baking and forming a partition is known (for example, refer patent document 1). However, if the amount of glass particles added is increased in order to obtain a denser partition wall, not only the sensitivity is remarkably lowered, but it may be difficult to form a pattern. In order to avoid this reduction in sensitivity, when the amount of the photosensitive agent in the photosensitive paste is increased, there are problems such as an increase in residue and a decrease in resolution.

JP 2004-177921 A

  An object of the present invention is to provide a photosensitive paste capable of forming a denser partition for a plasma display without lowering the sensitivity even when the amount of glass particles added is increased from that of a conventional photosensitive paste. .

  As a result of intensive studies to find a photosensitive paste that can solve the above-mentioned problems, the present inventors have completed the present invention.

That is, the present invention provides [1] a photosensitive paste containing the following (A) to (D).
(A) Glass particles surface-modified with an organic compound (B) Alkali-soluble resin or resin that becomes alkali-soluble by the action of acid (C) Compound that generates acid upon irradiation with ionizing radiation (D) Organic solvent Above (A) By using glass particles whose surface is modified with an organic compound such as (C), patterning can be performed with low sensitivity to compounds that generate an acid upon irradiation with ionizing radiation and with a stable sensitivity during exposure. It becomes possible.

Moreover, this invention provides the following [2]-[7] as a suitable embodiment which concerns on said [1].
[2] The photosensitive paste according to [1], wherein (A) comprises glass particles whose surface has been modified with an organic polymer compound.
[3] The photosensitive paste according to [1], wherein (A) includes glass particles that are surface-modified with an organic polymer compound having an acidic group in the molecule.
[4] (A) includes glass particles surface-modified with an organic polymer compound obtained by polymerizing at least one monomer selected from the group consisting of methacrylic acid, acrylic acid, vinyl acetic acid and vinyl benzoic acid. [1] Photosensitive paste
[5] The photosensitive paste according to [1], wherein (A) includes glass particles obtained by a production method including the following steps:
1) Step of adsorbing an organic compound having a carbon-carbon unsaturated bond on the surface of glass particles
2) From the group consisting of methacrylic acid, acrylic acid, vinyl acetic acid and vinyl benzoic acid, through the carbon-carbon unsaturated bond of the organic compound adsorbed on the surface of the glass particles, the glass particles obtained in 1) above Reacting at least one selected monomer
[6] The photosensitive paste according to any one of [1] to [5], wherein (A) includes glass particles obtained by surface-modifying glass particles having a softening point of 400 ° C. or higher with an organic compound.
[7] The content ratio of (A) to (D) with respect to the photosensitive paste is (A) 10 to 80% by mass, (B) 3 to 30% by mass, and (C) 0.01 to 20 respectively. The photosensitive paste according to any one of [1] to [6], wherein the photosensitive paste is 1% by mass and (D) 1 to 30% by mass.

Furthermore, the present invention provides the following [8] to [10] using any of the photosensitive pastes described above.
[8] Partition for plasma display panel manufactured using the photosensitive paste according to any one of the above
[9] A member for a plasma display comprising the partition for a plasma display panel according to [8]
[10] A plasma display panel comprising the member for plasma display according to [9]

  According to the photosensitive paste of the present invention, a pattern can be formed with a single exposure even with a thick film exceeding 50 μm, and a dense partition for a plasma display can be produced by increasing the content of glass particles. It becomes possible.

  Hereinafter, preferred embodiments of the present invention will be described.

  The glass particles surface-modified with the organic compound (A) in the present invention are obtained by adsorbing an organic compound on the surface of the glass particle. More specifically, the organic compound is adsorbed on the surface by physical adsorption or chemical bonding. It is the retained glass particles. Here, physical adsorption means that the glass surface and an organic compound are adsorbed and held by van der Waals force, and chemical bond means glass bonding by hydrogen bond, covalent bond, ionic bond or coordinate bond. Saying that the surface and organic compound are combined.

  The present inventor examined the cause of a significant decrease in sensitivity when a large amount of glass particles were blended in the photosensitive paste when the photosensitive paste was applied to a substrate to obtain a coated film and then the coated film was exposed. However, an idea was obtained that an alkali component flows out from the glass particles into the coating film, and that the alkali component lowers the sensitivity. Based on this, various studies are made on the means for suppressing the outflow of alkali, and by blending the above (A) into the photosensitive paste, it is possible to suppress the decrease in sensitivity during exposure of the coating film using the photosensitive paste. I found it.

  As the organic compound for modifying the surface of the glass particles, an organic polymer compound is particularly preferable. An organic polymer compound is easy to have a plurality of functional groups that can be physically adsorbed or chemically bonded to the surface of glass particles in one molecule, and polymer chain coils of organic polymer compounds are generally solid. Since it is easy to form a loop on the surface, the number of bonding groups themselves between the glass particle surface and the polymer chain increases, and the bonding force with the glass surface becomes stronger, which is preferable.

  As described above, the method for retaining the organic compound on the surface of the glass particles may be either a method using physical adsorption or a method using chemical bonding, but as the photosensitive paste of the present invention (A), A surface-modified organic compound having an acidic group is preferably used because it is easily adsorbed or bonded to the glass particle surface. In particular, glass particles that are surface-treated by adsorbing or bonding an organic polymer compound having an acidic group to the glass particle surface via the acidic group are preferable. Thus, the photosensitive paste which contains the glass particle surface-treated with the organic polymer compound which has an acidic group as (A) can suppress the said sensitivity fall further.

Examples of the acidic group include a carboxyl group (—COOH), a phosphoric acid group (—OPO ₃ H ₂ ), a phosphonic acid group (—PO ₃ H ₂ ), a sulfonic acid group (—SO ₃ H), and a sulfuric acid group (—OSO). ₃ H) or a phenolic hydroxyl group, among others, a carboxyl group and a phosphate group are particularly preferred, and a carboxyl group is particularly preferred.
An organic polymer compound having a plurality of these acidic groups in the molecule can be particularly preferably used.

  In particular, the organic polymer compound for surface treatment of glass particles is preferably an organic polymer compound obtained by addition polymerization of at least one monomer selected from the group consisting of methacrylic acid, acrylic acid, vinyl acetic acid and vinyl benzoic acid. . The organic polymer compound obtained by addition polymerization of the above monomer has a carboxyl group which is a suitable acidic group in the molecule, and includes glass particles surface-treated with such an organic polymer compound as (A) In particular, it is preferable because a decrease in sensitivity is suppressed.

  Next, a method for retaining the organic polymer on the glass particle surface by physical adsorption or chemical bonding will be described. Among such methods, a particularly simple method includes a method in which an organic polymer compound having an acidic group in the molecule is prepared in advance, and the glass particle surface is modified with the organic polymer compound. Then, when the glass particles and the organic polymer compound are mixed, the viscosity of the system increases and stirring becomes difficult. As a result, the surface modification of the glass particles itself may be insufficient.

(A) of the present invention is preferably glass particles obtained by a production method including the following steps.
1) Step of adsorbing glass particles with an organic compound having a carbon-carbon unsaturated bond (hereinafter sometimes referred to as “linker compound”)
2) The glass of the linker compound adsorbed on the glass particle surface by bringing the glass particles obtained in 1) above into contact with at least one monomer selected from the group consisting of methacrylic acid, acrylic acid, vinyl acetic acid and vinyl benzoic acid. -The step of polymerizing the monomer through a carbon unsaturated bond As described above, when the monomer is polymerized on the surface of the glass particle through the linker compound, the formation reaction of the organic polymer compound occurs on the surface of the glass particle. The glass particle surface-modified with the organic polymer compound can be efficiently obtained. In addition, such a method is preferable because problems such as thickening do not occur during the polymerization reaction.

  The linker compound is preferably an organic compound having a carbon-carbon unsaturated bond, particularly preferably an organic compound having a carbon-carbon double bond (hereinafter simply referred to as “double bond”), and an acidic group. As such, it preferably has a carboxyl group and / or a phosphate group. As the acidic group, an acid halide group or an ester group that easily becomes a carboxyl group by hydrolysis or the like can also be used.

The linker compound is preferably a compound having a carboxyl group and a polymerizable double bond in the molecule. Examples of the linker compound include acrylic acid, methacrylic acid, vinyl acetic acid, 2- (methacryloyloxy) ethyl phthalate, 2- ( Examples include methacryloyloxy) ethyl succinate, 2- (methacryloyloxy) ethyl maleate, 2- (acryloyloxy) ethyl succinate, and the like. Here, as a linker compound having an acid halide group or an ester group that can be easily converted into a carboxylic acid group by hydrolysis or the like, methyl acrylate, ethyl acrylate, acrylic acid chloride, acrylic acid bromide, methyl methacrylate And ethyl methacrylate, methacrylic acid chloride, methacrylic acid bromide, vinyl acetate, vinyl acetate, vinyl acetate, vinyl benzoate, vinyl benzoate and the like.
Furthermore, examples of the linker compound having a phosphate group and a polymerizable double bond in the molecule include 2- (methacryloyloxy) ethyl phosphate and bis [2- (methacryloyloxy) ethyl] phosphate.

  As a method of adsorbing the linker compound on the surface of the glass particles, a method of stirring in the presence or absence of a solvent, reaction temperature, usually 0 to 100 ° C., reaction time, usually 10 minutes to 2 hours, or these linkers When the compound can be vaporized, a method in which a gas obtained by vaporizing the linker compound is brought into contact with glass particles can be used. The glass particles obtained by performing such treatment and having the linker compound adsorbed on the surface can be used for the next reaction without removing the excess linker compound used.

  Next, in the glass particles having the linker compound adsorbed on the surface, a method of reacting the double bonds of the adsorbed linker compound or a monomer having a double bond polymerizable with the adsorbed linker compound double bond is added, By copolymerizing via the double bond group of the linker compound, glass particles surface-modified with an organic polymer compound can be obtained. The glass particles thus obtained are particularly preferable as (A) in the photosensitive paste of the present invention.

  As the monomer polymerizable via the double bond of the linker compound, a monomer selected from the group consisting of methacrylic acid, acrylic acid, vinyl acetic acid and vinyl benzoic acid is particularly preferable.

As a method of reacting the double bonds of the adsorbed linker compound or a method of copolymerizing a monomer having a polymerizable carbon-carbon double bond with a carbon-carbon double bond of the adsorbed linker compound, Although any method of radical polymerization, ionic polymerization, thermal polymerization, photopolymerization or coordination polymerization in which bonds can be addition-polymerized can be applied, radical polymerization is preferred because of its simple operation, and in particular, a radical initiator is used. The radical polymerization that has been used is preferred.
Examples of the radical initiator include 2,2′-azobisisobutyronitrile and benzoyl peroxide. The preferred monomers can be easily radical polymerized by using such a radical initiator.
The glass particles on which the linker compound is adsorbed and the radical polymerizable monomer are mixed in the presence or absence of a solvent, and the reaction temperature, usually 40 to 100 ° C., reaction time, usually 1 to 6 hours, Polymerization can be performed. Further, the radical initiator may be charged simultaneously with the monomer, or may be a method in which glass particles adsorbed with a linker compound and a radical generator are mixed in advance, and then the monomer capable of radical polymerization is charged.

  The glass particles of the present invention that have been surface modified with an organic compound only need to have the organic compound adsorbed on a part of the surface of the glass particle. For example, the organic compound is contained on the entire surface area (S1) of the glass particle. The area ratio (S2 / S1) of the area (S2) of the surface-modified part is particularly preferably 1 as a matter of course, but may not be completely covered. Preferably it is 0.2 or more, more preferably 0.5 or more.

Here, the glass particles to be surface-modified with an organic compound preferably include glass particles having a softening point of 400 ° C. or higher, low melting glass particles having a softening point of 400 ° C. to 600 ° C., and a softening temperature of 601 ° C. or higher. It is preferably at least one selected from the group consisting of glass particles.
Examples of the low melting point glass particles include zinc oxide glass particles, bismuth oxide glass particles, lithium oxide glass particles, and boron oxide zinc oxide glass. On the other hand, examples of the glass particles having a softening temperature of 601 ° C. or higher include soda glass particles, alkali-free glass particles, and Pyrex (registered trademark) particles.

  The volume average particle size of the glass particles is preferably 0.1 to 20 μm, more preferably 0.1 to 10 μm at a measurement temperature of 25 ° C. It is preferable that the volume average particle size is in the above range because a denser partition wall can be obtained. The volume average particle diameter can be measured using a commercially available light scattering particle diameter measuring apparatus (for example, model number DLS-7000, manufactured by Otsuka Electronics Co., Ltd.).

  The content ratio of (A) used in the photosensitive paste of the present invention is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, based on the total amount of the photosensitive paste.

Next, (B) an alkali-soluble resin or a resin that becomes alkali-soluble by the action of an acid will be described. Here, the notation of “alkali-soluble” indicates that it can be dissolved in any one of an alkaline aqueous solution, an organic solvent exhibiting alkalinity, or an organic solvent-water mixed solution exhibiting alkalinity.
The alkali-soluble resin is prepared by adding a crosslinking agent that causes a crosslinking reaction with the alkali-soluble resin by the action of an acid, so that the ionizing radiation exposure part is alkalinized by the compound (C) that generates an acid upon irradiation with ionizing radiation. Insoluble and ionized radiation unexposed areas become alkali-soluble. In this way, a difference in solubility with respect to the alkaline solution occurs between the exposed portion and the unexposed portion, so that a negative ionizing radiation-sensitive resin capable of photolithography can be obtained.
On the other hand, a resin that becomes alkali-soluble by the action of an acid is a resin that does not exhibit alkali-solubility by itself, but undergoes a chemical reaction in the presence of an acid and becomes alkali-soluble. (C) Irradiation with ionizing radiation Due to the compound that generates an acid, the ionizing radiation exposed part becomes alkali-soluble and the ionizing radiation unexposed part becomes alkali-insoluble. Thus, a difference in solubility with respect to the alkaline solution occurs between the exposed portion and the unexposed portion, so that a positive ionizing radiation-sensitive resin capable of photolithography can be obtained.

Preferable alkali-soluble resins include, for example, resins having a carboxyl group and / or a phenolic hydroxyl group in the molecule. Examples of such an alkali-soluble resin include resins obtained by addition polymerization of at least one monomer selected from acrylic acid, methacrylic acid, vinyl acetic acid, vinyl benzoic acid, and hydroxystyrene, and include polyacrylic acid and polymethacrylic acid. , Polyvinyl acetic acid, polyvinyl benzoic acid, polyhydroxystyrene, acrylic acid-vinyl acetic acid copolymer, methacrylic acid-vinyl acetic acid copolymer, methacrylic acid-vinyl benzoic acid copolymer, methacrylic acid-hydroxy styrene copolymer, vinyl Examples thereof include benzoic acid-hydroxystyrene copolymer and methacrylic acid-vinylbenzoic acid-hydroxystyrene copolymer.
In addition, a resin called a novolac resin is also suitable as an alkali-soluble resin, and phenol (hydroxybenzene), o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2, A novolak resin obtained by polycondensation of a phenol compound such as 3-xylenol, 2-butylphenol, 2-isobutylphenol, 2-cyclohexylphenol, 2-phenylphenol and an aldehyde compound such as formaldehyde, acetaldehyde, benzaldehyde, 1-naphthylaldehyde, etc. It can be illustrated. As the novolak resin, a phenol novolak resin and a cresol novolak resin are particularly preferably used.

As a crosslinking agent for forming a negative ionizing radiation-sensitive resin and causing a crosslinking reaction with the alkali-soluble resin by the action of an acid, a melamine compound, a glycolurea compound, an alkoxymethyl-substituted aromatic compound, an acetoxymethyl-substituted An aromatic compound, a methylol substituted aromatic compound, an epoxy compound, etc. are mentioned.
Examples of the melamine compound include hexakis (methoxymethyl) melamine and hexakis (ethoxymethyl) melamine.
Examples of the glycol urea compound include 1,3,4,6-tetrakis (methoxymethyl) glycol urea, 1,3,4,6-tetrakis (ethoxymethyl) glycol urea, 1,3,4,6-tetrakis (butoxymethyl) Examples include glycol urea.
Examples of the alkoxymethyl-substituted aromatic compound include 1,4-dimethoxymethylbenzene, 1,2-dimethoxymethylbenzene, 1,3-dimethoxymethylbenzene, 1,3,5-trimethoxymethylbenzene, 1,4-dibutoxy. Examples thereof include methylbenzene, 1,2-dibutoxymethylbenzene, 1,3-dibutoxymethylbenzene, 1,3,5-tributoxymethylbenzene and the like.
Examples of the acetoxymethyl-substituted aromatic compound include 1,4-diacetoxymethylbenzene, 1,2-diacetoxymethylbenzene, 1,3-diacetoxymethylbenzene, 1,3,5-triacetoxymethylbenzene, and the like. .
Examples of the methylol-substituted aromatic compound include 1,4-dimethylolbenzene, 1,2-dimethylolbenzene, 1,3-dimethylolbenzene, 1,3,5-trimethylolbenzene and the like. Examples of the epoxy compound include 1,3-bis (glycidyloxypropyl) -1,1,3,3-tetramethyldisiloxane.

As the resin capable of forming the positive ionizing radiation-sensitive resin and becoming alkali-soluble by the action of an acid, a resin having a carboxyl group protected by a group capable of leaving by the action of an acid in the molecule, or an intramolecular And a resin having a phenolic hydroxyl group protected by a group capable of leaving by the action of an acid. Here, examples of the group capable of leaving by the action of an acid include a tertiary butyl group, a methoxymethyl group, and a 2-ethyladamantyl group. Resins having a carboxyl group protected by a group capable of leaving by the action of acid in the molecule include polyacrylic acid-poly (tertiary butyl acrylate) copolymer, polyacrylic acid-poly (methoxymethyl acrylate) copolymer Polymer, polyacrylic acid-poly (2-ethyladamantyl acrylate) copolymer, polymethacrylic acid-poly (tertiary butyl methacrylate) copolymer, polymethacrylic acid-poly (methoxymethyl acrylate) copolymer, polyacrylic acid -Poly (2-ethyladamantyl acrylate) copolymer, polyvinyl acetate-poly (tertiary butyl acrylate) copolymer, polyvinyl acetate-poly (methoxymethyl acrylate) copolymer, and the like.
Examples of the resin having a phenol group protected by a group capable of leaving by the action of an acid in the molecule include polyhydroxystyrene-poly (tertiary butoxystyrene) copolymer, polyhydroxystyrene-poly (2-ethyladamantyloxystyrene). ) Copolymers and the like.

The content ratio of (B) used in the photosensitive paste of the present invention is preferably 3 to 30% by mass and more preferably 5 to 20% by mass with respect to the total amount of the photosensitive paste.
Moreover, as mentioned above, when adding the compound which reacts with binder resin by the effect | action of an acid, Preferably it is 1-15 mass% with respect to the photosensitive paste whole quantity, More preferably, it is 2-10 mass%. Can be added in a range.

Next, (C) a compound that generates an acid upon irradiation with ionizing radiation will be described.
Examples of the compound that generates an acid upon irradiation with electromagnetic radiation include a photoacid generator and a photocationic polymerization initiator.

  The irradiation amount of the ionizing radiation is not particularly limited as long as the compound generating an acid by irradiation with ionizing radiation is not less than the amount generating an acid and does not impair the effects of the present invention. Absent.

  Examples of the photoacid generator include [cyclohexyl- (2-cyclohexanonyl) -methyl] sulfonium trifluoromethanesulfonate, bis (p-tolylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and tertiary butylcarbonylmethyl. -Tetrahydrothiophenium trifluoromethanesulfonate etc. are mentioned. As the photoacid generator, in addition to the above, compounds described in JP-A-11-202495 can also be used.

  Examples of the photocationic polymerization initiator include iodonium salts, sulfonium salts, phosphate salts, and antimonate salts. Specifically, Rhodesyl Photoinitiator 2074 (manufactured by Rodel), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172, Adeka Opton CP series (any) Asahi Denka Kogyo Co., Ltd.). In addition to the above, compounds described in JP-A-9-118663 can also be used.

  The content ratio of the compound that generates an acid upon irradiation with ionizing radiation is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, based on the total amount of the photosensitive paste. When the content is in the above range, a pattern can be formed with good productivity, which is preferable.

Next, (D) the organic solvent will be described.
The organic solvent of the present invention is not particularly limited, but preferably the refractive index of the organic solvent at 25 ° C. is 1.40 to 1.80, more preferably 1.43 to 1.70, More preferably from 1.44 to 1.60. When the refractive index of the organic solvent is within the above range, the transparency of the photosensitive paste after film formation tends to be high, which is preferable. The refractive index of the organic solvent can be measured using a refractometer (RA-520N manufactured by Kyoto Electronics Industry Co., Ltd.) at 25 ° C. The refractive index of the organic solvent is described, for example, in documents such as Revised 4th edition, Chemical Handbook, Basics II, pages 514-520 (edited by the Chemical Society of Japan, Maruzen Co., Ltd., issued on September 30, 1993). From the values described in this document, an organic solvent having a refractive index of 1.40 to 1.80 may be selected and used.

  Here, examples of the organic solvent having a refractive index of 1.40 to 1.80 include propylene glycol monobutyl ether (refractive index 1.42), polypropylene glycol dibenzoate (refractive index 1.52), 2-heptanone ( Refractive index 1.41), propylene glycol methyl ether acetate (refractive index 1.40), gamma-butyrolactone (refractive index 1.44), 1,2-propanediol dibenzoate (refractive index 1.54), polyethylene glycol di Benzoate (refractive index 1.53) and the like, preferably polypropylene glycol dibenzoate, gamma-butyrolactone, 1,2-propanediol dibenzoate, polyethylene glycol dibenzoate having a refractive index of 1.43 to 1.70. More preferably, the refractive index is 1. Polypropylene glycol dibenzoate is from 44 to 1.60, 1,2-propanediol dibenzoate, polyethylene glycol dibenzoate.

  The content ratio of (D) in the photosensitive paste of the present invention is usually 1% by mass or more and 30% by mass or less, preferably 3% by mass or more and 25% by mass or less, based on the total amount of the photosensitive paste. Preferably they are 5 mass% or more and 20 mass% or less.

Furthermore, inorganic particles other than (A) may be added to the photosensitive paste of the present invention.
Here, the relative dielectric constant of the inorganic particles other than (A) is preferably 4.0 or more and 9.5 or less, and more preferably 4.0 or more and 9.0 or less. The relative dielectric constant can be measured at 20 ° C. using a bridge type dielectric constant measuring apparatus (for example, model No. TR-10C manufactured by Ando Electric Co., Ltd.).

  The refractive index of the inorganic particles other than (A) is preferably 1.40 to 2.50, more preferably 1.43 to 2.20, and particularly preferably 1.43 to 1.80. It is. When the refractive index of the inorganic particles is in the above range, light scattering is small at the time of exposure, and a good pattern tends to be formed, which is preferable. The refractive index can be measured at 25 ° C. using a prism refractive index measuring device (for example, model number GP1-P manufactured by OPTEC).

  The volume average particle diameter of the inorganic particles other than (A) is preferably 0.01 to 40 μm, more preferably 0.1 to 10 μm, and particularly preferably 1.0 to 8.0 μm. When the volume average particle diameter of the inorganic particles is in the above range, the amount of inorganic particles in the partition formed using the photosensitive paste can be increased, so that the shrinkage during firing is small, In addition, since light scattering during exposure is small, a good pattern tends to be formed, which is preferable. Here, the volume average particle diameter can be determined by the same method as that for the glass particles.

  In the photosensitive paste of this invention, you may mix and use the inorganic particle from which an average particle diameter differs in arbitrary ratios. Moreover, what differs in the average particle diameter of inorganic particles other than (A) and (A) can also be used.

  The shape of the inorganic particles other than (A) is not particularly limited, and may be crushed or spherical, but is preferably spherical.

  Specific examples of inorganic particles other than (A) include silica particles derived from colloidal silica, silica particles such as aerosil and silica gel, glass particles mainly composed of silicon oxide, or a mixture thereof.

  When inorganic particles other than (A) are used in the photosensitive paste of the present invention, the content ratio is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, based on the total amount of the photosensitive paste. is there. When inorganic particles other than (A) are used in the above-mentioned content ratio, the film shrinkage during firing tends to be small and it tends to be difficult to peel off from the substrate, and the light scattering during exposure is small, resulting in a good pattern. It tends to be formed and is preferable.

  Furthermore, you may add additives, such as a light absorber, a photosensitizer, a plasticizer, a dispersing agent, a precipitation inhibitor, a leveling agent, to the photosensitive paste of this invention as needed.

Next, preferred examples of the method for patterning using the photosensitive paste of the present invention include the following steps (1) to (4).
(1) Step of applying the photosensitive paste of the present invention on a substrate to form a coating film (2) Step of exposing the coating film obtained in (1) (3) Obtained in (2) Step of developing the coating film (4) Step of baking the substrate at a temperature of 400 ° C. to 600 ° C. after the development of (3) above

  First, (1) will be described. First, a photosensitive paste is applied on the entire surface or partially on the substrate. As a coating method, for example, a bar coater, a roll coater, a die coater, a screen printing method or the like can be used. The coating thickness can be adjusted by selecting the number of coatings and the viscosity of the paste, and is usually about 5 to 500 μm.

  When the photosensitive paste is applied on the substrate, the surface of the substrate may be treated with a surface treatment liquid in order to improve the adhesion between the substrate and the coating film.

  Examples of the surface treatment liquid include silane coupling agents such as glycidyloxypropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, and oxetanyloxypropyltriethoxysilane. As the silane coupling agent, for example, a solution diluted with an organic solvent such as ethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol to a concentration of 0.1 to 5% by mass is used as the surface treatment liquid. It is preferable.

  Examples of the surface treatment method include a method in which a surface treatment liquid is uniformly applied on a substrate with a spinner or the like and then dried at 80 to 140 ° C. for 5 to 60 minutes. As a drying method, a hot plate, a far-infrared oven, or the like is preferable.

  As described above, if necessary, a photosensitive paste is applied to a surface-treated substrate, and is usually dried at 80 to 130 ° C. for 5 to 100 minutes using a far infrared oven or the like.

  The dried coating film is exposed using (2) an exposure apparatus. Examples of the exposure apparatus include a proximity exposure machine.

  When exposing a large area, a large area can be exposed with an exposure machine having a small exposure area by applying a photosensitive paste on a substrate and then performing exposure while moving the photosensitive paste. The exposure is to transfer or draw the mask pattern to be created on the photosensitive paste coating film with ionizing radiation. Examples of the ionizing radiation include ultraviolet rays, electron beams, X-rays, visible light, near infrared light, etc. Can be used.

  The amount of irradiation in the exposure can be appropriately optimized depending on the type of ionizing radiation used or the type of (C) used in the photosensitive paste, but the effect of the present invention can be achieved if (C) is greater than the amount capable of generating an acid. It can be optimized within the range that does not interfere.

In particular, by using the wavelength 365nm of light source using a high pressure mercury lamp as an exposure source, the temperature is at room temperature (25 ± 5 ℃), it is preferable to carry out the exposure at an exposure dose ^{100mJ / cm 2 ~2000mJ / cm 2} .

  After the exposure, (3) development is performed. By such development, the exposed portion remains, the unexposed portion is dissolved, and a pattern is formed on the substrate. The development is performed by using a developing solution by a dipping method, a spray method, a brush method, or the like.

  Examples of the developer include alkaline aqueous solutions such as tetramethylammonium hydroxide, monoethanolamine, diethanolamine, sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate.

  The alkali concentration in the aqueous solution is preferably 0.05 to 5% by mass, more preferably 0.1 to 5% by mass. When the alkali concentration is in the above range, the removability of the portion to be developed and removed is good, and the pattern to be left is less likely to be peeled off or eroded, which is preferable.

  The temperature during development is preferably 15 to 50 ° C. in terms of process control.

  After the pattern is formed as described above, the partition walls can be produced by (4) firing in a firing furnace. The firing atmosphere and firing temperature vary depending on the type of photosensitive paste and substrate, but can usually be fired at 400 to 600 ° C. in an atmosphere such as air or nitrogen. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

  In particular, when patterning on a glass substrate, it is usually preferable to perform baking at a temperature of 400 to 600 ° C. for 10 to 60 minutes, and a partition for a plasma display can be obtained by baking.

A coat layer may be further formed on the surface of the partition wall obtained as described above. Examples of the coating layer include a paste agent and a ceramic coating agent made of low melting point glass particles and a binder resin.
The coating layer using the paste agent can be formed by applying, drying, and baking the coating agent. After manufacturing the partition wall, the coating agent is applied to the formed partition wall and fired. A coating method may be used, and the coating layer may be formed simultaneously with the production of the partition walls by applying the coating agent to a pattern obtained by exposure and development and firing. The firing temperature for forming the coat layer using the paste is usually about 250 to 600 ° C., and preferably 400 to 600 ° C. when it is performed simultaneously with the production of the partition walls.

  Here, examples of the low melting point glass particles in the paste include the same examples as described above.

  Examples of the binder resin in the paste agent include butyral resin, polyvinyl alcohol, acrylic resin, and poly α-methylstyrene.

  As the ceramic coating agent, an aqueous metal salt-based coating agent, an alkoxy metal salt-based coating agent, or the like can be used. Specifically, as an aqueous metal salt-based coating agent, MS-1700, as an alkoxy metal salt-based coating agent. Can include G-301, G-401 (both manufactured by Nippon Ceramic Co., Ltd.), and the like.

  When the ceramic coating agent is used, the coating layer can usually be formed at room temperature to 500 ° C.

In the partition wall obtained by the above pattern processing method, the amount of change in the top width dimension, bottom width dimension and height dimension of the partition wall before and after firing is preferably within ± 30%, more preferably Within ± 10%.
Furthermore, according to the photosensitive paste of the present invention, it is possible to form a pattern with a single exposure even with a thick film exceeding 50 μm, and to manufacture a dense plasma display partition by increasing the content of glass particles. Is possible.

The partition obtained as described above can be suitably used as a partition for a back plate which is a member for plasma display. The manufacturing method of the back plate is achieved by subjecting the substrate on which the partition walls are formed to a known process such as forming a fluorescent layer.
The back plate manufactured in this way is sealed with a front plate for plasma display manufactured by a known method, and discharge gas is sealed in a space formed between the front plate and the back plate. A plasma display panel can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Example 1
Zinc oxide low melting glass particles (NLPF023 made by Asahi Glass Co., Ltd.) 50.00 g, 100 ml of dehydrated toluene was put into a 200 ml four-necked flask equipped with a three-way cock and a Dimroth, and nitrogen gas was bubbled while stirring with a magnetic stirrer. Dissolved oxygen was purged. 0.25 g of methacrylic acid chloride was added and stirred at room temperature for 1 hour. 2.00 g of methacrylic acid and 0.1 g of 2,2′-azobisisobutyronitrile were added and reacted for 5 hours at 70 ° C. in an oil bath while stirring. After completion of the reaction, the reaction mixture was transferred to a 300 ml eggplant flask, and toluene was distilled off with a rotary evaporator and concentrated to obtain glass particles whose surface was modified with an organic compound mainly composed of polymethacrylic acid.

  7.60 g of the above glass particles, crosslinking agent 1,3-bis (3′-glycidyloxypropyl) -1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .; LS-7970) 45 g, spherical silica having an average particle size of 2.0 μm (manufactured by Admatechs Co., Ltd .; SO-C6) 5.13 g, 50 wt% gamma butyrolactone solution of phenol novolac resin (manufactured by Gunei Chemical Industry Co., Ltd., PSM-4261) 1.80 g, photoinitiator (PI-2074 manufactured by Rhodia Japan) 0.14 g, sensitizer (DBA, manufactured by Kawasaki Kasei Kogyo) 0.03 g, titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) 0.05 g, Poly (propylene glycol) dibenzoate (Aldrich) 0.15 g, 1,2-propanedibenzoate 0.72 g, γ-buty for viscosity adjustment Lactone 1.13g placed in a polypropylene sealed container, stirrer deaerator (KEYENCE Corp.; HM-500) to prepare a uniform photosensitive paste was stirred with. The content ratio of (A) to (D) in the obtained photosensitive paste was (A) 44.19% by mass, (B) 5.23% by mass, (C) 1.34% by mass, and (D) 16. It was .86% by mass.

  The prepared photosensitive paste was applied once on a glass substrate using an applicator having a gap of 200 μm. After coating, the coating film was prepared by drying in an oven at 110 ° C. for 30 minutes.

The dried coating film was exposed with a proximity exposure machine (manufactured by Dainippon Screen Mfg. Co., Ltd .; MAP-1300) using a 50 μm line, 240 μm pitch mask. The irradiation exposure dose was 500 mJ / cm ² . After exposure, the substrate was baked at 130 ° C. for 10 minutes, and then developed with a 0.5 wt% aqueous sodium hydroxide solution to obtain a pattern having a pattern upper width of 59 μm, a pattern lower width of 99 μm, and a height of 100 μm. By baking the pattern thus obtained at about 580 ° C., a partition wall suitable as a member for a plasma display can be produced.

Example 2
Zinc oxide low melting glass particles (NLPF023 made by Asahi Glass Co., Ltd.) 50.00 g, 100 ml of dehydrated toluene was put into a 200 ml four-necked flask equipped with a three-way cock and a Dimroth, and nitrogen gas was bubbled while stirring with a magnetic stirrer. Dissolved oxygen was purged. 0.25 g of methacrylic acid chloride was added and stirred at room temperature for 1 hour. Methacrylic acid (1.00 g) and 2,2′-azobisisobutyronitrile (0.042 g) were added, and the mixture was reacted in an oil bath at 70 ° C. for 5 hours with stirring. After completion of the reaction, the reaction mixture was transferred to a 300 ml eggplant flask, and toluene was distilled off with a rotary evaporator and concentrated to obtain glass particles whose surface was modified with an organic compound mainly composed of polymethacrylic acid.

  8.48 g of the above glass particles, crosslinking agent 1,3-bis (3′-glycidyloxypropyl) -1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .; LS-7970) 70 g, spherical silica having an average particle size of 2.0 μm (manufactured by Admatechs Co., Ltd .; SO-C6) 5.68 g, phenol novolak resin 50 wt% gamma butyrolactone solution (manufactured by Gunei Chemical Industry Co., Ltd., PSM-4324), 2.00 g of heat softening temperature (about 100 ° C.), 50 wt% gamma-butyrolactone solution of phenol novolak resin (manufactured by Gunei Chemical Industry Co., Ltd., PSM-4326, heat softening temperature about 120 ° C.) 0.40 g, photoinitiator (rhodia) Japan PI-2074) 0.24g, sensitizer (DBA, Kawasaki Chemical Industries) 0.06g, titanium oxide (CR-EL, 0.05 g of raw industrial company), 0.12 g of poly (propylene glycol) dibenzoate (manufactured by Aldrich), 0.60 g of 1,2-propanedibenzoate, and 0.50 g of γ-butyrolactone for viscosity adjustment are sealed in polypropylene. The mixture was stirred using a stirring deaerator (manufactured by Keyence Corporation; HM-500) to prepare a uniform photosensitive paste. The content ratio of (A) to (D) in the obtained photosensitive paste was (A) 45.03 mass%, (B) 6.37 mass%, (C) 1.22 mass%, and (D) 12. It was 0.85% by mass.

  The prepared photosensitive paste was applied once on a glass substrate using an applicator having a gap of 200 μm. After coating, the coating film was prepared by drying in an oven at 110 ° C. for 30 minutes.

The dried coating film was exposed with a proximity exposure machine (manufactured by Dainippon Screen Mfg. Co., Ltd .; MAP-1300) using a 50 μm line, 240 μm pitch mask. The irradiation exposure dose was 300 mJ / cm ² . After the exposure, the substrate was baked at 130 ° C. for 10 minutes and then developed with a 0.5 wt% aqueous sodium hydroxide solution to obtain a pattern having a pattern upper width of 75 μm, a pattern lower width of 105 μm, and a height of 98 μm. By baking the pattern thus obtained at about 580 ° C., a partition wall suitable as a member for a plasma display can be produced.

Example 3
Zinc oxide low melting glass particles (NLPF023 made by Asahi Glass Co., Ltd.) 50.00 g, 100 ml of dehydrated toluene was put into a 200 ml four-necked flask equipped with a three-way cock and a Dimroth, and nitrogen gas was bubbled while stirring with a magnetic stirrer. Dissolved oxygen was purged. 0.25 g of methacrylic acid chloride was added and stirred at room temperature for 1 hour. 2.00 g of methacrylic acid and 0.1 g of 2,2′-azobisisobutyronitrile were added and reacted for 5 hours at 70 ° C. in an oil bath while stirring. After completion of the reaction, the reaction mixture was transferred to a 300 ml eggplant flask, and toluene was distilled off with a rotary evaporator and concentrated to obtain glass particles whose surface was modified with an organic compound mainly composed of polymethacrylic acid.

  8.48 g of the above glass particles, crosslinking agent 1,3-bis (3′-glycidyloxypropyl) -1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .; LS-7970) 90 g, spherical silica having an average particle size of 2.0 μm (manufactured by Admatechs Co., Ltd .; SO-C6) 5.68 g, phenol novolak resin 50 wt% gamma butyrolactone solution (manufactured by Gunei Chemical Industry Co., Ltd., PSM-4326), 1.80 g of heat softening temperature (about 120 ° C.), 0.24 g of photoinitiator (PI-2074 manufactured by Rhodia Japan), 0.06 g of sensitizer (DPA, manufactured by Kawasaki Kasei Kogyo), titanium oxide (CR-EL, Ishihara Sangyo) 0.05g, 1,2-propanedibenzoate 0.80g in a polypropylene sealed container, stirring defoaming machine (manufactured by Keyence Co., Ltd .; H Stirred using a -500) to prepare a uniform photosensitive paste. The content ratio of (A) to (D) in the obtained photosensitive paste was (A) 47.08% by mass, (B) 5.00% by mass, (C) 1.28% by mass, and (D) 9. .44% by mass.

  The prepared photosensitive paste was applied once on a glass substrate using an applicator having a gap of 200 μm. After coating, the coating film was prepared by drying in an oven at 110 ° C. for 30 minutes.

The dried coating film was exposed with a proximity exposure machine (manufactured by Dainippon Screen Mfg. Co., Ltd .; MAP-1300) using a 50 μm line, 240 μm pitch mask. The irradiation exposure dose was 1000 mJ / cm ² . After the exposure, the substrate was baked at 130 ° C. for 10 minutes and then developed with a 0.5 wt% aqueous sodium hydroxide solution to obtain a pattern having a pattern upper width of 68 μm, a pattern lower width of 108 μm, and a height of 90 μm. By baking the pattern thus obtained at about 580 ° C., a partition wall suitable as a member for a plasma display can be produced.

Comparative Example 1
A paste was prepared in the same manner as in Example 1 except that glass particles whose surface was not modified with an organic compound (NLPF023 manufactured by Asahi Glass) were used.
The obtained paste was applied and exposed under the same conditions as in Example 1. However, the pattern was dissolved during development, and no pattern was obtained.

In Comparative Example 1, at the same exposure amount as in Example 1, the crosslinking reaction between the crosslinking agent and the phenol novolac resin, which is an alkali-soluble binder resin, hardly progressed, and pattern dissolution occurred during development. With the photosensitive paste to which glass particles whose surface is modified with an organic compound is added, partition walls can be manufactured even with a pattern height of 100 μm, and dense partition walls can be manufactured by highly filling glass particles. .

Claims (10)

A photosensitive paste containing the following (A) to (D).
(A) Glass particles surface-modified with an organic compound (B) Alkali-soluble resin or resin that becomes alkali-soluble by the action of an acid (C) A compound that generates an acid upon irradiation with ionizing radiation (D) An organic solvent   The photosensitive paste of Claim 1 in which (A) contains the glass particle surface-modified with the organic polymer compound.   The photosensitive paste of Claim 1 in which (A) contains the glass particle surface-modified by the organic polymer compound which has an acidic group in a molecule | numerator.   2. The photosensitive film according to claim 1, wherein (A) comprises glass particles surface-modified with an organic polymer compound obtained by polymerizing at least one monomer selected from the group consisting of methacrylic acid, acrylic acid, vinyl acetic acid and vinyl benzoic acid. Sex paste. The photosensitive paste of Claim 1 in which (A) contains the glass particle obtained by the manufacturing method including the following process.
1) Step of adsorbing an organic compound having a carbon-carbon unsaturated bond on the surface of glass particles
2) From the group consisting of methacrylic acid, acrylic acid, vinyl acetic acid and vinyl benzoic acid, through the carbon-carbon unsaturated bond of the organic compound adsorbed on the surface of the glass particles, the glass particles obtained in 1) above Reacting at least one selected monomer   The photosensitive paste in any one of Claims 1-5 in which (A) contains the glass particle which surface-modified the glass particle whose softening point is 400 degreeC or more with the organic compound.   The content ratios of (A) to (D) with respect to the photosensitive paste are (A) 10 to 80% by mass, (B) 3 to 30% by mass, and (C) 0.01 to 20% by mass, respectively. And (D) 1-30 mass%, The photosensitive paste in any one of Claims 1-6.   The partition for plasma display panels manufactured using the photosensitive paste in any one of Claims 1-7.   A member for a plasma display, comprising the partition for a plasma display panel according to claim 8. A plasma display panel comprising the member for plasma display according to claim 9.