CN101206404A - Photosensitive resin composition containing inorganic particles, photosensitive film, pattern forming method, and method for producing flat panel display - Google Patents

Abstract

The present invention provides a photosensitive resin composition capable of forming high-precision patterns, having excellent thermal decomposability of organic components, and having little shrinkage after firing. The above photosensitive resin composition is a composition containing (A) inorganic particles; (B) alkali-soluble resin; (C) multifunctional (meth)acrylate; (D) photopolymerization initiator; and (E) sensitizer. The photosensitive resin composition containing inorganic particles is characterized in that: the (D) photopolymerization initiator is the compound shown in the above formula (1), the (E) sensitizer is the compound shown in the above formula (2) and A compound represented by the above formula (3).

Description

Photosensitive resin composition containing inorganic particles, photosensitive film, pattern forming method, and method for producing flat panel display

technical field

The present invention relates to a photosensitive resin composition, a photosensitive film, a method for forming a pattern, and a method for preparing a flat panel display. Excellent thermal decomposition properties of organic components such as photopolymerization initiators in the production of display panels such as flat panel displays that constitute display units, or in the production of circuit boards with minute circuit patterns used in advanced mounting materials for electronic components Photosensitive resin composition suitable for use in the case of forming a high-precision pattern, a photosensitive film having a photosensitive resin layer composed of the composition, a pattern forming method using the composition or a photosensitive film, and a part of the process including the A method of manufacturing a flat panel display of a pattern forming method.

Background technique

In recent years, in the patterning of circuit boards and display panels, there has been an increasing demand for higher density and finer detail. Among such demanding display panels, flat panel displays such as plasma display panels (hereinafter also referred to as "PDP") or field emission displays (hereinafter also referred to as "FED") are popular.

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1 , 101 and 102 are oppositely arranged glass substrates, 103 and 111 are spacers, and glass substrate 101 , glass substrate 102 , spacer 103 , and spacer 111 are used to divide and form cells. 104 is a transparent electrode fixed on the glass substrate 101 , 105 is a bus electrode formed on the transparent electrode 104 for the purpose of reducing the resistance of the transparent electrode 104 , and 106 is an address electrode fixed on the glass substrate 102 . 107 is a fluorescent substance kept in the unit, 108 is a dielectric layer formed by covering the transparent electrode 104 and bus electrode 105 on the surface of the glass substrate 101, 109 is a dielectric layer formed by covering the address electrode 106 on the surface of the glass substrate 102, 110 is a protective film made of magnesium oxide, for example. In addition, in color FPDs, in order to obtain images with high contrast, color filters (red, green, blue) or black matrices are provided between the glass substrate and the dielectric layer.

As a method for forming FPD components such as spacers, electrodes, resistors, phosphor color filters, and black matrices, it is well known that: (1) screen printing a non-photosensitive resin on a substrate to form a desired pattern, and then The screen printing method of firing, (2) forming a photosensitive resin layer on a substrate, irradiating infrared rays or ultraviolet rays to the photosensitive resin layer through a photomask drawn with a desired pattern, and then developing, thereby making the desired A photolithography method in which a pattern is left on a substrate and then fired (see, for example, Patent Document 1).

However, as the size and precision of display panels increase, the requirements for pattern accuracy become very strict, and there is a problem that general screen printing cannot cope with the above-mentioned screen printing method. In addition, although the above photolithography method is excellent in pattern accuracy, when the thickness of the film is thick, the sensitivity in the depth direction is insufficient, the pattern accuracy deteriorates, and the thermal decomposability of the photosensitive resin composition in the firing process is poor.

[Patent Document 1] Japanese Unexamined Patent Publication No. 11-44949

Contents of the invention

The present invention aims to solve the above-mentioned problems associated with the prior art, and an object thereof is to provide an inorganic fine particle-containing photosensitive resin composition capable of forming high-precision patterns and having excellent thermal decomposability of organic components such as photopolymerization initiators. .

In addition, an object of the present invention is to provide an inorganic fine particle-containing photosensitive resin composition composed of the above-mentioned inorganic fine particle-containing photosensitive resin composition, capable of forming a high-precision pattern, and having excellent thermal decomposability of organic components such as a photopolymerization initiator. A photosensitive film of a resin layer, and a pattern forming method using the composition or photosensitive film of the present invention and a method for preparing a flat panel display including the pattern forming method are provided.

The inventors of the present invention have conducted earnest research to solve the above-mentioned problems, and as a result, found that a photosensitive resin composition containing inorganic fine particles capable of forming a high-precision pattern can be provided by including a specific photopolymerization initiator and a sensitizer, thereby completing the present invention. invention.

That is, the inorganic fine particle-containing photosensitive resin composition of the present invention contains (A) inorganic fine particles; (B) alkali-soluble resin; (C) polyfunctional (meth)acrylate; (D) photopolymerization initiator; ) sensitizer, characterized in that:

The (D) photopolymerization initiator is a compound represented by the following formula (1),

The (E) sensitizer is a compound shown in the following formula (2) and a compound shown in the following formula (3),

In formula (1), R ¹ and R ² independently represent an alkyl group with 1 to 4 carbon atoms,

In formula (2), R ³ and R ⁴ independently represent hydrogen or an alkyl group with 1 to 4 carbon atoms,

In formula (3), R ⁵ represents fluorine, chlorine, bromine, iodine, or trifluoromethanesulfonate, R ⁶ represents hydrogen or an alkyl group with 1 to 4 carbon atoms,

With respect to 100 parts by weight of the (C) polyfunctional (meth)acrylate, it is preferable to contain: 3.0 to 10.0 parts by weight of the compound represented by formula (1), 0.5 to 2.0 parts by weight of the compound represented by formula (2) Compounds represented by formula (3) in the range of 0.2 to 1.0 parts by weight.

The present invention includes a photosensitive film characterized by having an inorganic fine particle-containing photosensitive resin composition layer obtained from the inorganic fine particle-containing photosensitive resin composition.

The present invention also includes a pattern forming method, which is characterized in that it includes: (I) the step of forming a photosensitive resin composition layer containing inorganic particles obtained from the photosensitive resin composition containing inorganic particles on a substrate; (II) A step of exposing the photosensitive resin composition layer containing inorganic particles to form a pattern latent image; (III) developing a photosensitive resin composition layer containing inorganic particles after exposure to form a pattern; (IV) The process of firing the pattern.

In the above step (I), the photosensitive film may be used to form a photosensitive resin composition layer containing inorganic fine particles on a substrate.

The present invention also includes a method for preparing a flat panel display, which is characterized in that: it includes using the pattern forming method to form at least one selected from the group consisting of dielectrics, electrodes, resistors, phosphors, spacers, color filters and black matrices. A process for a member for a display panel.

The display panel can also be a plasma display panel.

The photosensitive resin composition and photosensitive film containing inorganic fine particles of the present invention can form high-precision patterns, and at the same time have excellent thermal decomposition properties of organic components such as photopolymerization initiators, so they are suitable for the formation of constituent members of each display unit of flat panel displays and electronic components. Used in the formation of components of highly solid materials.

【Description of drawings】

[ Fig. 1] Fig. 1 is a schematic view showing a cross-sectional shape of an AC type FPD (specifically, a PDP).

[ Fig. 2] Fig. 2 shows the measurement results of thermogravimetric analysis of MTPMP.

[ Fig. 3] Fig. 3 shows the measurement results of thermogravimetric analysis of BDPPB.

[ Fig. 4] Fig. 4 shows the measurement results of thermogravimetric analysis of BTPP.

[FIG. 5] FIG. 5 is a schematic diagram showing locations to be evaluated in the evaluation of the pattern of the example.

【Symbol Description】

101 glass substrate

102 glass substrate

103 back spacer

104 transparent electrode

105 bus electrodes

106 address electrodes

107 fluorescent substances

108 dielectric layer

109 dielectric layer

110 layers of protection

111 front spacer

A Spacer pattern

B Section Details

Detailed ways

The photosensitive resin composition containing inorganic microparticles, the photosensitive film and the pattern forming method involved in the present invention will be described in detail below.

[Photosensitive resin composition containing inorganic fine particles]

The photosensitive resin composition containing inorganic microparticles of the present invention contains (A) inorganic microparticles; (B) alkali-soluble resin; (C) multifunctional (meth)acrylate; (D) photopolymerization initiator; agent.

<(A) Inorganic particles>

The (A) inorganic fine particles used in the composition of the present invention vary depending on the type of forming material. In particular, glass powder and the like are exemplified as inorganic fine particles used in the dielectric and spacer forming materials constituting the FPD.

Examples of the glass powder used in the present invention include low-melting glass powders having a thermal softening point of 300 to 650°C, preferably 350 to 600°C. If the thermal softening point of the glass powder is lower than the above range, the glass powder will melt when the organic substances such as resin are not completely decomposed and removed in the firing process of the photosensitive resin layer formed from the above composition. Therefore, in the formed member, a part of the organic substance remains, and as a result, members such as the dielectric layer and the spacer may be colored and the light transmittance may be lowered. On the other hand, if the thermal softening point of the glass powder exceeds the above-mentioned range, high-temperature firing is necessary, so deformation and the like are likely to occur on the glass substrate.

As said _glass powder, the following glass powder can _be mentioned, for example: (1) _{Bi2O3 -} ZnO- _{B2O3 system} , (2) _Bi2O3 - _SiO2 - _B2O3 system, (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 system, (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 system, (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 system} O ₃ -ZrO ₂ -CaO system, (15) SiO ₂ -B ₂ O ₃ -ZrO ₂ -MaO system, (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 system, (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 -ZnO system, (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 system, etc.

The shape of the glass powder is not particularly limited. The above-mentioned glass powders may be used alone or in combination of two or more glass powders having different glass powder compositions, different softening points, different shapes, and different average particle diameters.

In order to obtain a more precise pattern, the glass powder preferably contains silicon oxide in a range of 5 to 50% by weight, and more preferably contains silicon oxide in a range of 10 to 30% by weight. Silica has the effect of improving the density, strength, and stability of glass, and is also effective in reducing the refractive index of glass. In addition, controlling the coefficient of thermal expansion can also prevent peeling and the like caused by mismatch with the glass substrate. By setting the content of silicon oxide at 5% by weight or more, the coefficient of thermal expansion can be suppressed to be small, and the occurrence of cracks during baking onto the glass substrate can be reduced, and the refractive index can be suppressed to be low. In addition, by making the content of silicon oxide 50% by weight or less, the glass transition temperature and the softening point under load can be suppressed low, and the baking temperature for baking onto the glass substrate can be lowered.

The above glass powder preferably contains boron oxide in an amount of 10 to 50% by weight, more preferably in a range of 20 to 45% by weight. By making content of boron oxide 10 weight% or more, glass transition temperature and load softening point can be suppressed low, and baking to a glass substrate can be made easy. Moreover, the chemical stability of glass can be maintained by making content of boron oxide 50 weight% or less. In addition, boron oxide is also effective for lowering the refractive index.

The above-mentioned glass powder preferably contains at least one of barium oxide and strontium oxide in a total amount of 1 to 30% by weight, more preferably in a total amount of 2 to 20% by weight. These components are effective in adjusting the coefficient of thermal expansion, and have the effect of preventing deformation of the substrate during firing, imparting electrical insulation, improving the stability and density of formed spacers, and the like. By making these contents 1% by weight or more, devitrification caused by crystallization of the glass can also be prevented. In addition, by making these contents 30% by weight or less, the thermal expansion coefficient and the refractive index can be suppressed low, and at the same time, Maintain chemical stability.

It is preferable that the said glass powder contains alumina in the range of 1-40 weight%. Alumina has the effect of expanding the vitrification range and stabilizing the glass, and is also effective for prolonging the application time of the composition. By setting the content of alumina within the above range, the glass transition temperature and the softening point under load can be kept low, and the adhesiveness with the substrate can be improved.

The above-mentioned glass powder preferably contains at least one of calcium oxide and magnesium oxide in a total amount of 1 to 20% by weight. These components easily melt the glass and at the same time have the effect of controlling the coefficient of thermal expansion. By making these contents 1 weight% or more, devitrification by crystallization of glass can be prevented, and by making these contents 15 weight% or less, the chemical stability of glass can be maintained.

The above-mentioned glass powder preferably contains alkali metal oxides of lithium oxide, sodium oxide, and potassium oxide in a range of 1 to 20% by weight. Alkali metal oxides facilitate the control of the thermal softening point and thermal expansion coefficient of glass, and have the effect of lowering the refractive index as glass powder. Since alkali metal oxides can promote the movement or diffusion of ions, the thermal expansion coefficient can be suppressed low while maintaining the chemical stability of glass by making the total amount 20 weight% or less.

The above-mentioned glass powder may contain zinc oxide, titanium oxide, zirconium oxide, etc. in addition to the above-mentioned components.

The average particle diameter of the glass powder is selected depending on the shape of the pattern to be produced, but is preferably 0.01 to 10 μm, more preferably 0.1 to 8 μm, from the viewpoint of pattern formation. In addition, from the viewpoint of pattern formation, the specific surface area of the glass powder is preferably 0.1 to 300 m ² /g.

The above-mentioned glass powder may be contained in a composition for forming components other than the FPD dielectric and spacer (for example, electrodes, resistors, phosphors, color filters, and black matrix). The content of the glass powder at this time varies depending on the application, but is usually 90 wt. or less, preferably 80 wt. or less, based on 100 wt. parts of the total amount of inorganic fine particles including the glass powder.

Al, Ag, Ag-Pd alloy, Au, Ni are examples of inorganic fine particles used in electrode formation materials such as FPD, LCD, organic EL, printed circuit board, multilayer circuit board, device, sensor, and LSI. , Cr, Cu, etc. Among these, it is preferable to use Ag, which does not cause a decrease in electrical conductivity due to oxidation even when fired in the air, and is relatively cheap. The shape of the inorganic fine particles used in the electrode forming material includes granular, spherical, and flake shapes, and is not particularly limited. Inorganic fine particles of the same shape may be used, or two or more kinds of inorganic fine particles of different shapes may be mixed and used. In addition, the average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 8 μm, and inorganic fine particles having different average particle diameters may be mixed and used.

Inorganic fine particles used as transparent electrode forming materials for FPD, LCD, organic EL elements, etc. include indium oxide, tin oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), and fluorine-doped indium oxide. (FIO), fluorinated tin oxide (FTO), fluorinated zinc oxide (FZO), and zinc oxide particles containing one or more metals selected from Al, Co, Fe, In, Sn, and Ti, etc. . Examples of inorganic fine particles used in the resistance forming material of the PDP include fine particles composed of RuO ₂ and the like.

Examples of inorganic fine particles used in the phosphor forming material of PDP 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, etc. For green, 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. . 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, etc.

Inorganic fine particles used in color filter forming materials such as PDP, LCD, and organic EL elements include Fe ₂ O ₃ for red, Cr 2 O 3 for green, and Cr ₂ O ₃ for blue. Examples thereof include CoO·Al ₂ O ₃ and the like.

Examples of inorganic fine particles used in black stripe (matrix) forming materials such as PDP, LCD, and organic EL elements include metals such as Co, Cr, Cu, Fe, Mn, Ni, Ti, Zn, and their oxides. compounds, composite oxides, carbides, nitrides, sulfides, silicides, borides, or carbon black, graphite, etc. These may be used individually or in mixture of 2 or more types. Among these, metal fine particles, metal oxide fine particles, and composite oxide fine particles selected from the group of Co, Cr, Cu, Fe, Mn, Ni, and Ti are preferable. In addition, the average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, particularly preferably 0.1 to 2 μm.

Content of (A) inorganic fine particle in the composition of this invention is 100-2000 weight part with respect to 100 weight part of (B) alkali-soluble resins, Preferably it is the range of 130-1000 weight part. By making content of (A) inorganic fine particles into the said range, the pattern with favorable shape can be formed.

<(B) Alkali-soluble resin>

Various resins can be used as (B) alkali-soluble resin used for the inorganic fine particle containing photosensitive resin composition. The term "alkali solubility" in the present invention refers to the property of dissolving in an alkaline developing solution within the limit that the intended developing treatment can be performed.

Said (B) alkali-soluble resin can be obtained by copolymerizing the monomer (B1) and (meth)acrylic acid derivative (B2) which contain an alkali-soluble functional group.

As the above-mentioned monomer (B1) containing an alkali-soluble functional group, the following monomers containing an alkali-soluble functional group and an unsaturated bond can be mentioned:

(Meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, mono(2-(meth)acryloyloxyethyl)succinate , 2-methacryloyloxyethyl phthalate, hydrogenated phthalate (2-acryloyloxyethyl) ester (2-acryloyloxy ethyl hydrogen phthalate), hydrogenated phthalate (2-acryloyl oxypropyl) ester, (2-acryloyloxypropyl) hexahydrophthalate, (2-acryloyloxypropyl) tetrahydrophthalate, (meth)acrylate mono( Carboxyl-containing monomers such as ω-carboxypolycaprolactone;

(2-hydroxy)ethyl (meth)acrylate, (2-hydroxy)propyl (meth)acrylate, (3-hydroxy)propyl (meth)acrylate, (α-hydroxymethyl)acrylate, etc. Hydroxyl-containing monomers;

Phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

Among these monomers, (meth)acrylic acid, 2-methacryloyloxyethyl phthalate, (2-acryloyloxyethyl) hydrogenated phthalate, hydrogenated phthalate (2 - Acryloyloxypropyl) ester, (2-acryloyloxypropyl) hexahydrophthalate, (2-acryloyloxypropyl) tetrahydrophthalate, (methyl) (2-Hydroxyethyl) acrylate.

In all the structural units of the (B) resin, the content of the structural unit derived from the alkali-soluble functional group-containing monomer (B1) is generally 5 to 90% by weight, preferably 10 to 80% by weight, particularly preferably 15 to 80% by weight. 70% by weight.

The above-mentioned (meth)acrylic acid derivative (B2) is not particularly limited as long as it is a (meth)acrylic derivative that can be copolymerized with the above-mentioned alkali-soluble functional group-containing monomer (B1), but examples include: Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, lauryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate ester, cresyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. (meth)acrylates other than the body (B1).

In addition, in the present invention, it is also possible to use, for example, polymers obtained from styrene, methyl (meth)acrylate, ethyl (meth)acrylate, benzyl (meth)acrylate at one end of the chain end of which has (form Macromonomers of polymerizable unsaturated groups such as acryloyl groups, allyl groups, vinyl groups, etc., instead of the above-mentioned (meth)acrylic acid derivatives (B2), or the above-mentioned macromonomers and the above-mentioned (meth)acrylic acid derivatives (B2) base) acrylic acid derivatives (B2).

(radical polymerization initiator)

In the above-mentioned copolymerization, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, radical polymerization initiators used for polymerization of vinyl monomers can be used. Examples include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethyl valeronitrile), 1,1'-azobis(1-cyclohexanenitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanopentyl acid) and other azo compounds; peroxidized Organic peroxides of esters, etc. These radical polymerization initiators may be used alone or in combination of two or more. The usage-amount of these radical polymerization initiators is about 0.1-10 weight part with respect to 100 weight part of all the said monomers used for polymerization.

The weight-average molecular weight (hereinafter also referred to as "Mw") of the (B) alkali-soluble resin thus obtained is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and is preferably 5,000 to 100,000, more preferably 10,000 ~50,000. Mw can be controlled by appropriately selecting conditions such as the copolymerization ratio, composition, chain transfer agent, and polymerization temperature of the above-mentioned monomers. If the Mw is lower than the above range, the film after development tends to be rough, and if the Mw exceeds the above range, the solubility of the developing solution to the unexposed part may decrease, and the resolution may decrease.

The glass transition temperature (Tg) of said (B) alkali-soluble resin is 0-120 degreeC, Preferably it is 10-100 degreeC. When the glass transition temperature is lower than the above-mentioned range, wrinkles tend to be easily generated on the coating film, and handling tends to be difficult. On the other hand, if the glass transition temperature exceeds the above-mentioned range, the adhesion with the glass substrate as a support may deteriorate, and transfer may not be possible. In addition, the said glass transition temperature can be adjusted suitably by changing the quantity of the said compound (B1) and (meth)acrylate derivative (B2).

The acid value of the above-mentioned (B) alkali-soluble resin is preferably 20 to 200 mgKOH/g, more preferably 30 to 160 mgKOH/g. When the acid value is 20 mgKOH/g or less, it tends to be difficult to remove the unexposed part after exposure in an alkaline developing solution immediately, and it tends to be difficult to form a high-definition pattern. On the other hand, if the acid value is 200 mgKOH/g or more, the part cured by the exposed light tends to be easily corroded by an alkaline developing solution, and it tends to be difficult to form a high-definition pattern.

<(C) Multifunctional (meth)acrylate>

As the (C) polyfunctional (meth)acrylate constituting the photosensitive resin composition containing inorganic fine particles, as long as it has an ethylenically unsaturated group and can undergo a radical polymerization reaction with a photopolymerization initiator described later, The polyfunctional (meth)acrylate compound is not particularly limited, but generally the following (meth)acrylate compounds can be used:

Specific examples of (C) polyfunctional (meth)acrylate used in the present invention include: allylcyclohexyl di(meth)acrylate, 2,5-hexyl di(meth)acrylate Diester, (1,4-butanediol) di(meth)acrylate, (1,3-butanediol) di(meth)acrylate, ethylene glycol di(meth)acrylate, di( Diethylene glycol methacrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glyceryl di(meth)acrylate, methyl di(meth)acrylate Oxycyclohexyl ester, neopentyl glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, triglyceride di(meth)acrylate, etc. Meth)acrylates; pentaerythritol tri(meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane PO modified (meth)acrylate, trimethylolpropane EO modified Tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, di(trimethylol)propane tetra(meth)acrylate, trimethylol Polyfunctional (meth)acrylates such as propyl propane tri(meth)acrylate, benzyl mercaptan (meth)acrylate, etc.

In addition, a compound represented by the following formula (4) can also be used.

ZOCH(CH ₂ OZ) ₂ (4)

(In formula (4), Z is a group represented by the following formula (5))

(In formula (5), n is a real number from 1 to 10)

Generally, the said (C) polyfunctional (meth)acrylate can be used individually by 1 type, and can also use it in combination of 2 or more types. In the composition of the present invention, the content of the above-mentioned (C) polyfunctional (meth)acrylate is generally 20 to 200 parts by weight, preferably 30 to 100 parts by weight, relative to 100 parts by weight of the (B) alkali-soluble resin. range of servings. (C) When there is too little content of a polyfunctional (meth)acrylate, an exposed part will be easily corroded by a developing solution, and a pattern cannot be formed. If the content is too large, the development process will take a long time, which is not preferable from the viewpoint of production. In addition, the shrinkage is large during firing, leading to the occurrence of peeling.

<(D) Photopolymerization Initiator>

The (D) photopolymerization initiator constituting the inorganic fine particle-containing photosensitive resin composition of the present invention is a compound represented by the aforementioned formula (1) (hereinafter also referred to as photopolymerization initiator (1)).

The photopolymerization initiator (1) is preferable because it initiates polymerization efficiently through the sensitizer represented by the above-mentioned formulas (2) and (3). ^R1 and ^R2 in the above formula (1) are independently an alkyl group with 1 to 4 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl group, sec-butyl group, tert-butyl group, particularly preferably methyl group.

The photopolymerization initiator (1) has a weight loss rate of 90% or more at 400°C, and a weight loss rate of 99% or more at 550°C. Therefore, the inorganic fine particle-containing photosensitive resin composition containing the photopolymerization initiator (1) can provide an inorganic fine particle-containing photosensitive resin composition that forms a pattern with high precision and is excellent in thermal decomposability.

Here, the so-called "weight loss at 400°C" means that the photopolymerization initiator is subjected to thermogravimetric analysis at a heating rate of 10°C/min and a flow rate of 60ml/min, according to [1-(weight/weight at 400°C Weight at 40°C)] × 100% of the calculated value.

In addition, the so-called "weight reduction at 550°C" means that the photopolymerization initiator is subjected to thermogravimetric analysis at a temperature increase rate of 10°C/min and a flow rate of 60 ml/min, according to [1-(weight at 550°C/40 weight at °C)] × 100% to obtain the value.

<(E) Sensitizer>

When the photopolymerization initiator constituting the inorganic fine particle-containing photosensitive resin composition of the present invention contains a sensitizer, it is possible to provide an inorganic fine particle-containing photosensitive resin composition that forms a high-precision pattern and is excellent in thermal decomposability.

As the sensitizer, a compound represented by the above formula (2) (hereinafter also referred to as "sensitizer 1") and a compound represented by the above formula (3) (hereinafter also referred to as "sensitizer 2") are used.

R ³ and R ⁴ in the above formula (2) independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl radical, isobutyl, sec-butyl, tert-butyl, particularly preferably ethyl and isopropyl. R ⁵ in the above formula (3) represents fluorine, chlorine, bromine, iodine, or trifluoromethanesulfonate, and R ⁶ represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Specifically, methane is preferably Oxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-propoxy is particularly preferred.

In the photosensitive resin composition containing inorganic microparticles of the present invention, the above photopolymerization initiator (1) is used as (D) photopolymerization initiator, and sensitizer (1) and sensitizer (2) are used as (E) sensitizer agent. By using the photopolymerization initiator (1), the sensitizer (1) and the sensitizer (2), the sensitivity of the photopolymerization initiator (1) to ultraviolet rays is improved even when the amount of the photopolymerization initiator is small Under this condition, sufficient polymerization can also be performed. Accordingly, the inorganic fine particle-containing photosensitive resin composition of the present invention can provide an inorganic fine particle-containing photosensitive resin composition that forms a pattern with high precision and is excellent in thermal decomposability.

Especially in order to obtain a high-precision pattern, it is preferable to contain: 3.0 to 10.0 parts by weight of photopolymerization initiator (1), 0.5 to 2.0 parts by weight of The sensitizer (1), the sensitizer (2) of 0.2～1.0 parts by weight, particularly preferably contains: the photopolymerization initiator (1) of 5.5～9.0 parts by weight, the sensitizer (1) of 0.8～1.8 parts by weight, 0.5-0.9 parts by weight of the sensitizer (2).

With respect to 100 parts by weight of (C) multifunctional (meth)acrylate, if the photopolymerization initiator (1) exceeds 10.0 parts by weight, the sensitizer (1) exceeds 2.0 parts by weight, and the sensitizer (2) exceeds 1.0 parts by weight If the content is less than the weight part, the internal curability tends to decrease, making it difficult to obtain a development margin. With respect to 100 parts by weight of (C) multifunctional (meth)acrylate, if the photopolymerization initiator (1) is less than 3.0 parts by weight, the sensitizer (1) is less than 0.5 parts by weight, and the sensitizer (2) is less than 0.2 If the weight part is lower, not only the exposure sensitivity will decrease, but also the chemical resistance of the exposed part to the developer will decrease, which will easily cause film roughness.

<Ultraviolet absorber>

It is also effective to add an ultraviolet absorber to the inorganic fine particle-containing photosensitive resin composition of the present invention. By adding a compound with a high ultraviolet absorbing effect, high aspect ratio, high precision, and high resolution can be obtained. As the ultraviolet absorber, an organic dye or an inorganic dye can be used, and an organic dye or an inorganic dye having a high ultraviolet absorption coefficient in a wavelength range of 350 to 450 nm is particularly preferably used. Specifically, it is possible to use: azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, benzoquinone dyes, aminoketone dyes, anthraquinone dyes, benzophenone dyes, cyano Organic dyes such as biphenyl acrylate, triazine, and p-aminobenzoic acid dyes, and inorganic dyes such as zinc oxide, titanium oxide, and cerium oxide. Among these dyes, organic dyes are preferred because they do not remain in the insulating film after firing, and thus can reduce the degradation of the properties of the insulating film. However, from the viewpoint of reliability of flat panel displays, zinc oxide, Inorganic dyes of titanium, cerium oxide, etc.

0.01-10 weight part of said inorganic dyes can be added with respect to 100 weight part of (C) polyfunctional (meth)acrylates, Preferably it adds 0.03-5 weight part. If the addition amount of the inorganic dye is too small, the effect of adding the ultraviolet absorber decreases, and if the addition amount is too large, the properties of the insulating film after firing may decrease or the film formation strength may not be maintained.

<Inhibitor>

In the inorganic fine particle-containing photosensitive resin composition of the present invention, a polymerization inhibitor may be added in order to improve thermal stability during storage. Examples of polymerization inhibitors include: hydroquinone, monoesters of hydroquinone, N-nitrosodiphenylamine, phenothiazine, p-tert-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-cresol, chloranil, 1,2,3-glucinol, etc. In the composition, a polymerization inhibitor can usually be added in an amount in the range of 0.001 to 5% by weight.

<Antioxidant>

In the inorganic fine particle-containing photosensitive resin composition of the present invention, an antioxidant may be added thereto in order to prevent oxidation of the (B) alkali-soluble resin during storage. Examples of antioxidants include 2,6-di(tert-butyl)-p-cresol, butylated hydroxyanisole, propionic acid [stearyl-β-(3,5-di-tert-butyl- 4-hydroxyphenyl)] ester, 2,6-di-tert-butyl-4-ethylphenol, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), 2,2- Methylene-bis(4-ethyl-6-tert-butylphenol), 4,4-butylene-bis(3-methyl-6-tert-butylphenol), 4,4-thio-bis(3 -methyl-6-tert-butylphenol), 4,4-bis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-6-tert-butylphenol ), 1,1,3-tris(2-methyl-4-hydroxy-tert-butylphenyl)butane, bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butanoic acid] Ethylene glycol ester, dilauryl mercaptan dipropionate, triphenyl phosphate, etc. In the composition, an antioxidant may generally be added in an amount ranging from 0.001 to 5% by weight.

<Organic solvent>

In the inorganic fine particle-containing photosensitive resin composition of the present invention, an organic solvent may be added in order to adjust the viscosity of the solution. Examples of organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, 3-ethoxy ethyl propionate, propylene glycol monomethyl ether , propylene glycol monoethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropyl acetate, diethyl ketone, methyl butyl ketone, diacetone, methyl ethyl ketone, dioxane , acetone, cyclohexanone, cyclopentanone, n-pentanol, diacetone alcohol, 4-methyl-2-pentanol, cyclohexanol, isobutanol, isopropanol, tetrahydrofuran, dimethylsulfoxide, γ- Butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, n-butyl acetate, amyl acetate, ethyl lactate, n-butyl lactate, etc. The above-mentioned organic solvents may be used alone or in combination of two or more.

<Adhesion Auxiliary>

In the inorganic fine particle-containing photosensitive resin composition of the present invention, an adhesion assistant may be added in order to improve the adhesion with the support. As an adhesion aid, a silane compound is suitably used. Specific examples of silane compounds include: n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethoxysilane Methylmethoxysilane, n-eicosyldimethylmethoxysilane, n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane N-ylsilane, n-hexadecyldiethylmethoxysilane, n-eicosyldiethylmethoxysilane, n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane , n-hexadecyldipropylmethoxysilane, n-eicosyldipropylmethoxysilane, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n- Decyldimethylethoxysilane, n-hexadecyldimethylethoxysilane, n-eicosyldimethylethoxysilane, n-propyldiethylethoxysilane, n-butyl Diethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-eicosyldiethylethoxysilane, n-butyldipropylene ethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-eicosyldipropylethoxysilane, n-propyldimethylpropane Oxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, n-hexadecyldimethylpropoxysilane, n-eicosyldimethylpropoxysilane Silane, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, n-hexadecyldiethylpropoxysilane, Decyldiethylpropoxysilane, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-eicosane Dipropylpropoxysilane, n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane N-ylsilane, n-eicosylmethyldimethoxysilane, n-propylethyldimethoxysilane, n-butylethyldimethoxysilane, n-decylethyldimethoxysilane, n- Hexadecylethyldimethoxysilane, n-eicosylethyldimethoxysilane, n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecyl Alkylpropyldimethoxysilane, n-eicosylpropyldimethoxysilane, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane Oxysilane, n-Hexadecylmethyldiethoxysilane, n-Eicosylmethyldiethoxysilane, n-Propylethyldiethoxysilane, n-Butylethyldiethoxysilane Silane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-eicosylethyldiethoxysilane, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-eicosylpropyldiethoxysilane, n-propylmethyldipropoxysilane, n-butylmethyl Dipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-eicosylmethyldipropoxysilane, n-propylethyldipropoxysilane Propoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-eicosylethyldipropoxysilane N-butylsilane, n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n-eicosylpropyldipropoxysilane , n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-eicosyltrimethoxysilane, n-propyltriethyl Oxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-eicosyltriethoxysilane, n-propyltriethoxysilane N-butylsilane, n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexadecyltripropoxysilane, n-eicosyltripropoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-( 1,3-Dimethylbutylene)-3-(triethoxysilyl)-1-propylamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine wait. These may be used alone or in combination of two or more.

The content of the adhesion assistant in the inorganic fine particle-containing photosensitive resin composition is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the (B) alkali-soluble resin.

<Dissolution Accelerator>

The composition of the present invention preferably contains a dissolution accelerator for the purpose of exhibiting sufficient solubility in a developer to be described later. As solvent accelerators, surfactants are preferably used. As such a surfactant, a fluorine-type surfactant, a silicon-type surfactant, and a nonionic surfactant are mentioned, for example.

Examples of the above-mentioned fluorine-based surfactants include the following commercially available products: "BM-1000" and "BM-1100" manufactured by BMCHIMIE Co., Ltd., and "Megafact F142D" manufactured by Dainippon Ink Chemical Industry Co., Ltd. , "Megafact F172", "Megafact F173", "Megafact F183", "Florrad FC-135", "Florrad FC-170", "Florrad FC- 430", "Florrad FC-431", "Surflun S-112", "Surflun S-113", "Surflun S-131", "Surflun S" manufactured by Asahi Glass Co., Ltd. -141", "Surfuln S-145", "Surfuln S-382", "Surfuln SC-101", "Surfuln SC-102", "Surfuln SC-103", " Surflon SC-104", "Surflun SC-105", "Surflun SC-106" and the like.

Examples of the silicon-based surfactant include commercially available products such as "SH-28PA", "SH-190", "SH-193", "SZ -6032", "SF-8428", "DC-57", "DC-190", "SH-8400", "FZ-7001", "KP341" manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Akita Chemicals "Eftop EF301", "Eftop EF303", "Eftop EF352" etc. manufactured by the company.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene Polyoxyethylene aryl ethers such as distyrenated phenylene ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc.; polyoxyethylene dilaurate, polyoxyethylene distearic acid Polyoxyethylene dialkyl esters such as esters, etc.

As commercially available products of the above-mentioned nonionic surfactants, for example: "EMARGEN A-60", "A-90", "A-550", "B-66" manufactured by Kao Corporation, "PP-99", "(meth)acrylic acid copolymer polyflor-1 No. 57", "(meth)acrylic acid copolymer polyflour-1 No. 90" manufactured by Kyoeisha Chemical Co., Ltd., etc.

Among the above-mentioned surfactants, nonionic surfactants are preferable, polyoxyethylene aryl ethers are more preferable, and the following: Compound shown in formula (6):

In the above formula (6), ^R is an alkyl group with 1 to 5 carbon atoms, preferably a methyl group, p is an integer of 1 to 5, s is an integer of 1 to 5, preferably 2, and t is 1 to 100 An integer of , preferably an integer of 10-20.

The content of the dissolution accelerator in the composition of the present invention is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the above (B) alkali-soluble resin . By making content of a dissolution accelerator into the said range, the composition excellent in the solubility to a developing solution can be obtained.

<Preparation of Photosensitive Resin Composition>

The photosensitive resin composition containing inorganic microparticles of the present invention is the above (A) inorganic microparticles; (B) alkali-soluble resin; (C) multifunctional (meth)acrylate; (D) photopolymerization initiator; (E ) sensitizer and solvent, and various components according to the needs are compounded according to a fixed composition ratio, and then homogeneously mixed and dispersed with 3 rollers and a mixer.

The viscosity of the above composition can be appropriately adjusted according to the addition amount of inorganic fine particles, thickener, organic solvent, plasticizer and anti-sedimentation agent, but the range is 100 to 200,000 cps (centipoise).

[photosensitive film]

The photosensitive film of the present invention usually has a support film and an inorganic particle-containing photosensitive resin composition layer formed on the support film and composed of the above-mentioned inorganic particle-containing photosensitive resin composition, and may also be formed on the surface of the photosensitive resin composition layer. Set up a protective film.

<Support film>

The supporting film constituting the photosensitive film is preferably a resin film having heat resistance and solvent resistance and flexibility. By making the support film flexible, the paste composition can be applied using a roll coater, and the photosensitive film can be stored and supplied in a roll-wound state. Moreover, as thickness of a support film, what is necessary is just to use suitably, for example, it is 20-100 micrometers.

As the resin forming the support film, for example: polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, poly Fluorine-containing resins such as vinyl chloride, nylon, cellulose, etc.

On the support film, the side on which the inorganic fine particle-containing photosensitive resin composition layer is formed is preferably subjected to a release treatment. Thereby, when forming the member for display panels and the member for electronic components, the peeling operation of a support film can be performed easily.

Furthermore, as the protective film layer that can also be provided on the surface of the photosensitive resin composition layer containing inorganic fine particles, the same flexible resin film as the above-mentioned support film can be used, and the surface (and the photosensitive resin layer) The contact side) is subjected to release treatment.

<Preparation method of photosensitive film>

The above-mentioned photosensitive film is obtained by coating the above-mentioned photosensitive resin composition containing inorganic fine particles on the above-mentioned support film to form a coating film, and drying the coating film to form a photosensitive resin layer containing inorganic fine particles. Dried and rolled into a roll, or laminated with a protective film. In addition, the support film and the protective film are respectively coated with a photosensitive resin composition containing inorganic particles to form a photosensitive resin layer containing inorganic particles, and then the resin layers of each other are laminated and pressure-bonded. Photosensitive film.

The method of applying the above-mentioned composition to the support film is not particularly limited as long as it can efficiently form a coating film having a large film thickness (for example, 10 μm or more) and excellent uniformity. Examples include: a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, and a coating method using a die coater, A coating method using a cable coater or the like.

The drying conditions of the coating film may be appropriately adjusted so that the residual solvent ratio after drying is within 2% by weight, for example, about 0.5 to 60 minutes at a drying temperature of 50 to 150°C.

The photosensitive resin layer containing inorganic fine particles formed as above has a thickness of 30 to 300 μm, preferably 50 to 200 μm.

[Pattern Formation Method]

The pattern forming method of the present invention is characterized in that it includes the step of forming an inorganic fine particle-containing photosensitive resin layer composed of the above-mentioned inorganic fine particle-containing photosensitive resin composition on a substrate (resin layer forming step); The process of exposing the resin layer to form a pattern latent image (exposure process); the process of developing the photosensitive resin layer containing inorganic particles to form a pattern (development process); and the process of firing the pattern (firing process). process).

In the above-mentioned resin layer forming step of the present invention, the above-mentioned photosensitive resin composition containing inorganic particles can be coated on a substrate to form a coating film, and then the coating film is dried to form a photosensitive resin layer containing inorganic particles. Using the above-mentioned photosensitive film, the inorganic fine particle-containing photosensitive resin layer constituting the photosensitive film is transferred onto a substrate, thereby forming the inorganic fine particle-containing photosensitive resin layer on the substrate.

<Resin layer formation process>

In this step, an inorganic fine particle-containing photosensitive resin layer composed of the above-mentioned inorganic fine particle-containing photosensitive resin composition is formed on a substrate. As a method for forming the photosensitive resin layer containing inorganic fine particles, for example, a method of coating the above-mentioned photosensitive resin composition containing inorganic fine particles on a substrate to form a coating film, and drying the coating film, or by Using the above-mentioned photosensitive film, the formation method of transferring the photosensitive resin layer containing inorganic fine particles constituting the photosensitive film onto a substrate.

The method of coating the above-mentioned composition on the substrate is not particularly limited as long as it can efficiently form a coating film having a large film thickness (for example, 10 μm or more) and excellent uniformity. Examples include: a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, and a coating method using a die coater, A coating method using a cable coater or the like.

The drying conditions of the coating film may be appropriately adjusted so that the residual solvent ratio after drying is within 2% by weight, for example, about 0.5 to 60 minutes at a drying temperature of 50 to 150°C.

The photosensitive resin layer containing inorganic fine particles formed as above has a thickness of 30 to 300 μm, preferably 50 to 200 μm. In addition, it is also possible to form a laminate having n layers (n represents an integer of 2 or more) of resin layers by repeating the application of the composition n times.

On the other hand, by laminating the above-mentioned photosensitive film on the substrate and transferring the photosensitive resin layer containing inorganic fine particles to the substrate, a resin layer with excellent film thickness uniformity can be easily formed on the substrate, and a patterned film can be achieved. Uniform thickness. When transferring the photosensitive resin layer containing inorganic fine particles, it is also possible to form a laminate having n layers (n represents an integer of 2 or more) of resin layers by repeating transfer n times using the photosensitive film. Alternatively, the above-mentioned laminate is formed by using a photosensitive film in which a laminate composed of n resin layers has been formed on a support film and transferring the entirety onto a substrate.

An example of the transfer process using a photosensitive film is shown below: peel off the protective layer of the photosensitive film used as needed, then laminate the photosensitive film on the substrate surface, and bring the surface of the photosensitive resin layer containing inorganic fine particles into contact with the photosensitive film , the photosensitive film is thermocompression-bonded using a heating roller or the like, and then the support film is peeled and removed from the resin layer. Thereby, the photosensitive resin layer is transferred on the surface of the board|substrate, and it assumes the state of adhesion.

As the transfer conditions, for example, the surface temperature of the heating roller is 40-140° C., the roller pressure of the heating roller is 0.1-10 kg/cm ² , and the moving speed of the heating roller is 0.1-10 m/min. In addition, the substrate may also be preheated, and the preheating temperature is, for example, 40 to 140°C.

Examples of substrate materials used in the present invention include plate-shaped members made of insulating materials such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, and polyimide. . Chemical treatment using silane coupling agents, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum evaporation, etc., can also be applied to the surface of these plate-shaped members as needed. pre-processing. In the present invention, it is preferable to use a heat-resistant glass substrate as the substrate. As such a glass substrate, "PD200" by Asahi Glass Co., Ltd. etc. are mentioned, for example.

<Exposure process>

After the photosensitive resin layer containing inorganic fine particles is formed on the substrate through the above-mentioned resin layer forming step, exposure is performed using an exposure device. Exposure can be performed by a mask exposure method using a photomask as in photolithography. The mask to be used can be either a negative type or a positive type according to the type of organic components in the inorganic particle-containing photosensitive resin layer. The exposure pattern of the exposure mask varies depending on the purpose, and is, for example, a stripe or a grating with a width of 10 to 500 μm.

In addition, a method of directly drawing with a red or blue visible laser, an Ar ion laser, or the like without using a mask may also be employed.

The surface of the photosensitive resin layer containing inorganic fine particles is selectively irradiated (exposed) with rays such as ultraviolet rays through an exposure mask to form a pattern latent image on the resin layer. In addition, it is preferable to perform exposure without peeling off the support film coated on the resin layer.

As the exposure apparatus, a parallel light exposure machine, a scattered light exposure machine, a stepper exposure machine, a proximity exposure machine, etc. can be used. In addition, when exposing a large area, after applying the inorganic fine particle-containing photosensitive resin composition on a substrate such as a glass substrate, exposing while transporting it, it is possible to expose a large area with an exposure machine with a small exposure area.

The active light source used during exposure includes, for example: visible rays, near ultraviolet rays, ultraviolet rays, electron rays, X-rays, lasers, etc., but among these, ultraviolet rays are preferred, and as the light source, for example: low-pressure mercury lamps, high-pressure mercury lamps, ultra- High-pressure mercury lamps, halogen lamps, etc. Among these, ultra-high pressure mercury lamps are preferred.

The exposure conditions vary with the thickness of the coating, but an ultra-high pressure mercury lamp with an output power of 1-100mW/cm ² is used for exposure of 0.05-1 minute. In this case, by using a wavelength filter to narrow the wavelength region of the exposure light, scattering of light can be suppressed and pattern formation properties can be improved. Specifically, a filter that blocks i-ray (365 nm) light, or a filter that blocks i-ray or h-ray (405 nm) light can be used to improve the pattern formability.

<Development process>

After the above-mentioned exposure, the resin layer is developed to form a pattern of the resin layer by utilizing the difference in solubility of the photosensitive part and the non-photosensitive part to the developing solution. Developing method (such as immersion method, shaking method, shower method, spray method, padding method, magnetic brush method, etc.) and developing treatment conditions (such as: type, composition, concentration, developing time, developing temperature, etc. What is necessary is just to select and set suitably according to the kind of resin layer.

An organic solvent capable of dissolving an organic component in the resin layer can be used as a developing solution used in the image development step. In addition, water may be added to the above-mentioned organic solvent within the range where the dissolving power of the above-mentioned organic solvent is not lost. When a compound having an acidic group such as a carboxyl group exists in the resin layer, it can be developed with an aqueous alkali solution.

Examples of the alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate , sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia solution , tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, Diethanolamine, triethanolamine, etc.

The concentration of the aqueous alkali solution is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble portion cannot be removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the insoluble portion may be corroded, which is not preferable. Moreover, it is preferable to perform image development temperature at the time of image development at 20-50 degreeC from the viewpoint of process control.

Additives, such as a nonionic surfactant and an organic solvent, may be contained in the said alkaline aqueous solution. In addition, after the development treatment with an alkali developing solution, washing treatment with water can usually be given.

<Firing process>

The pattern of the resin layer is fired in a firing furnace in order to burn off the organic substances in the remaining portion of the resin layer after the development (pattern of the resin layer).

The firing atmosphere differs depending on the composition or the type of substrate, but firing is carried out in an atmosphere of air, ozone, nitrogen, hydrogen, or the like. As the firing furnace, a batch type firing furnace or a belt type continuous type firing furnace can be used.

Since it is necessary to burn off the organic substances in the remaining part of the resin layer, the firing treatment conditions are generally firing temperature 300-1000° C., and firing time 10-90 minutes. For example, when forming a pattern on a glass substrate, it holds at 350-600 degreeC for 10-60 minutes, and bakes.

According to the pattern forming method of the present invention including the above steps, circuit patterns of display panel components or electronic components such as dielectrics, electrodes, resistors, phosphors, spacers, color filters, and black matrices can be formed. In addition, in each of the above-mentioned steps of transfer, exposure, development, and firing, a heating step at 50 to 300° C. may be introduced for drying or preliminary reaction.

The method for preparing a flat display panel of the present invention, as described above, includes the step of forming at least one member for a display panel selected from dielectrics, electrodes, resistors, phosphors, spacers, color filters, and black matrices, and is suitable for Fabrication of plasma display panels.

[Example]

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited by these examples. In addition, "part" and "%" in an Example and a comparative example represent "part by weight" and "% by weight", respectively, unless otherwise specified.

First, measurement methods and evaluation methods of physical properties will be described.

[Measurement method of thermogravimetric analysis]

Thermogravimetric analysis was performed using a thermogravimetric analysis device ("Hi-ResTGA2950" manufactured by TA instruments) at a temperature increase rate of 10°C/min and a flow rate of 60 ml/min.

The measurement results of the following three photopolymerization initiators are shown in Figures 2 to 4:

MTPMP: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propan-1-one

BDPPB: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1

BTPP: bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.

[Measuring method of weight average molecular weight (Mw)]

Mw is a value in terms of polystyrene measured by gel permeation chromatography (GPC) ("HLC-8220GPC" manufactured by Toray Corporation). In addition, the GPC measurement was carried out using "TSK guard column Super HZM-M" manufactured by Toray Co., Ltd. as a GPC column, using tetrahydrofuran (THF) as a solvent, and performing the measurement at a temperature of 40°C.

[Evaluation method of pattern after development]

Cut the developed display panel to make a test piece (15cm x 15cm x 2.8cm), observe the pattern section at the position shown in Fig. 5 with a scanning electron microscope ("S4200" manufactured by Hitachi, Ltd.), and measure the width and height of the pattern. Evaluation was performed according to the following criteria, respectively. In addition, the desired specifications are pattern width of 50 μm, height of 180 μm, and interval of 200 μm.

A: The desired specification is within ±3 μm.

B: Exceeds the desired specification by ±3 µm but is within ±5 µm.

C: Exceeds the desired specification by ±5 µm but is within ±10 µm.

D: Exceeds the desired specification by ±10 μm.

[Evaluation method of pattern after firing]

Cut the fired panel to make a test piece (15cm x 15cm x 2.8cm), observe the pattern section at the position shown in Fig. 5 with a scanning electron microscope ("S4200" manufactured by Hitachi, Ltd.), and measure the width and height of the pattern. Evaluation was performed according to the following criteria, respectively. In addition, desired specifications are pattern width of 50 μm, height of 120 μm, and interval of 200 μm.

A: The desired specification.

B: The desired specification is within ±3 μm.

C: Exceeds the desired specification by ±3 µm but is within ±5 µm.

D: Exceeds the desired specification by ±5 μm.

[Reflectivity of fired substrate]

Using a spectrophotometer (UV-2450PC manufactured by Shimadzu Corporation, multi-functional large sample chamber unit MPC-2200 accessories manufactured by Shimadzu Corporation) to the obtained 5 × 5cm shape firing The reflectance of the substrate at a wavelength of 550 nm was measured.

[Synthesis Example B-1]

55 g of benzyl methacrylate, 45 g of 2-methacryloyloxyethyl phthalic acid, 1 g of azobisisobutyronitrile (AIBN), 5 g of tetra( 3-Mercaptopropionic acid) pentaerythritol ester (manufactured by Sakai Chemical Industry Co., Ltd.), was stirred in 150 parts of propylene glycol monomethyl ether until uniformly mixed under a nitrogen atmosphere. Then polymerize at 70°C for 4 hours, and then continue to polymerize at 100°C for 1 hour, then cool to room temperature to obtain methacrylic resin (B-1) (hereinafter referred to as "alkali-soluble resin (B-1)). The alkali The polymerization rate of the soluble resin (B-1) was 98%, and the weight average molecular weight of the alkali-soluble resin (B-1) was 20,000.

[Synthesis Example B-2]

Except using 5 g of Nofuma-NSD (manufactured by NOF Co., Ltd.) instead of pentaerythritol tetrakis (3-mercaptopropionate), others were carried out in the same manner as in Synthesis Example B-1 to obtain methacrylic resin (B-2) ( Hereinafter, it is called "alkali-soluble resin (B-2)). The polymerization rate of this alkali-soluble resin (B-2) was 98%, and the weight average molecular weight of this alkali-soluble resin (B-2) was 25000.

[Synthesis Example C-1]

In a 1-liter flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen inlet tube, 300 g (hydroxyl = 3 mol) of tris(polyoxypropylene) glyceryl ether (Mw300) (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.56 g hydrochloric acid (35% aqueous solution, containing 0.015 mol of HCl), stirred, and slowly added 600 g (3 mol) of [2-(ethyleneoxyethoxy)] ethyl methacrylate dropwise while paying attention to heat release. When the heat release was slow, the temperature was raised to 60° C., and the reaction was carried out for 4 hours. As a result of IR analysis of the reactant obtained as above, the peak around 3500 cm ^-1 due to the hydroxyl group almost disappeared, and the intended polyfunctional methacrylate (C-1) was obtained.

[Synthesis Example C-2]

In the same manner as in Synthesis Example C, except that 700 g (hydroxyl group = 3 mol) of tris(polyoxypropylene) glyceryl ether of Mw 700 (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of tris(polyoxypropylene) glyceryl ether of Mw of 300, -1 was carried out in the same manner to obtain a polyfunctional methacrylate (C-2). When this polyfunctional methacrylate (C-2) was analyzed by IR, the peak around 3500 cm ^-1 due to the hydroxyl group almost disappeared.

[Example 1]

100 g of organic components shown in Table 1 (alkali-soluble resin (B-1)) (63.5% by weight), polyfunctional methacrylate (TMP) (35% by weight), photopolymerization initiator (MTPMP) (1.2% by weight) ) and sensitizer (2,4-diethylthioxanthone) (DETX) (0.2% by weight), sensitizer (1-chloro-4-propoxythioxanthone) (CPTX) (0.1% by weight ), dissolved in 30 g of propylene glycol monomethyl ether (PGME), and then, 300 g of glass powder shown in Table 1 as inorganic fine particles, 5 g of surfactant A-60 (manufactured by Kao Corporation) and 0.05 g UV absorber TTO-V-4 (manufactured by Ishihara Sangyo Co., Ltd.), kneaded in a kneader to prepare a photosensitive resin composition containing inorganic fine particles (hereinafter also referred to as "photosensitive paste").

Prepare 2 sheets of polyethylene terephthalate (PET) films (200 mm wide, 10 m long, and 50 μm thick) that have been pre-released as supporting films, and apply the above-mentioned A photosensitive paste containing inorganic fine particles was used to form a coating film, and the formed coating film was dried at 90° C. for 10 minutes to remove the solvent, thereby forming a photosensitive resin layer containing inorganic fine particles with a thickness of 90 μm. Then, the inorganic fine particle-containing photosensitive resin layers formed on the two PET films were bonded to each other, and thermocompression bonding was performed using a heating roll. The pressure-bonding conditions were as follows: the surface temperature of the heating roll was 90°C, the roll pressure was 4 kg/cm ² , and the moving speed of the heating roll was 0.5 m/min. In this way, a photosensitive film having a photosensitive resin layer (thickness: 180 μm) containing inorganic fine particles was produced.

Then, one of the support films is peeled off, and the above-mentioned photosensitive resin layer containing inorganic particles is laminated on the surface of a glass substrate for a 6-inch display panel. After the remaining support film is peeled off, the photosensitive resin layer containing inorganic particles is bonded with a heating roller by thermocompression. resin layer. The pressure-bonding conditions were as follows: the surface temperature of the heating roll was 90°C, the roll pressure was 4 kg/cm ² , and the moving speed of the heating roll was 0.5 m/min. Thereby, the photosensitive resin layer containing inorganic fine particles was transferred on the surface of the glass substrate, and it became the state which adhered. It was measured that the thickness of the transferred photosensitive resin layer containing inorganic particles was in the range of 180 μm±3 μm in Examples 1 to 12.

Then, using a negative chromium mask (pattern width 50 μm, pattern interval 200 μm), the photosensitive resin layer containing inorganic particles was exposed to ultraviolet rays from above with an ultra-high pressure mercury lamp with an output power of 25 mJ/cm ² . The exposure amount was 200 mJ/cm ² .

Then, the exposed inorganic fine particle-containing photosensitive resin layer was sprayed with a 0.5% aqueous solution of sodium carbonate maintained at 23° C. using a shower for development. Thereafter, it was washed with water using a shower spray to remove voids that were not photocured, and a grid-like photosensitive resin pattern containing inorganic fine particles was formed on the glass substrate for a display panel. The pattern after the development was evaluated by the above-mentioned evaluation method. The results are shown in Table 1.

Then, the obtained inorganic fine particle-containing photosensitive resin pattern was fired at 580° C. for 30 minutes to form a spacer pattern, and the fired pattern was evaluated by the above-mentioned evaluation method.

As another method, except for exposing to ultraviolet light without using a negative chrome mask, it was performed in the same preparation method as the above-mentioned spacer pattern to obtain a fired substrate. This fired substrate was cut into 5×5 cm, and the reflectance of the fired substrate was evaluated by the above-mentioned evaluation method. The results are shown in Table 1.

[Embodiments 2-14]

Except for changing the organic component as shown in Table 1, it carried out similarly to Example 1, and produced the pattern and baked the board|substrate, and it evaluated. The results are shown in Table 1.

In the pattern evaluation, the patterns of Examples 7 to 10 were particularly excellent after image development and after firing.

Table 1

Inorganic particles Alkali soluble resin Multifunctional (meth)acrylate Photoinitiator Relative to 100 parts by weight of acrylate Sensitizer Relative to 100 parts by weight of acrylate Sensitizer Relative to 100 parts by weight of acrylate pattern evaluation Reflectivity% After development after firing Width high Width high 1 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 35 2 SiO2-B2O3-Li2O series 300 B-1 63.5 C-1 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 45 3 SiO2-B2O3-Li2O series 300 B-1 63.5 C-2 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 45 4 SiO2-B2O3-Li2O series 300 B-2 63.5 TMP 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 35 5 SiO2-B2O3-Li2O series 300 B-2 63.5 C-1 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 45 6 SiO2-B2O3-Li2O series 300 B-2 63.5 C-2 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 45 7 SiO2-B2O3-Li2O series 300 B-2 63.5 C-2 35 MTPMP 3.0 8.57 DETX 0.6 1.71 CPTX 0.3 0.86 A A A A 40 8 SiO2-B2O3-Li2O series 300 B-2 63.5 C-2 35 MTPMP 3.0 8.57 DETX 0.5 1.43 CPTX 0.3 0.86 A A A A 40 9 SiO2-B2O3-Li2O series 300 B-2 63.5 C-2 35 MTPMP 2.5 7.14 DETX 0.4 1.14 CPTX 0.2 0.57 A A A A 40 10 SiO2-B2O3-Li2O series 300 B-2 63.5 C-2 35 MTPMP 2.0 5.71 DETX 0.3 0.86 CPTX 0.2 0.57 A A A A 40 11 SiO2-B2O3-K2O series 300 B-1 63.5 C-2 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 45 12 SiO2-B2O3-Na2O series 300 B-1 63.5 C-2 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 45 13 SiO2-Al2O3-B2O3 series 300 B-1 63.5 C-2 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 45 14 SiO2-Al2O3-Bi2O3 series 300 B-1 63.5 C-2 35 MTPMP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 B B B B 45

TMP: Trimethylolpropane Triacrylate

MTPMP: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propan-1-one

DETX: 2,4-Diethylthioxanthone

CPTX: 1-chloro-4-propoxythioxanthone

The numbers represent parts by mass.

[Comparative examples 1 to 11]

Except for changing the organic component as shown in Table 2, it carried out similarly to Example 1, and produced the pattern and baked the board|substrate, and it evaluated. The results are shown in Table 2.

In the pattern evaluation after image development of Comparative Examples 1-11, the unfavorable pattern in which the aspect ratio was insufficient or image development residue was observed was observed. In addition, in the pattern evaluation after firing, a pattern with an insufficient aspect ratio was observed.

Table 2

Inorganic particles Alkali soluble resin Multifunctional (meth)acrylate photopolymerization initiator Relative to 100 parts by weight of acrylate Sensitizer Relative to 100 parts by weight of acrylate Sensitizer Relative to 100 parts by weight of acrylate pattern evaluation Reflectivity% After development after firing Width high Width high 1 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 BDPPB 5 14.29 DETX 0.2 0.57 CPTX 0.1 0.29 C C D D 5 2 SiO2-B2O3-Li2O series 300 B-1 63.5 C-1 35 BDPPB 5 14.29 DETX 0.2 0.57 CPTX 0.1 0.29 C C D D 15 3 SiO2-B2O3-Li2O series 300 B-1 63.5 C-2 35 BDPPB 5 14.29 DETX 0.2 0.57 CPTX 0.1 0.29 C C D D 15 4 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 BDPPB 1.2 3.43 0.00 CPTX 0.1 0.29 C C D D 10 5 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 BDPPB 1.2 3.43 DETX 0.2 0.57 0.00 C C D D 10 6 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 0.00 DETX 0.2 0.57 CPTX 0.1 0.29 D D D D 10 7 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 BTPP 1.2 3.43 DETX 0.2 0.57 CPTX 0.1 0.29 D D D D 10 8 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 BDPPB 1.2 3.43 0.00 CPTX 0.1 0.29 C C D D 10 BTPP 1.2 3.43 9 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 BDPPB 1.2 3.43 DETX 0.2 0.57 0.00 C C D D 10 BTPP 1.2 3.43 10 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 BDPPB 1.2 3.43 0.00 0.00 D D D D 10 11 SiO2-B2O3-Li2O series 300 B-1 63.5 TMP 35 MTPMP 1.2 3.43 0.00 0.00 D D D D 10

TMP: Trimethylolpropane Triacrylate

MTPMP: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propan-1-one

BDPPB: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1

DETX: 2,4-Diethylthioxanthone

CPTX: 1-Chloro-4-propoxythioxanthone

BTPP: bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide

The numbers represent parts by mass.

Claims (7)

1. photosensitive resin composition that contains inorganic particles, this photosensitive resin composition that contains inorganic particles contains (A) inorganic particles, (B) alkali soluble resin, (C) multifunctional (methyl) acrylate, (D) Photoepolymerizationinitiater initiater and (E) sensitizer, it is characterized in that:

Described (D) Photoepolymerizationinitiater initiater is a compound shown in the following formula (1),

Described (E) sensitizer is a compound shown in compound shown in the following formula (2) and the following formula (3),

In the formula (1), R ¹And R ²The alkyl of representing carbon number 1～4 independently of each other,

In the formula (2), R ³And R ⁴The alkyl of representing hydrogen or carbon number 1～4 independently of each other,

In the formula (3), R ⁵Expression fluorine, chlorine, bromine, iodine or fluoroform sulphonate, R ⁶The alkyl of expression hydrogen or carbon number 1～4,

2. the described photosensitive resin composition that contains inorganic particles of claim 1, it is characterized in that: with respect to described (C) multifunctional (methyl) acrylate of 100 weight portions, contain: compound shown in the formula of 3.0～10.0 weight portions (1), 0.5 compound shown in the formula of～2.0 weight portions (2), compound shown in the formula of 0.2～1.0 weight portion (3).

3. a light-sensitive surface is characterized in that: have the photosensitive resin composition layer that contains inorganic particles that is obtained by claim 1 or the 2 described photosensitive resin compositions that contain inorganic particles.

4. pattern formation method is characterized in that comprising:

(I) on substrate, form the operation of the photosensitive resin composition layer that contains inorganic particles that obtains by claim 1 or the 2 described photosensitive resin compositions that contain inorganic particles,

(II) this photosensitive resin composition layer that contains inorganic particles is carried out the operation of exposure-processed with formation pattern sub-image,

(III) photosensitive resin composition layer that contains inorganic particles after the exposure is carried out the operation of development treatment with the formation pattern, and

(IV) burn till the operation of handling this pattern.

5. the described pattern of claim 4 formation method is characterized in that: in above-mentioned operation (I), use the described light-sensitive surface of claim 3 to form the photosensitive resin composition layer that contains inorganic particles on substrate.

6. the preparation method of a flat-panel monitor is characterized in that: comprise that adopting claim 4 or 5 described pattern formation methods to form is selected from the operation of the central at least a display panel of dielectric, electrode, resistance, fluorophor, partition, colored filter and black matrix" with member.

7. the preparation method of the described flat-panel monitor of claim 6, it is characterized in that: described display panel is a Plasmia indicating panel.

Images