JP5169757B2 - Photosensitive composition, method for forming fired body, and method for producing flat display panel - Google Patents

Description

  The present invention relates to a photosensitive composition, a method for forming a fired body, and a method for producing a flat display panel. More specifically, the present invention is suitably used as a material for forming a component of a display panel of a flat panel display such as a plasma display. Photosensitive composition, a method for forming a fired body for forming a fired body having a pattern from the photosensitive composition, and a flat display panel comprising components using the photosensitive composition as a material It relates to the manufacturing method.

In recent years, a plasma display has attracted attention as a flat fluorescent display.
This plasma display has a flat display panel as a display panel.
FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel (hereinafter also referred to as “PDP”) which is a kind of flat display panel. In the figure, 1 and 2 are glass substrates facing each other, 3 is a partition, and cells are partitioned by the glass substrate 1, the glass substrate 2 and the partition 3. 4 is a transparent electrode fixed to the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of reducing the resistance of the transparent electrode 4, 6 is an address electrode fixed to the glass substrate 2, and 7 is Fluorescent material held in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, 9 is a surface of the glass substrate 2 so as to cover the address electrode 6 The formed dielectric layer, P, is a protective film made of, for example, magnesium oxide.
In the color PDP, a color filter (red, green, blue) or a black matrix may be provided between the glass substrate 1 and the dielectric layer 8 in order to obtain a high contrast image.

  In a PDP provided with a black matrix, a method for forming the black matrix is, for example, a paste-like photosensitivity containing a black pigment, glass powder, an alkali-soluble polymer, a photopolymerizable monomer, and a photopolymerization initiator. A composition is prepared, and the photosensitive composition is applied to the surface of the glass substrate 1 by a screen printing method and dried to form a photosensitive resin layer. A predetermined pattern is formed on the photosensitive resin layer. A black matrix is formed as a layer made of a fired body of the photosensitive composition by forming a pattern layer by performing an exposure process by irradiating light through a photomask and then developing the pattern layer, and baking the pattern layer. A photolithographic method for forming is known.

  Thus, in the photosensitive composition used for forming the constituent elements of PDP by the photolithography method, the developer is polymerized by exposure in the presence of a photopolymerization initiator as a photopolymerizable monomer. From the viewpoint that the solubility in (alkaline developer) decreases to become alkali-insoluble or alkali-insoluble, and it is easy to provide contrast between the exposed and unexposed areas of the developer, so that a sufficient development margin can be obtained. Polyfunctional acrylate compounds are used (for example, see Patent Document 1).

  However, in such a photosensitive composition, in order to increase the viscosity of the composition itself from the viewpoint of coating properties, a development treatment is performed on the photosensitive resin layer formed on the substrate. In the process of forming the pattern, there is a problem that a development residue is generated in a portion where the unexposed portion is formed on the substrate surface.

JP 2006-8792 A

This invention is made | formed based on the above situations, Comprising: The objective is to provide the photosensitive composition which can suppress generation | occurrence | production of a development residue while having a high viscosity.
Another object of the present invention is to provide a method for forming a fired body that can easily obtain a fired body having a pattern having a good shape.
Still another object of the present invention is to provide a method of manufacturing a flat display panel that can easily form a component having a good shape.

The photosensitive composition of the present invention comprises
(A) inorganic particles containing at least glass powder,
(B) an alkali-soluble polymer,
(C) A compound represented by the following general formula (1) and (D) a photopolymerization initiator are contained.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and X represents an —O— group, —O (CH ₂ CH ₂ ) _a O— group (where a is an integer of 1 to 8). Or —O (CH ₂ CH ₂ CH ₂ ) _b O— group (where b is an integer of 1 to 8), Y represents a methylene group, an alkylene group having 2 to 8 carbon atoms, and 2 carbon atoms. A group selected from the group consisting of an alkenylene group of -8, an unsubstituted or substituted phenylene group, an unsubstituted or substituted cyclohexylene group, and a cyclohexylene group, a part of which is an unsaturated bond; Show. n is an integer of 1 to 4. ]

  The photosensitive composition of the present invention preferably contains an acrylate compound having 2 to 3 functional groups.

  It is preferable that the photosensitive composition of this invention contains 0.1-10 mass% of hydroxypropyl cellulose with respect to the whole composition.

  In the method for forming a fired body according to the present invention, a photosensitive resin layer made of the photosensitive composition is formed on a substrate, and the formed photosensitive resin layer is exposed to light to form a latent image having a pattern. Then, the photosensitive resin layer is developed to form a pattern layer corresponding to the pattern formed by the exposure process, and the pattern layer is fired to obtain a fired body having a pattern. To do.

  In the method for producing a flat display panel of the present invention, a photosensitive resin layer made of the photosensitive composition is formed on a substrate, and the formed photosensitive resin layer is subjected to an exposure process to form a latent image having a pattern. After the formation, the photosensitive resin layer is developed to form a pattern layer corresponding to the pattern formed by the exposure process, and the pattern layer is fired to form a partition, an electrode, a resistor, and a dielectric layer And a step of forming a component selected from a phosphor, a color filter, and a black matrix.

  According to the photosensitive composition of the present invention, a polyfunctional acrylate compound having a specific structure is contained as a photopolymerizable monomer, and the polyfunctional acrylate compound having the specific structure is carboxylated as a functional group. Since it has an acid group and has good solubility in the developer, it can increase the viscosity of the composition based on the interaction with the glass powder constituting the inorganic particles. In the case where the photosensitive resin layer made of the photosensitive composition has a high viscosity, the development residue can be prevented from being generated.

  Moreover, in the photosensitive composition of this invention, the other acrylate compound which has 2-3 functional groups must be contained with the polyfunctional acrylate compound which has a specific structure as a photopolymerizable monomer. Thus, the viscosity of the composition can be adjusted so as not to be excessively increased by the action of the polyfunctional acrylate compound having a specific structure by the other acrylate compound having 2 to 3 functional groups. In addition, when developing a photosensitive resin layer made of a photosensitive composition having a high viscosity, generation of development residues can be sufficiently suppressed.

  According to the method for forming a fired body of the present invention, the photosensitive composition described above is used as a constituent material thereof. Therefore, when the photosensitive composition in the forming process is applied onto a substrate, the coating property is good. In addition, since the development residue is suppressed from being generated in the development process, a fired body having a pattern having a good shape can be easily obtained.

  According to the flat display panel manufacturing method of the present invention, since the photosensitive composition is used as a constituent material of the constituent element, the photosensitive composition in the process of forming the constituent element is applied onto a substrate. At the same time, good coatability is obtained, and generation of development residue is suppressed in the development process, so that a component having a desired shape can be easily formed.

Hereinafter, the photosensitive composition of the present invention will be described in detail.
The photosensitive composition of the present invention comprises a component A composed of inorganic particles containing at least glass powder, a component B composed of an alkali-soluble polymer, and a compound represented by the above general formula (1) (hereinafter referred to as “specific polyfunctional”). Also referred to as “acrylate compound”.) And a D component comprising a photopolymerizable initiator.
This photosensitive composition is suitably used as a material for forming a component of a display panel (flat display panel) of a flat panel display such as PDP (plasma display panel).

[Component A]
The inorganic particles used as the component A contain glass powder as an essential component, but depending on the intended use of the fired body formed by the photosensitive composition of the present invention (type of components of the flat display panel). You can choose.
Here, the inorganic particles contained in the composition for forming the “dielectric” or “partition” constituting the flat display panel are preferably made of only glass powder.

Examples of the glass powder used as the component A include a low melting point glass powder having a heat softening point of 300 to 650 ° C, preferably 350 to 600 ° C.
When the thermal softening point of the glass powder is lower than the above range, organic substances such as resin (alkali-soluble polymer) are not completely decomposed and removed in the baking step of the photosensitive resin layer formed by the photosensitive composition. Due to the melting of the glass powder at the stage, a part of the organic substance remains in the formed member, and as a result, the members such as the dielectric layer and the partition are colored, and the light transmittance thereof May decrease. On the other hand, when the thermal softening point of the glass powder exceeds the above range, the photosensitive resin layer is formed because the photosensitive resin layer formed of the photosensitive composition needs to be fired at a high temperature. Distortion or the like is likely to occur in a substrate (eg, a glass substrate).

Examples of the glass powder include (1) Bi ₂ O ₃ —ZnO—B ₂ O ₃ series, (2) Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ series, and (3) Bi ₂ O ₃ —SiO _2. -B ₂ O ₃ -Li ₂ O _{system, (4) Bi 2 O 3} -SiO 2 -B 2 O 3 -Na 2 O _{based, (5) Bi 2 O 3} -SiO 2 -B 2 O 3 -K 2 O system, (6) Bi ₂ O ₃ —SiO ₂ —Li ₂ O system, (7) Bi ₂ O ₃ —SiO ₂ —Na ₂ O system, (8) Bi ₂ O ₃ —SiO ₂ —K ₂ O system (9) Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ —ZnO system, (10) SiO ₂ —B ₂ O ₃ —Li ₂ O system, (11) SiO ₂ —B ₂ O ₃ —Na ₂ O (12) SiO ₂ —B ₂ O ₃ —K ₂ O system, (13) SiO ₂ —B ₂ O ₃ —ZrO ₂ —MgO system, (14) SiO ₂ —B ₂ O ₃ —ZrO ₂ —CaO (15) SiO ₂ —B ₂ O ₃ —ZrO _{2-MAO type, (16) SiO 2 -B 2} O 3 -ZrO 2 -SrO _{system, (17) SiO 2 -B 2} O 3 -ZrO 2 -Li 2 O _{system, (18) SiO 2 -B 2} O ₃ -ZrO ₂ -Na _{2 O-based, (19) SiO 2 -B 2} O 3 -ZrO 2 -K 2 O _{system, (20) Al 2 O 3} -B 2 O 3 -SiO 2 -BaO-CaO-Li ₂ O—MgO—Na ₂ O—SrO—TiO ₂ —ZnO system, (21) Al ₂ O ₃ —B ₂ O ₃ —SiO ₂ —BaO—CaO—Li ₂ O—MgO—Na ₂ O—TiO ₂ — List glass powders of ZnO, (22) Al ₂ O ₃ —B ₂ O ₃ —SiO ₂ —BaO—CaO—Li ₂ O—MgO—Na ₂ O—Fe ₂ O ₃ —TiO ₂ —ZnO Can do.

In the composition for forming the “dielectric” or “partition” constituting the flat display panel, the shape of the glass powder constituting the inorganic particles as the component A is not particularly limited.
Further, as the glass powder, one kind alone or a combination of two or more kinds, that is, those having different compositions, those having different heat softening points, those having different shapes, those having different average particle diameters, etc. Can be used in combination.

The glass powder preferably contains silicon oxide in the range of 5 to 50% by mass, and more preferably in the range of 10 to 30% by mass, in order to obtain patterning with higher definition. Silicon oxide has a function of improving the denseness, strength and stability of the glass, and is also effective in reducing the refractive index of the glass. Further, by controlling the thermal expansion coefficient, it is possible to prevent peeling due to mismatch with a glass substrate as a substrate on which a photosensitive resin layer is formed.
When the silicon oxide content is 5% by mass or more, the coefficient of thermal expansion is kept small, and when a glass substrate is used as a substrate for forming the photosensitive resin layer, this occurs when the glass substrate is baked. The occurrence of cracks can be reduced and the refractive index can be kept low. Moreover, when the content of silicon oxide is 50% by mass or less, the glass transition point and the load softening point are kept low, and this glass is used when a glass substrate is used as a substrate for forming the photosensitive resin layer. The baking temperature on the substrate can be lowered.

Further, the glass powder preferably contains boron oxide in the range of 10 to 50% by mass, and more preferably in the range of 20 to 45% by mass.
When the content of boron oxide is 10% by mass or more, the glass transition point and the load softening point are kept low, and when a glass substrate is used as a substrate for forming the photosensitive resin layer, Can be easily baked. Moreover, the chemical stability of glass can be maintained because content of a boron oxide is 50 mass% or less. Boron oxide is also effective for lowering the refractive index.

The glass powder preferably contains at least one of barium oxide and strontium oxide so that the total amount is in the range of 1 to 30% by mass, and more preferably in the range of 2 to 20% by mass. It is more preferable to contain. These components are effective in adjusting the coefficient of thermal expansion, are effective in preventing deformation of the substrate on which the photosensitive resin layer is formed at the time of firing, the effect of imparting electrical insulation, and formed members (for example, For improving the stability and denseness of the partition walls.
When the content is 1% by mass or more, devitrification due to crystallization of the glass can be prevented, and when the content is 30% by mass or less, the thermal expansion coefficient and the refractive index can be reduced. At the same time, chemical stability can be maintained.

Moreover, it is preferable that glass powder contains aluminum oxide in 1-40 mass%. Aluminum oxide has the effect of stabilizing the glass by expanding the vitrification range, and is also effective in extending the pot life of the photosensitive composition.
When the content of aluminum oxide is within the above range, the glass transition point and the load softening point can be kept low, and the adhesion to the substrate on which the photosensitive resin layer is formed can be improved.

Moreover, it is preferable that glass powder contains at least 1 sort (s) among calcium oxide and magnesium oxide so that the total amount may be 1-20 mass%. These components have the effect of making the glass easier to melt and controlling the thermal expansion coefficient.
When the content is 1% by mass or more, devitrification due to crystallization of the glass can be prevented, and when the content is 20% by mass or less, the chemical stability of the glass can be maintained. .

  The glass powder preferably contains an alkali metal oxide of lithium oxide, sodium oxide and potassium oxide in the range of 1 to 20% by mass. Alkali metal oxides have the effect of facilitating control of the thermal softening point and thermal expansion coefficient of glass and lowering the refractive index as glass powder. Since alkali metal oxides may promote ion migration and diffusion, the total amount of 20% by mass or less can maintain the chemical stability of the glass and keep the thermal expansion coefficient small. .

  The glass powder may contain zinc oxide, titanium oxide, zirconium oxide and the like in addition to the above components.

The average particle size of the glass powder is selected in consideration of the shape of the pattern to be produced, but is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm for pattern formation. Moreover, it is preferable that the specific surface area of glass powder is 0.1-300 m < ² > / g.

Such a glass powder may be contained in a composition for forming a constituent element (for example, an electrode, a resistor, a phosphor, a color filter, a black matrix, etc.) other than the dielectric and barrier rib of the flat display panel. Good.
The content of the glass powder in this case varies depending on the application, but is usually 60 to 90 parts by mass, preferably 70 to 90 parts by mass with respect to 100 parts by mass of the total amount of inorganic particles including the glass powder.

The inorganic particles other than the glass powder contained in the composition for forming the “electrode” constituting the flat display panel are composed of metals such as Ag, Au, Al, Ni, Ag—Pd alloy, Cu and Cr. Examples thereof include conductive particles.
Among these, it is preferable to use Ag which is relatively inexpensive and does not cause a decrease in conductivity due to oxidation even when baked in the air.

In the composition for forming the “electrode” constituting the flat display panel, the shape of the conductive particles constituting the inorganic particles as the component A is not particularly limited, and for example, granular, spherical, flakes, etc. In addition, even if all of them have the same shape, two or more types having different shapes can be used in combination.
The average particle diameter of the conductive particles is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, and two or more kinds having different average particle diameters can be used in combination.

  Thus, when using electroconductive particle with glass powder as an inorganic particle as A component, the content rate of glass powder is usually 45-90 normally with respect to 100 mass parts of whole quantity of an inorganic particle. It is a mass part, Preferably it is 50-90 mass parts, More preferably, it is 55-86 mass parts.

The inorganic particles contained in the composition for forming the “transparent electrode” among the “electrodes” constituting the flat display panel include indium oxide, tin oxide, tin-containing indium oxide (ITO), and antimony content. One selected from tin oxide (ATO), fluorine-added indium oxide (FIO), fluorine-added tin oxide (FTO), fluorine-added zinc oxide (FZO), and Al, Co, Fe, In, Sn and Ti Examples thereof include zinc oxide fine particles containing two or more metals.
Here, LCD (liquid crystal display), organic EL (electroluminescence) elements, printed circuit boards, multilayer circuit boards, modules, inductors, LSIs (large scale) can be used as flat display panels with “transparent electrodes” as components. Integration).

Examples of inorganic particles other than glass powder contained in the composition for forming the “resistor” constituting the flat display panel include particles made of RuO ₂ or the like.
As inorganic particles contained in the composition for forming the “phosphor” constituting the flat display panel, particles made of fluorescent materials of various colors such as a red fluorescent material, a green fluorescent material, and a blue fluorescent material, etc. Can be mentioned.
Examples of the red fluorescent material include Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ³⁺ , YVO ₄ : Eu ³⁺ , (Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ ) ₂ : Mn and the like.
Examples of green fluorescent materials include Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : Tb, etc. Is mentioned.
As the fluorescent material for blue, Y ₂ SiO ₅ : Ce, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , (Ca, Sr, Ba) ₁₀ (PO ₄ ) _{6 Cl 2} : Eu ^{2 +} , (Zn, Cd) S: Ag and the like.
Examples of inorganic particles other than glass powder contained in the composition for forming the “color filter” constituting the flat display panel include red substances such as Fe ₂ O ₃ and Pb ₃ O ₄ , Cr ₂ O _3, etc. And particles made of blue materials such as 2 (Al ₂ Na ₂ Si ₃ O ₁₀ ) · Na ₂ S ₄ .
Examples of inorganic particles other than glass powder contained in the composition for forming the “black matrix” constituting the flat display panel include metals such as Co, Cr, Cu, Fe, Mn, Ni, Ti, Zn, and the like. Examples of the particles include oxides, composite oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, and graphite. Among these, Co, Cr, Cu, Fe, Mn Metal particles, metal oxide particles and composite oxide particles selected from the group consisting of Ni and Ti are preferred. These can be used alone or in combination of two or more.
Moreover, as the average particle diameter, Preferably it is 0.01-10 micrometers, More preferably, it is 0.05-5 micrometers, Most preferably, it is 0.1-2 micrometers.
Thus, when using particles other than these glass powders together with the glass powder as the inorganic particles as the component A, the content ratio of the glass powder is usually based on 100 parts by mass of the total amount of the inorganic particles. It is 45-90 mass parts, Preferably it is 50-90 mass parts, More preferably, it is 55-86 mass parts.

[Component B] The alkali-soluble polymer used as the component B is dissolved in an alkaline developer and is soluble to such an extent that the desired development processing is performed.
Specific examples of the alkali-soluble polymer include (meth) acrylic resins, hydroxystyrene resins, novolac resins, and polyester resins.
Among such alkali-soluble polymers, particularly preferred are the following copolymer of monomer (a) and monomer (c), monomer (a), monomer (b) and monomer (c) Acrylic resins such as coalescence can be mentioned.

Monomer (I):
Monomers (I) are carboxyl group-containing monomers, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid. Examples include acid mono (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono (meth) acrylate, and the like.
Monomer (b):
The monomer (b) is an OH group-containing monomer, and specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. Hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and the like.
Monomer (C):
The monomer (c) is a monomer copolymerizable with the monomer (b) or the monomer (b). Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic. N-butyl acid, 2-ethylhexyl (meth) acrylate, ethoxyethyl (meth) acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters other than monomer (ii) such as dicyclopentanyl; methyl-α- (hydroxymethyl) acrylate, ethyl-α- (hydroxymethyl) acrylate, n-butyl-α- (hydroxymethyl) Acrylate having α-hydroxymethyl group such as acrylate; Fragrance such as styrene and α-methylstyrene Group vinyl monomers; conjugated dienes such as butadiene and isoprene; one end of a polymer chain such as polystyrene, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate benzyl ( And macromonomers having a polymerizable unsaturated group such as a (meth) acryloyl group.

  The copolymer of monomer (a) and monomer (c), and the copolymer of monomer (a), monomer (b) and monomer (c) are due to the presence of copolymer components derived from monomer (a). , Having alkali solubility. Among these, the copolymer of the monomer (a), the monomer (b), and the monomer (c) is excellent in dispersion stability of inorganic particles as component A and solubility in an alkali developer described later. Particularly preferred.

  The content of the copolymer component derived from the monomer (a) in such a copolymer is preferably 5 to 60% by mass, particularly preferably 10 to 40% by mass, and the copolymer derived from the monomer (b). The content of the component is preferably 1 to 60% by mass, particularly preferably 5 to 50% by mass.

  Particularly preferable as the alkali-soluble polymer used in the photosensitive composition of the present invention is methacrylic acid / (meth) acrylic acid 2-hydroxypropyl / (meth) acrylic acid n-butyl copolymer, methacrylic acid / Examples include succinic acid mono (2- (meth) acryloyloxyethyl) / (meth) acrylic acid 2-hydroxypropyl / (meth) acrylic acid n-butyl copolymer.

As the molecular weight of the alkali-soluble polymer, the weight average molecular weight Mw is preferably 5,000 to 5,000,000, more preferably 10,000 to 300,000.
Moreover, as a content rate of the alkali-soluble polymer in the photosensitive composition of this invention, it is 5-70 mass parts normally with respect to 100 mass parts of inorganic particles, Preferably, it is 5-50 mass parts, Especially preferably. Is 10-40 parts by mass.

[C component]
The specific polyfunctional acrylate compound used as component C is a photopolymerizable monomer, and its solubility in a developer is reduced by polymerization by exposure in the presence of a photopolymerization initiator described later, that is, an alkali. It is a substance that becomes insoluble or hardly soluble in alkali. By using a substance that becomes alkali-insoluble or hardly soluble by such exposure, it becomes easier to provide contrast between the exposed portion and the unexposed portion with respect to the alkaline developer, and it becomes easier to enhance the pattern and control the pattern shape. There are advantages.

In the general formula (1) representing the specific multifunctional acrylate compounds, n is an integer of 1 to 4, R ¹ is one in which a hydrogen atom or a methyl group.
In the general formula (1), X, -O- _{group, -O (CH 2 CH 2)} a O- group (where, a is an integer from 1 to 8.) Or -O (CH ₂ CH ₂ CH ₂ ) _b O— group (where b is an integer of 1 to 8).
In the general formula (1), Y represents a methylene group, an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, an unsubstituted or substituted phenylene group, and an unsubstituted or substituted group. And a group selected from the group consisting of a cyclohexylene group and a cyclohexylene group, a part of which is an unsaturated bond (hereinafter also referred to as “unsaturated hexylene group”).

The alkylene group having 2 to 8 carbon atoms representing the group Y may be either a straight chain or branched chain, such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc. Among these, an alkylene group having 2 to 4 carbon atoms is preferable.
The alkenylene group having 2 to 8 carbon atoms representing the group Y may be either a straight chain or a branched chain. For example, a vinyl group, 1-methylidene-ethylene group (—C (═CH ₂ ) CH ₂ —) Etc.
Examples of the unsaturated bond cyclohexylene group representing the group Y include a cyclohexenylene group.
Examples of the group that can be substituted with a phenylene group, a cyclohexylene group, or an unsaturated cyclohexylene group include, for example, an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Etc.
The group Y is preferably a methylene group or an alkylene group having 2 to 4 carbon atoms, and is preferably a methylene group.

  Preferable specific examples of such a specific polyfunctional acrylate compound include compounds represented by the following formula (1-1).

Moreover, as a content rate of the specific polyfunctional acrylate compound in the photosensitive composition of this invention, it is 1-50 mass parts normally with respect to 100 mass parts of inorganic particles, Preferably, 1-30 mass parts, Especially Preferably, it is 5-20 mass parts.
When the content ratio of the specific polyfunctional acrylate compound is excessive, an unexposed portion on the substrate surface is formed in the process of developing the photosensitive resin layer formed on the substrate to form a pattern. There is a possibility that a development residue may be generated in the portion that has been left.
On the other hand, when the content ratio of the specific polyfunctional acrylate compound is too small, it is difficult to provide contrast between the exposed portion and the unexposed portion with respect to the developer, and a sufficient development margin may not be obtained.

[Component D] Specific examples of the photopolymerization initiator used as the component D include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl. Ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morphol Carbonyl compounds such as linophenyl) -butan-1-one; azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; mercaptan disulfide, bis (2,4,6-trimethylbenzoyl) -phen Organic sulfur compounds such as ruphosphine oxide; organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and paraffin hydroperoxide; 1,3-bis (trichloro Methyl) -5- (2′-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine Trihalomethanes such as: 2,2′-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl 1,2′-biimidazole and other imidazole dimers; 2,4-dimethylthioxanthone, 2 , 4-diethylxanthone, 2-chlorothioxanthone, 2,4-diisopropylthiol Thioxanthone such as cantonal can be mentioned. These can be used alone or in combination of two or more.

  As a content rate of the photoinitiator in the photosensitive composition of this invention, it is 5-100 mass parts normally with respect to 100 mass parts of specific polyfunctional acrylate compounds, Preferably, it is 10-70 mass parts. is there.

[E component]
The photosensitive composition of the present invention preferably contains an acrylate compound having 2 to 3 functional groups (hereinafter also referred to as “specific 2 to 3 functional acrylate compound”) as the E component.
The specific 2-3 functional acrylate compound as the E component is a photopolymerizable monomer, and in the same manner as the specific polyfunctional acrylate compound used as the C component, by exposure in the presence of the photopolymerization initiator described above. Polymerization reduces the solubility in a developer, that is, a substance that becomes alkali-insoluble or alkali-insoluble.

This specific 2-3 functional acrylate compound has 2 to 3 functional groups. Preferred specific examples of the functional group possessed by the specific 2-3 functional acrylate compound include -O- group, -O (CH ₂ CH ₂ ) _a O— group (where a is an integer of 1 to 8) or —O (CH ₂ CH ₂ CH ₂ ) _b O— group (where b is an integer of 1 to 8). There are).

Specific examples of such specific 2-3 functional acrylate compounds include di (meth) acrylates related to alkylene glycol such as ethylene glycol and propylene glycol; di (meth) related to polyalkylene glycol such as polyethylene glycol and polypropylene glycol. ) Acrylates; Poly (meth) acrylates related to polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc .; polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, spirane resins Oligo (meth) acrylates such as: both terminal hydroxy poly-1,3-butadiene, both terminal hydroxy polyisoprene, both terminal hydroxy such as hydroxy polycaprolactone Of polymer di (meth) acrylates according to, tris [2- (meth) acryloyloxyethyl] phosphate and the like. These can be used alone or in combination of two or more.
Of these, poly (meth) acrylates relating to trihydric or higher polyhydric alcohols are preferred, and specific examples thereof include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate. , Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc., among these, trimethylolpropane triacrylate , Pentaerythritol triacrylate and dipentaerythritol Sa acrylate is particularly preferably used.
Moreover, it is preferable that the molecular weight of a specific 2-3 trifunctional acrylate compound is 200-1000.

Moreover, as a content rate of the specific 2-3 functional acrylate compound in the photosensitive composition of this invention, it is 1-50 mass parts with respect to 100 mass parts of inorganic particles, Preferably, 1-40 mass parts, especially Preferably, it is 3-30 mass parts.
When the content ratio of the specific 2-3 functional acrylate compound is excessive, there is a fear that a sufficiently high viscosity cannot be obtained in the photosensitive composition, and development processing is performed on the photosensitive resin layer formed on the substrate. In the process of forming a pattern, the contrast between the exposed portion and the unexposed portion becomes difficult to provide due to the fact that this specific 2-3-functional acrylate compound has an effect of promoting dissolution in the developer. There is a risk that a sufficient development margin cannot be obtained.
On the other hand, when the content ratio of the specific 2-3 functional acrylate compound is excessively small, the viscosity of the composition may become extremely large based on the specific multifunctional acrylate compound having a large viscosity, and the specific Since the development residue is generated by adsorbing the polyfunctional acrylate compound to the glass powder, the generation of the development residue may not be sufficiently suppressed.

[F component]
The photosensitive composition of the present invention preferably contains hydroxypropyl cellulose as the F component.
This hydroxypropyl cellulose is a polymer compound having a polar group and acts as a thickener. By being contained in the photosensitive composition, the viscosity of the composition is low even if the content ratio is small. In addition, the thixotropy required when the composition is applied to the substrate by a screen printing method can be imparted.
Here, in the photosensitive composition of the present invention, the viscosity of the composition can be increased by increasing the polar group content of the alkali-soluble polymer as component B without containing hydroxypropylcellulose. However, since the content ratio of the alkali-soluble polymer in the photosensitive composition is large, the alkali-soluble polymer reacts with the glass powder constituting the component A, so that Viscosity may change over time. Therefore, it is preferable to use hydroxypropyl cellulose to adjust the viscosity of the composition because such a harmful effect does not occur and a sufficient effect can be obtained even if the addition amount is small. .

  As a content rate of the hydroxypropyl cellulose in the photosensitive composition of this invention, it is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of photosensitive compositions.

  When the content of hydroxypropyl cellulose is less than 0.1 part by mass, the viscosity of the photosensitive composition becomes extremely small, and uneven coating occurs when the photosensitive composition is applied to a substrate, resulting in a uniform film. May not be formed. On the other hand, when the content ratio of hydroxypropyl cellulose exceeds 10 parts by mass, the viscosity of the photosensitive composition becomes extremely large, and when the photosensitive composition is applied to a substrate, particularly when applied by a screen printing method. In some cases, the releasability from the plate is poor and a uniform film cannot be formed.

〔solvent〕
The photosensitive composition of the present invention usually contains a solvent for imparting appropriate fluidity or plasticity and good film forming properties. The solvent used has good affinity with inorganic particles, good solubility with alkali-soluble polymers, etc., and can impart appropriate viscosity to the resulting photosensitive composition, and can be easily dried. Preferably, it can be removed by evaporation.

  Particularly preferred solvents include ketones, alcohols and esters (hereinafter referred to as “specific solvents”) having a normal boiling point (boiling point at 1 atm) of 100 to 200 ° C.

  Specific examples of the specific solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; n-pentanol, 4-methyl-2-pentanol, cyclohexanol, diacetone alcohol, dihydroxyterpineol, Alcohols such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. Ether-based alcohols; saturated aliphatic monocarboxylic acid alkyl esters such as n-butyl acetate and amyl acetate; lactic acid esters such as ethyl lactate and lactic acid n-butyl Examples: ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, among which methyl butyl ketone, cyclohexanone, diacetone alcohol , Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, dihydroxyterpineol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate Etc. are preferable. These specific solvents can be used alone or in combination of two or more.

  Specific examples of the solvent that can be used other than the specific solvent include ethyl cellosolve, methyl cellosolve, terpineol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol, and benzyl alcohol.

  The content ratio of the solvent in the photosensitive composition of the present invention can be appropriately selected within a range in which good film formability (fluidity or plasticity) is obtained.

〔Additive〕
In addition, the photosensitive composition of the present invention includes, as optional components, a plasticizer, a dispersant, a development accelerator, an adhesion assistant, a coupling agent, an antihalation agent, a leveling agent, a storage stabilizer, an antifoaming agent, an oxidation agent. Various additives such as an inhibitor, an ultraviolet absorber, a sensitizer, and a chain transfer agent may be contained.

[Photosensitive composition]
The photosensitive composition of the present invention comprises the above-mentioned inorganic particles, alkali-soluble polymer, specific polyfunctional acrylate compound, photopolymerization initiator, solvent, and specific 2-3 functional acrylate compound used as necessary, hydroxypropylcellulose And the additive can be prepared by kneading using a kneader such as a roll kneader, a mixer, a homomixer, a ball mill, or a bead mill.
The photosensitive composition thus prepared has a viscosity of usually 3,000 to 50,000 cP, preferably 5,000 to 30,000 cP.

According to the above photosensitive composition, the specific polyfunctional acrylate compound as C component is contained as a photopolymerizable monomer, and the specific polyfunctional acrylate compound has a carboxylic acid group as a functional group. And having a good solubility in the developer, and having a viscosity that can be increased on the basis of the interaction with the glass powder constituting the inorganic particles as the component A, 3,000 cP ( In addition to having a viscosity as high as 3,000 mPa · s), it is possible to suppress the occurrence of development residues when developing a photosensitive resin layer made of a photosensitive composition.
Further, according to this photosensitive composition, when the photosensitive resin layer made of the photosensitive composition is subjected to a baking treatment, excellent defoaming property can be obtained in the photosensitive resin layer. Even when the laminated body formed by laminating the conductive resin layer is collectively fired, bubbles do not remain in the obtained fired body.

  Furthermore, in this photosensitive composition, the specific 2-3 functional acrylate compound as E component is contained with the specific polyfunctional acrylate compound as C component as a photopolymerizable monomer, and this specific 2 The trifunctional acrylate compound can be adjusted so that the viscosity of the composition does not become excessively large due to the action of the specific polyfunctional acrylate compound, so that it has a high viscosity and is made of a photosensitive composition comprising a photosensitive composition. In the case of developing the functional resin layer, generation of development residues can be sufficiently suppressed.

[Method of forming fired body]
In the method for forming a fired body of the present invention, a photosensitive resin layer comprising the above-described photosensitive composition of the present invention is formed on a substrate, and the formed photosensitive resin layer is exposed to light to form a latent image having a pattern. After the formation, the photosensitive resin layer is developed to form a pattern layer corresponding to the pattern formed by the exposure process, and the pattern layer is fired to obtain a fired body having a pattern. It is what.
That is, the photosensitive composition is applied to the surface of the substrate and dried to form a photosensitive resin layer on the substrate, and the photosensitive resin layer is exposed to light to form the photosensitive resin layer. A latent image of a pattern to be formed is formed and developed to form a resin pattern layer, and the resin pattern layer is baked to form a target pattern.

(I) Resin layer forming step:
Formation of the photosensitive resin layer is performed by applying a photosensitive composition on a substrate and drying the obtained coating film.
The photosensitive resin layer may be formed as a single photosensitive resin layer by performing the steps of coating the photosensitive composition and drying the coating film once. By repeating the drying process step a plurality of times, a photosensitive resin layer made of a laminate may be obtained.
As a method for applying the photosensitive composition to the substrate, various methods such as a screen printing method, a roll coating method, a spin coating method, and a casting coating method can be used.
As drying treatment conditions for the coating film, for example, the drying temperature is 50 to 150 ° C., and the drying time is 0.5 to 30 minutes. Further, the residual ratio of the solvent after drying (content in the photosensitive resin layer) is usually within 2% by mass.
The thickness of the photosensitive resin layer varies depending on the content and size of the inorganic particles, but is, for example, 1 to 500 μm.

  As the substrate, for example, a plate-like member made of an insulating material such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, or polyimide can be used. For the surface of the plate-like member, chemical treatment with a silane coupling agent or the like, if necessary, plasma treatment; thin film formation treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, etc. Such an appropriate pretreatment may be performed.

(Ii) Exposure process:
The exposure treatment of the photosensitive resin layer is performed by a method of selectively irradiating the photosensitive resin layer with radiation such as ultraviolet rays through an exposure mask or a method of scanning the photosensitive resin layer with laser light.
Here, as the radiation irradiation apparatus, an ultraviolet irradiation apparatus generally used in a photolithography method, an exposure apparatus used when manufacturing a semiconductor and a liquid crystal display device, a laser apparatus, and the like can be used. There is no particular limitation.

(Iii) Development processing step:
The development processing of the photosensitive resin layer is performed by, for example, washing with water after dissolving the unexposed portion of the photosensitive resin layer with an alkali developer.
As an active ingredient of the alkaline developer, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate , Inorganic such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia Alkaline compounds; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Triethanolamine, and organic alkaline compounds such as ethanol amine.
The alkaline developer can be prepared by dissolving one or more of the above alkaline compounds in water or the like.
As a development processing method, an immersion method, a rocking method, a shower method, a spray method, a paddle method, or the like can be used.
Specific conditions for the development processing, such as development time and development temperature, are appropriately set according to the type of photosensitive composition used, the type of developer, the composition and concentration, the development method, and the like.

(Iv) Firing process:
The baking process of the resin pattern layer is performed by heating the resin pattern layer.
Moreover, a baking process is performed on the conditions which the organic substance in a resin pattern layer burns, and a baking process temperature is 400-600 degreeC and baking time is 10 to 90 minutes normally.

According to such a method for forming a fired body, since the photosensitive composition of the present invention is used as a constituent material thereof, good coating properties can be obtained when the photosensitive composition in the formation process is applied onto a substrate. In addition, since development residue is suppressed in the development process, a fired body having a good pattern can be easily obtained.
Further, in the method for forming the fired body, when the photosensitive resin layer made of the photosensitive composition is fired, the photosensitive resin layer has excellent defoaming properties, and therefore, a plurality of photosensitive properties can be obtained. Even when the laminated body formed by laminating the resin layers is collectively fired, bubbles do not remain in the obtained fired body.

[Flat display panel]
The method for producing a flat display panel according to the present invention includes forming a photosensitive resin layer made of the above-described photosensitive composition of the present invention on a substrate, and exposing the formed photosensitive resin layer to a latent image having a pattern. Then, the photosensitive resin layer is developed to form a pattern layer corresponding to the pattern formed by the exposure process, and the pattern layer is baked to form partition walls, electrodes, resistors, and dielectrics. The method includes a step of forming a component selected from a layer, a phosphor, a color filter, and a black matrix.
That is, based on the above-described method for forming a fired body, specifically, a constituent element of a target flat display panel by going through a resin layer forming step, an exposure processing step, a development processing step, and a baking processing step in this order. (Specifically, partition walls, electrodes, resistors, dielectric layers, phosphors, color filters, and black matrices) can be formed.

  According to the flat display panel manufacturing method of the present invention, since the photosensitive composition of the present invention is used as a constituent material of the constituent element, the photosensitive composition in the process of forming the constituent element is applied onto a substrate. In this case, good coating properties can be obtained, and generation of development residues can be suppressed in the development process, so that a component having a desired shape can be easily formed. Here, according to this manufacturing method, a flat display panel constituting a flat display such as a liquid crystal display, an organic electroluminescence display, an FED display, and an SED display can be formed in addition to the PDP.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto. In the following, “part” means “part by mass”.

<Example 1>
(1) Preparation of photosensitive composition:
As component A, 100 parts of black pigment made of cobalt oxide and 450 parts of Bi ₂ O ₃ —ZnO—B ₂ O ₃ glass powder, and as component B, 10.0% by weight of methacrylic acid, (meth) acrylic acid 2 -Copolymer of 40.0% by mass of hydroxypropyl, 15.0% by mass of 2-ethylhexyl (meth) acrylate and 35.0% by mass of ethoxyethyl (meth) acrylate (Mw: 30,000, Tg: 8. 90 parts of an alkali-soluble polymer comprising 4 ° C.) and a polyfunctional acrylate compound “M520” (manufactured by Toagosei Co., Ltd.) as the C component, that is, in the general formula (1), R ¹ is a hydrogen atom, X is —O— 40 parts of a specific polyfunctional acrylate compound composed of a compound in which Y is an ethylene group and n is 1, and a polyfunctional acrylate compound “M321” (Toagosei Co., Ltd.) as an E component 20 parts of trimethylolpropane propylene oxide modified triacrylate (hereinafter also referred to as “acrylate compound (1)”), and a photopolymerization initiator “Irg. 970” (manufactured by Ciba Geigy) as a D component, 20 parts of 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone (hereinafter also referred to as “photopolymerization initiator (1)”), and photopolymerization initiator “DETX-S” (Manufactured by Nippon Kayaku Co., Ltd.), that is, 10 parts of 2,4-diethylthioxanthone (hereinafter also referred to as “photopolymerization initiator (2)”) and 100 parts of dihydroterpineol as a solvent in a stirring deaerator. After kneading, a photosensitive composition (1) was prepared by dispersing with three rolls.
About the obtained photosensitive composition (1), the viscosity was measured on the measurement conditions of the shear rate 20s < ^-1 > using the viscometer "TVE-33H" (made by Toki Sangyo Co., Ltd.). The results are shown in Table 1.

(2) Evaluation of photosensitive composition:
About the obtained photosensitive composition (1), the following method confirmed the development margin and the generation amount of the development residue, and the presence or absence of the bubble generation in a baked body. The results are shown in Table 1.

  After the photosensitive composition (1) is applied by screen printing on a glass substrate, it is dried in a clean oven at 120 ° C. for 20 minutes, thereby forming a 3.7 μm thick resin layer on the glass substrate. Three samples each having a structure in which a resin layer was formed on were prepared.

  Using the first sample, the resin layer formed on the glass substrate was developed with a 0.3 mass% sodium carbonate aqueous solution at a liquid temperature of 30 ° C. as a developer, and the resin layer was developed by the shower method. The time required for starting the development process (the moment when the developer touches the resin layer) and completely removing the resin layer (the moment when the resin layer is removed) (hereinafter also referred to as “TTC”). ) Was measured.

Using the second sample, first, g-line (436 nm) is applied to the resin layer formed on the glass substrate with an ultrahigh pressure mercury lamp through a striped negative exposure mask having a line width of 100 μm and a space width of 100 μm. ), H-line (405 nm), and i-line (365 nm) mixed light was applied to perform exposure treatment of the resin layer. The exposure amount was 150 mJ / cm ^{2 in} terms of illuminance measured with a 365 nm sensor.
Next, with respect to the exposed resin layer, a 0.3% by mass sodium carbonate aqueous solution having a liquid temperature of 30 ° C. is used as a developer, and the resin layer is developed by a shower method. Measure the time required until the exposed portion of the resin layer begins to peel (the moment when the exposed portion of the resin layer begins to peel) until the developer touches the resin layer, and the ratio of the measured value to TTC is the development margin. Calculated as

Using the third sample, first, a g-line (436 nm) is applied to the resin layer formed on the glass substrate by an ultrahigh pressure mercury lamp through a striped negative exposure mask having a line width of 100 μm and a space width of 100 μm. ), H-line (405 nm), and i-line (365 nm) mixed light was applied to perform exposure treatment of the resin layer. The exposure amount was 150 mJ / cm ^{2 in} terms of illuminance measured with a 365 nm sensor.
Next, with respect to the exposed resin layer, a 0.3 mass% sodium carbonate aqueous solution having a liquid temperature of 30 ° C. was used as a developer, and the resin layer was developed by a shower method for 1.5 times the TCC (TCC). × 1.5 seconds) and washed with ultrapure water. This removed the unexposed part of the resin layer that was not irradiated with ultraviolet rays, thereby forming a resin pattern layer.
When this resin pattern layer is observed with an optical microscope, the presence or absence of development residue in the portion where the unexposed portion of the substrate is formed is confirmed, and there is no development residue having an average particle size of about 1 μm. "○", the case where there are one or more less than five development residues per 10 [mu] m ² "△", was assessed if there are five or more development residues per 10 [mu] m ² and ×.

In addition, on the resin pattern layer having a thickness of 3.7 μm obtained above, Bi ₂ O ₃ —ZnO—BaO-based glass powder (thermal softening point: 575 to 580 ° C., average particle diameter: 2.3 μm), A glass paste layer made of a glass paste material containing ethyl cellulose and dihydroterpinyl acetate (hereinafter also referred to as “glass paste material (1)”) is laminated, and this laminate is subjected to a firing temperature of 580 ° C. By baking for 30 minutes, a black pattern layer having a thickness of 1.3 μm and a glass paste material having a thickness of 18.0 μm made of a glass sintered body derived from the photosensitive composition (1) is formed on the surface of the glass substrate. A fired body formed by laminating the dielectric layers derived from 1) was formed.
When the obtained fired body is observed with an optical microscope at a magnification of 500 times, there is no generation of bubbles having an outer diameter of 10 μm or more in the dielectric layer (on the black pattern layer or the black pattern layer). When it was obtained, “◯” was evaluated, and “×” was evaluated when bubbles having an outer diameter of 10 μm or more were generated in the dielectric layer.

<Example 2 and Example 3>
Amount of glass powder as component A, amount of polyfunctional acrylate compound “M520” (manufactured by Toa Gosei Co., Ltd.) as component C, and acrylate compound (1) as component E (polyfunctional acrylate compound “M321” (Toa A photosensitive composition (2) and a photosensitive composition (3) were prepared in the same manner as in Example 1 except that each of the amounts of Synthetic Co., Ltd.) was changed to the amounts shown in Table 1. The viscosity was measured.
Further, using the photosensitive composition (2) and the photosensitive composition (3), in the same manner as in Example 1, formation of a resin layer having the thickness shown in Table 1, exposure treatment and development treatment, and baking treatment The photosensitive composition was evaluated by performing the above. The results are shown in Table 1.

<Example 4>
As component A, 100 parts of silver particles having an average particle size of 2.2 μm and 8 parts of Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ —ZnO-based glass powder, and as component B, 2-ethylhexyl (meth) acrylate 35. Copolymer (Mw: 43, 0% by weight, 37.5% by weight of 2-ethoxyethyl (meth) acrylate, 15.0% by weight of 2-hydroxypropyl (meth) acrylate and 12.5% by weight of methacrylic acid) 000, Tg: 2.4 ° C.) 13 parts alkali-soluble polymer, 4 parts polyfunctional acrylate compound “M520” (manufactured by Toagosei Co., Ltd.) as C component, 2 parts acrylate compound (1) as E component , D component, 2 parts of photopolymerization initiator (1) and 1 part of photopolymerization initiator (2), 1 part of 3-methacryloxypropyltrimethoxysilane as a coupling agent, as solvent With 24 parts of dihydroterpineol, in the same manner as in Example 1, the photosensitive composition (4) was prepared and subjected to measurement of its viscosity.
Further, using the photosensitive composition (4), a resin layer having a thickness of 10 μm was formed in the same manner as in Example 1, and a striped negative exposure mask having a line width of 30 μm and a space width of 30 μm was used. Except for performing the exposure treatment with an exposure amount of 100 mJ / cm ² , the exposure treatment and the development treatment are performed by the same method as in Example 1, and the photosensitive composition is applied to the surface of the glass substrate by the same method as in Example 1. A fired body in which a 4.8 μm thick electrode pattern layer made of a glass sintered body derived from the product (4) and a dielectric layer derived from a 18.0 μm thick glass paste material (1) are laminated. The photosensitive composition was evaluated by performing the baking treatment to be formed. The results are shown in Table 1.

<Example 5>
As component A, 5 parts of a filler made of titanium dioxide (TiO ₂ ) and 50 parts of Bi ₂ O ₃ —SiO ₂ —Al ₂ O ₃ glass powder, as component B, 2-ethoxyethyl methacrylate 15.0% by mass, Alkali-soluble polymer 25 comprising a copolymer (Mw: 20000, Tg: 40 ° C.) of 35.0% by weight of 2-hydroxypropyl methacrylate, 10% by weight of methacrylic acid, 5% by weight of styrene and 35% by weight of benzyl methacrylate. Part, C component, polyfunctional acrylate compound “M520” (manufactured by Toa Gosei Co., Ltd.) 10 parts, E component, acrylate compound (1) 2.5 parts, D component, photopolymerization initiator (1) 0. 1 part and 0.04 part of photopolymerization initiator (2), 0.3 part of 3-methacryloxypropyltrimethoxysilane as a coupling agent, solvent Using dihydroterpineol 20 parts by, in the same manner as in Example 1, the photosensitive composition (5) was prepared and subjected to measurement of its viscosity.
Further, using the photosensitive composition (5), a resin layer having a thickness of 81 μm was formed in the same manner as in Example 1, and exposure for a lattice negative having a line width of 40 μm, a line width of 30 μm, and a space width of 200 μm. The surface of the glass substrate was subjected to the exposure process and the development process by the same method as in Example 1 except that the exposure process was performed with the exposure mask at an exposure amount of 110 mJ / cm ^2. The photosensitive composition was evaluated by performing a baking treatment for forming a sintered body in which a partition pattern layer having a thickness of 59.0 μm made of a glass sintered body derived from the photosensitive composition (5) was laminated. Went. The results are shown in Table 1.
Here, the presence or absence of generation of bubbles in the fired body according to the fired body obtained in the firing treatment was confirmed in the partition wall pattern layer.

<Example 6>
Photosensitive in the same manner as in Example 1, except that the polyfunctional acrylate compound as the E component was not used and the amount of the polyfunctional acrylate compound “M520” (manufactured by Toagosei Co., Ltd.) as the C component was 60 parts. A composition (6) was prepared and the viscosity was measured.
Further, by using the photosensitive composition (6), in the same manner as in Example 1, the formation of a resin layer having a thickness of 4.0 μm, exposure treatment and development treatment, and baking treatment were performed. Evaluation was performed. The results are shown in Table 1.

<Comparative example 1>
60 parts of acrylate compound (1) (polyfunctional acrylate compound “M321” (manufactured by Toagosei Co., Ltd.)) as the E component is used as the photopolymerizable monomer without using the polyfunctional acrylate compound as the C component. A comparative photosensitive composition (1) was prepared in the same manner as in Example 1 except that the viscosity was measured.
Further, by using the comparative photosensitive composition (1) and performing the formation of a resin layer having a thickness of 3.4 μm, exposure treatment and development treatment, and baking treatment in the same manner as in Example 1, the photosensitive composition was obtained. The product was evaluated. The results are shown in Table 1.

<Comparative example 2>
A polyfunctional acrylate compound “M360” (manufactured by Toagosei Co., Ltd.), that is, trimethylolpropane ethylene oxide-modified triacrylate (hereinafter referred to as “acrylate compound”) is used as a photopolymerizable monomer without using a polyfunctional acrylate compound as component C. (It is also referred to as “(2)”.) A comparative photosensitive composition (2) was prepared in the same manner as in Example 1 except that 60 parts were used, and the viscosity thereof was measured.
Further, by using the comparative photosensitive composition (2) and carrying out formation of a resin layer having a thickness of 3.5 μm, exposure treatment and development treatment, and baking treatment in the same manner as in Example 1, the photosensitive composition was obtained. The product was evaluated. The results are shown in Table 1.

<Comparative Example 3>
A polyfunctional acrylate compound “KAYARAD DPCA-60” (manufactured by Nippon Kayaku Co., Ltd.), ie, dipentaerythritol pentahexa modified acrylate (hereinafter, "It is also called an acrylate compound (3)." A comparative photosensitive composition (3) was prepared in the same manner as in Example 1 except that 60 parts were used, and the viscosity was measured.
Further, by using the comparative photosensitive composition (3) and performing the formation of a resin layer having a thickness of 3.5 μm, the exposure process and the development process, and the baking process in the same manner as in Example 1, the photosensitive composition was obtained. The product was evaluated. The results are shown in Table 1.

As is clear from the results in Table 1, it was confirmed that the photosensitive compositions according to Examples 1 to 6 have high viscosity and can suppress development residue. In addition, it was confirmed that any of the photosensitive compositions according to Examples 1 to 5 can obtain a sufficient development margin.
Moreover, since the photosensitive composition which concerns on Examples 1-5 contains the specific 2-3 functional acrylate compound with the specific multifunctional acrylate compound, although the specific multifunctional acrylate compound is contained, the specific 2 As compared with the photosensitive composition according to Example 6 containing no .about.trifunctional acrylate compound, it was confirmed that the composition had excellent characteristics particularly in the effect of suppressing development residue generation.
On the other hand, since Comparative Examples 1 to 3 do not contain a specific polyfunctional acrylate compound, both the viscosity of the composition is increased and the occurrence of development residue is sufficiently suppressed. It was not planned.

It is a schematic diagram which shows the cross-sectional shape of the alternating current type plasma display panel which is a kind of flat display panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Glass substrate 3 Partition 4 Transparent electrode 5 Bus electrode 6 Address electrode 7 Fluorescent substance 8 Dielectric layer 9 Dielectric layer P Protective layer

Claims (5)

(A) inorganic particles containing at least glass powder,
(B) an alkali-soluble polymer,
(C) A photosensitive composition comprising a compound represented by the following general formula (1) and (D) a photopolymerization initiator.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and X represents an —O— group, —O (CH ₂ CH ₂ ) _a O— group (where a is an integer of 1 to 8). Or —O (CH ₂ CH ₂ CH ₂ ) _b O— group (where b is an integer of 1 to 8), Y represents a methylene group, an alkylene group having 2 to 8 carbon atoms, and 2 carbon atoms. A group selected from the group consisting of an alkenylene group of -8, an unsubstituted or substituted phenylene group, an unsubstituted or substituted cyclohexylene group, and a cyclohexylene group, a part of which is an unsaturated bond; Show. n is an integer of 1 to 4. ]   The photosensitive composition according to claim 1, comprising an acrylate compound having 2 to 3 functional groups.   3. The photosensitive composition according to claim 1, wherein hydroxypropylcellulose is contained in an amount of 0.1 to 10% by mass with respect to the entire composition.   The photosensitive resin layer which consists of a photosensitive composition in any one of Claims 1-3 is formed on a board | substrate, the latent image which has a pattern by performing an exposure process with respect to the formed photosensitive resin layer is formed. After the formation, the photosensitive resin layer is developed to form a pattern layer corresponding to the pattern formed by the exposure process, and the pattern layer is fired to obtain a fired body having a pattern. A method for forming a fired body.   The photosensitive resin layer which consists of a photosensitive composition in any one of Claims 1-3 is formed on a board | substrate, the latent image which has a pattern by performing an exposure process with respect to the formed photosensitive resin layer is formed. After the formation, the photosensitive resin layer is developed to form a pattern layer corresponding to the pattern formed by the exposure process, and the pattern layer is fired to form a partition, an electrode, a resistor, and a dielectric layer A method for producing a flat display panel, comprising a step of forming a component selected from a phosphor, a color filter, and a black matrix.

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