JP5050784B2 - Inorganic particle-containing photosensitive resin composition, photosensitive film, pattern forming method, and flat panel display manufacturing method - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive film, a pattern forming method, and a method for producing a flat panel display. More specifically, it is used for a display panel such as a flat panel display having a display cell composed of a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix, and an advanced mounting material for electronic components. In the production of a circuit board having a fine circuit pattern, a photosensitive resin composition that is excellent in thermal decomposability of organic components such as a photopolymerization initiator and can be suitably used when forming a highly accurate pattern, The present invention relates to a photosensitive film having a photosensitive resin layer made of a composition, a pattern forming method using the composition or the photosensitive film, and a method for producing a flat panel display including the pattern forming method as a part of the steps.

  In recent years, there is an increasing demand for higher density and higher definition for pattern processing in circuit boards and display panels. Among such display panels that have been increasing in demand, particularly flat panel displays (hereinafter referred to as “FPD”) such as plasma display panels (hereinafter also referred to as “PDP”) and field emission displays (hereinafter also referred to as “FED”). ) Is attracting attention.

  FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1, reference numerals 101 and 102 denote opposing glass substrates, and reference numerals 103 and 111 denote partition walls. Cells are partitioned by the glass substrate 101, the glass substrate 102, the partition walls 103, and the partition walls 111. 104 is a transparent electrode fixed to 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 to the glass substrate 102. It is. 107 is a fluorescent material held in the cell, 108 is a dielectric layer formed on the surface of the glass substrate 101 so as to cover the transparent electrode 104 and the bus electrode 105, and 109 is used to cover the address electrode 106. A dielectric layer is formed on the surface of the glass substrate 102, and 110 is a protective film made of, for example, magnesium oxide. In a color FPD, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

  As a method for forming FPD members such as partition walls, electrodes, resistors, phosphors, color filters, and black matrices, (1) a non-photosensitive resin is screen-printed on a substrate to form a desired pattern; (2) A photosensitive resin layer is formed on a substrate, and the photosensitive resin layer is irradiated with infrared rays or ultraviolet rays through a photomask on which a desired pattern is drawn, and then developed. Thus, a photolithography method is known in which a desired pattern remains on a substrate and is baked (see, for example, Patent Document 1).

However, the screen printing method has a problem that the demand for pattern accuracy becomes very strict as the panel becomes larger and the definition becomes higher, and cannot be handled by ordinary screen printing. In addition, although the photolithography method is excellent in pattern accuracy, when the film thickness is large, the sensitivity of the depth method is insufficient and the pattern accuracy deteriorates, and the thermal decomposability of the photosensitive resin composition in the baking process. There was a problem that defects were observed.
Japanese Patent Laid-Open No. 11-44949

  The present invention is intended to solve the problems associated with the prior art as described above, can form a highly accurate pattern, and is excellent in thermal decomposability of organic components such as a photopolymerization initiator. An object is to provide a photosensitive resin composition containing inorganic particles.

  In addition, the present invention is formed from the above-mentioned inorganic particle-containing photosensitive resin composition, can form a highly accurate pattern, and has inorganic particle-containing photosensitivity excellent in the thermal decomposability of organic components such as a photopolymerization initiator. It is another object of the present invention to provide a photosensitive film having a resin layer, and to provide a pattern forming method using the composition or photosensitive film of the present invention and a method for producing a flat panel display including the pattern forming method. .

  As a result of intensive studies to solve the above problems, the present inventors have included inorganic photosensitizers capable of forming a highly accurate pattern by containing a specific photopolymerization initiator and sensitizer. The present inventors have found that a resin composition can be provided and completed the present invention.

That is, the inorganic particle-containing photosensitive resin composition of the present invention comprises inorganic particles (A), alkali-soluble resin (B), polyfunctional (meth) acrylate (C), photopolymerization initiator (D), and sensitizer ( E) containing inorganic resin-containing photosensitive resin composition,
The photopolymerization initiator (D) is a compound represented by the following formula (1),
The sensitizer (E) is a compound represented by the following formula (2) and a compound represented by the following formula (3).

（式（１）において、Ｒ¹およびＲ²は相互に独立に炭素数１〜４のアルキル基を示す。）

(In formula (1), R ¹ and R ² represents an alkyl group having 1 to 4 carbon atoms independently of one another.)

（式（２）において、Ｒ³およびＲ⁴は相互に独立に水素または炭素数１〜４のアルキル基を示す。）

(In Formula (2), R ³ and R ⁴ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.)

（式（３）において、Ｒ⁵は弗素、塩素、臭素、沃素、またはトリフラートを示し、Ｒ⁶は水素または炭素数１〜４のアルキル基を示す。）
前記多官能（メタ）アクリレート（Ｃ）１００重量部に対し、
式（１）で表される化合物を３．０〜１０．０重量部、
式（２）で表される化合物を０．５〜２．０重量部、
式（３）で表される化合物を０．２〜１．０重量部
の範囲で含有することが好ましい。

(In Formula (3), R ⁵ represents fluorine, chlorine, bromine, iodine, or triflate, and R ⁶ represents hydrogen or an alkyl group having 1 to 4 carbon atoms.)
For 100 parts by weight of the polyfunctional (meth) acrylate (C),
3.0 to 10.0 parts by weight of the compound represented by the formula (1),
0.5 to 2.0 parts by weight of the compound represented by formula (2),
It is preferable to contain the compound represented by Formula (3) in the range of 0.2 to 1.0 part by weight.

The present invention includes a photosensitive film having an inorganic particle-containing photosensitive resin composition layer obtained from the inorganic particle-containing photosensitive resin composition.
The present invention further includes (I) a step of forming an inorganic particle-containing photosensitive resin composition layer obtained from the inorganic particle-containing photosensitive resin composition on a substrate, and (II) the inorganic particle-containing photosensitive resin composition. A step of exposing the layer to form a latent image of the pattern, (III) a step of developing the exposed inorganic particle-containing photosensitive resin composition layer to form a pattern, and (IV) a baking treatment of the pattern The pattern formation method characterized by including the process to perform.

In the step (I), an inorganic particle-containing photosensitive resin composition layer may be formed on a substrate using the photosensitive film.
The present invention includes a step of forming at least one display panel member selected from a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix by the pattern forming method. Including a flat panel display manufacturing method.

  The display panel may be a plasma display panel.

  The inorganic particle-containing photosensitive resin composition and photosensitive film of the present invention can form a highly accurate pattern and are excellent in the thermal decomposability of organic components such as a photopolymerization initiator. It can be suitably used for forming members constituting each display cell as well as forming members for highly mounting materials for electronic components.

Hereinafter, the inorganic particle-containing photosensitive resin composition, the photosensitive film, and the pattern forming method according to the present invention will be described in detail.
[Inorganic particle-containing photosensitive resin composition]
The inorganic particle-containing photosensitive resin composition of the present invention comprises inorganic particles (A), alkali-soluble resin (B), polyfunctional (meth) acrylate (C), photopolymerization initiator (D), and sensitizer (E ).

<Inorganic particles (A)>
The inorganic particles (A) used in the composition of the present invention vary depending on the type of forming material. In particular, the inorganic particles used for the dielectric and the partition wall forming material constituting the FPD include glass powder.

  Examples of the glass powder used in the composition of the present invention include a low melting point glass powder having a heat 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 at the stage where the organic substance such as resin is not completely decomposed and removed in the baking process of the photosensitive resin layer formed from the composition. . Therefore, a part of the organic substance remains in the formed member, and as a result, members such as the dielectric layer and the partition are colored, and the light transmittance may be reduced. On the other hand, when the thermal softening point of the glass powder exceeds the above range, it is necessary to fire at a high temperature, so that the glass substrate is likely to be distorted.

Examples of the glass powder include (1) Bi ₂ O ₃ —ZnO—B ₂ O ₃ series and (2) Bi.
₂ O ₃ —SiO ₂ —B ₂ O ₃ 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 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 _{-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 —ZnO system, (22) Al ₂ O glass powder such as _{3 -B 2 O 3 -SiO 2 -BaO} -CaO-Li 2 O-MgO-Na 2 O-Fe 2 O 3 -TiO 2 -ZnO system can be mentioned.

  The shape of the glass powder is not particularly limited. The above 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.

  The glass powder preferably contains silicon oxide in the range of 5 to 50% by weight, and more preferably in the range of 10 to 30% by weight, in order to obtain higher definition patterning. Silicon oxide has a function of improving the denseness, strength and stability of the glass and is effective in reducing the refractive index of the glass. In addition, the thermal expansion coefficient can be controlled to prevent peeling due to mismatch with the glass substrate. When the content of silicon oxide is 5% by weight or more, the coefficient of thermal expansion can be suppressed to be small, the occurrence of cracks occurring when baked on a glass substrate can be reduced, and the refractive index can be suppressed to a low level. Moreover, when the content of silicon oxide is 50% by weight or less, the glass transition point and the load softening point can be kept low, and the baking temperature on the glass substrate can be lowered.

  The glass powder preferably contains boron oxide in the range of 10 to 50% by weight, and more preferably in the range of 20 to 45% by weight. When the content of boron oxide is 10% by weight or more, the glass transition point and the load softening point can be kept low, and baking onto the glass substrate can be facilitated. Further, when the content of boron oxide is 50% by weight or less, the chemical stability of the glass can be maintained. 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 weight, and is contained in the range of 2 to 20% by weight. More preferably. These components are effective in adjusting the thermal expansion coefficient, and have the effect of preventing deformation of the substrate during firing, the effect of imparting electrical insulation, the effect of improving the stability and denseness of the partition walls to be formed, etc. Have. When the content is 1% by weight or more, devitrification due to crystallization of the glass can be prevented, and when the content is 30% by weight or less, the thermal expansion coefficient and the refractive index can be kept small. At the same time, chemical stability can be maintained.

  The glass powder preferably contains aluminum oxide in the range of 1 to 40% by weight. Aluminum oxide has the effect of stabilizing the glass by expanding the vitrification range, and is effective in extending the pot life of the 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 can be improved.

  The glass powder preferably contains at least one of calcium oxide and magnesium oxide so that the total amount is 1 to 20% by weight. These components have the effect of making the glass easier to melt and controlling the thermal expansion coefficient. When the content is 1% by weight or more, devitrification due to crystallization of the glass can be prevented, and when the content is 15% by weight 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 weight. 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 weight 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 diameter 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 8 μm for pattern formation. Moreover, it is preferable on pattern formation that the specific surface area of glass powder is 0.1-300 m < ² > / g.

  The glass powder may be contained in a composition for forming components other than the FPD dielectric and barrier ribs (for example, electrodes, resistors, phosphors, color filters, and black matrix). In this case, the content of the glass powder varies depending on the use, but is usually 90 wt% or less, preferably 80 wt% or less with respect to 100 parts by weight of the total amount of inorganic particles including the glass powder.

  Inorganic particles used for electrode forming materials such as FPD, LCD, organic EL, printed circuit board, multilayer circuit board, module, inductor and LSI include Al, Ag, Ag-Pd alloy, Au, Ni, Cr, Cu And so on. 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. The shape of the inorganic particles used for the electrode forming material is not particularly limited, such as granular, spherical, flake, etc. Even if inorganic particles having the same shape are used, two or more different types of inorganic particles are mixed. It may be used. The average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 8 μm, and inorganic particles having different average particle diameters can be mixed and used.

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

The inorganic particles used for the phosphor-forming material of PDP are:
For red, 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.
Examples of green 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, and the like. And
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 particles used in color filter forming materials such as PDPs, LCDs, and organic EL elements are Fe ₂ O ₃ for red, Cr ₂ O ₃ for green, and CoO · Al ₂ O for blue. ₃ and so on.

  Examples of inorganic 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, and Zn, and oxides thereof. Examples thereof include composite oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, and graphite. These may be used singly or in combination of two or more. Among these, metal particles, metal oxide particles and composite oxide particles selected from the group of Co, Cr, Cu, Fe, Mn, Ni and Ti are preferable. Moreover, as an 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.

  Content of the inorganic particle (A) in the composition of this invention is the range of 100-2000 weight part with respect to 100 weight part of alkali-soluble resin (B), Preferably it is the range of 130-1000 weight part. When the content of the inorganic particles (A) is within the above range, a pattern having a good shape can be formed.

<Alkali-soluble resin (B)>
Various resins can be used as the alkali-soluble resin (B) used for the inorganic particle-containing photosensitive resin composition. In the present invention, “alkali-soluble” refers to a property of being dissolved in an alkaline developer to such an extent that the intended development processing is possible.

The alkali-soluble resin (B) can be obtained, for example, by copolymerizing an alkali-soluble functional group-containing monomer (B1) and a (meth) acrylic acid derivative (B2).
Examples of the alkali-soluble functional group-containing monomer (B1) include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, and succinic acid mono (2- (meth)). Acryloyloxyethyl), 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrophthalate, carboxyl group-containing monomers such as ω-carboxy-polycaprolactone mono (meth) acrylate;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (α-hydroxymethyl) acrylate;
Examples thereof include monomers having an alkali-soluble functional group and an unsaturated bond, such as phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. Among these monomers, (meth) acrylic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyl Oxypropyltetrahydrohydrogenphthalate and 2-hydroxyethyl (meth) acrylate are preferred.

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

  The (meth) acrylic acid derivative (B2) is not particularly limited as long as it is a (meth) acrylic acid derivative copolymerizable with the alkali-soluble functional group-containing monomer (B1). For example, methyl (meth) acrylate, Ethyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, totyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , (Meth) acrylates other than the monomer (B1) such as glycidyl (meth) acrylate and dicyclopentanyl (meth) acrylate.

  In the present invention, for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate instead of the (meth) acrylic acid derivative (B2) or in addition to the (meth) acrylic acid derivative (B2). Alternatively, a macromonomer having a polymerizable unsaturated group such as a (meth) acryloyl group, an allyl group, or a vinyl group may be used at one chain end of a polymer obtained from benzyl (meth) acrylate or the like.

(Radical polymerization initiator)
In the copolymerization, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, a radical polymerization initiator used for polymerization of a vinyl monomer can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutylnitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis Azo compounds such as (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid); t-butyl peroxybivalate, t-butyl Examples thereof include organic peroxides of peroxyesters such as peroxy 2-ethylhexanoate and cumylperoxy 2-ethylhexanoate. 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 with respect to 100 weight part of all the monomers used for the said copolymerization.

  The weight-average molecular weight (hereinafter also referred to as “Mw”) of the alkali-soluble resin (B) thus obtained is a polystyrene conversion value measured by gel permeation chromatography (GPC), preferably 5,000. ~ 100,000, more preferably 10,000 to 50,000. Mw can be controlled by appropriately selecting conditions such as the copolymerization ratio, composition, chain transfer agent, and polymerization temperature of the monomer. When Mw is lower than the above range, film roughness after development is likely to occur, and when Mw exceeds the above range, the solubility of the unexposed portion in the developer may be reduced and resolution may be reduced. .

  The glass transition temperature (Tg) of the alkali-soluble resin (B) is 0 to 120 ° C, preferably 10 to 100 ° C. When the glass transition temperature is lower than the above range, the coating film tends to be tacky and is difficult to handle. On the other hand, when the glass transition temperature exceeds the above range, the adhesiveness with the glass substrate as the support may be deteriorated and transfer may not be possible. In addition, the said glass transition temperature can be suitably adjusted by changing the quantity of the said compound (B1) and (meth) acrylic acid derivative (B2).

The acid value of the alkali-soluble resin (B) is preferably 20 to 200 mgKOH / g, more preferably 30 to 160 mgKOH / g. When the acid value is 20 mgKOH / g or less, the unexposed portion after exposure is not easily removed with an alkaline developer, and it tends to be difficult to form a high-definition pattern. On the other hand, when the acid value is 200 mgKOH / g or more, the portion cured by the exposure light is easily eroded by the alkali developer, and it tends to be difficult to form a high-definition pattern.

<Multifunctional (meth) acrylate (C)>
The polyfunctional (meth) acrylate (C) that constitutes the inorganic particle-containing photosensitive resin composition contains an ethylenically unsaturated group and can be subjected to radical polymerization reaction with a photopolymerization initiator described later. Although it is not particularly limited as long as it is an acrylate compound, the following (meth) acrylate compounds are usually used.

  Specific examples of the polyfunctional (meth) acrylate (C) used in the present invention include allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, and 1,4-butanediol di (meth) acrylate. 1,3-butylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol di (meth) Acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglycerol Di (meth) taacrylates such as (meth) acrylate; pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, benzyl mercaptan (meth) acrylate, etc. (Meth) acrylates; and the like.

  Moreover, you may use the compound shown by following formula (4).

（式（４）中、Ｚは下記式（５）で表される基である。）

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

（式（５）中、ｎは１〜１０の実数である）で表される化合物が挙げられる。
通常、上記多官能（メタ）アクリレート（Ｃ）は、１種単独で用いても、２種以上を組み合わせて用いてもよい。本発明の組成物における上記多官能（メタ）アクリレート（Ｃ）の含有量は、アルカリ可溶性樹脂（Ｂ）１００重量部に対して、通常２０〜２００重量部、好ましくは３０〜１００重量部の範囲である。多官能（メタ）アクリレート（Ｃ）の含有量が少なすぎると、露光部が現像液によって浸食されやすくなり、パターンを形成することができない。含有量が多すぎると、長時間の現像工程となり生産上好ましくない。さらに、焼成時に収縮が大きくなり、剥れの原因となる。

(In formula (5), n is a real number of 1 to 10).
Usually, the said polyfunctional (meth) acrylate (C) may be used individually by 1 type, or may be used in combination of 2 or more type. Content of the said polyfunctional (meth) acrylate (C) in the composition of this invention is 20-200 weight part normally with respect to 100 weight part of alkali-soluble resin (B), Preferably it is the range of 30-100 weight part. It is. When there is too little content of polyfunctional (meth) acrylate (C), an exposure part will become easy to be eroded by a developing solution, and a pattern cannot be formed. If the content is too large, the development process takes a long time, which is not preferable for production. Furthermore, shrinkage increases during firing, causing peeling.

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) constituting the inorganic particle-containing photosensitive resin composition of the present invention,
The compound represented by the formula (1) (hereinafter also referred to as photopolymerization initiator (1)).

The photopolymerization initiator (1) is preferable because the sensitizer represented by the above formulas (2) and (3) efficiently initiates polymerization. R ¹ and R ² in the above formula (1) are each independently an alkyl group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n -A butyl group, an i-butyl group, a sec-butyl group and a t-butyl group are preferable, and a methyl group is particularly preferable.

  The photopolymerization initiator (1) has a weight reduction rate at 400 ° C. of 90% or more and a weight reduction rate at 550 ° C. of 99% or more. Therefore, the inorganic particle-containing photosensitive resin composition containing the photopolymerization initiator (1) can form a highly accurate pattern and provide an inorganic particle-containing photosensitive resin composition excellent in thermal decomposability. it can.

Here, “weight reduction at 400 ° C.” means “1- (weight at 400 ° C./40/40° C./40° C./400° C./40° C./min. Weight at ° C)] × 100 (%)
The value obtained by.

In addition, “weight reduction at 550 ° C.” means “1- (weight at 550 ° C./40 at the time of thermogravimetric analysis of the photopolymerization initiator at a heating rate of 10 ° C./min and a flow rate of 60 ml / min”. Weight at ° C)] × 100 (%)
The value obtained by.

<Sensitizer (E)>
The photopolymerization initiator constituting the inorganic particle-containing photosensitive resin composition of the present invention contains a sensitizer, thereby forming a highly accurate pattern and having excellent thermal decomposability and containing an inorganic particle-containing photosensitive resin. A composition can be provided.

  Examples of the sensitizer include 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 referred to as “sensitizer ( 2) ") is used.

R ³ and R ⁴ in the above formula (2) are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-Butyl group, i-butyl group, sec-butyl group and t-butyl group are preferable, and ethyl group and i-propyl group are particularly preferable. R ⁵ in the above formula (3) is fluorine, chlorine, bromine,
Represents iodine or triflate, and R ⁶ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, i -Butoxy group, sec-butoxy group, and t-butoxy group are preferable, and n-propoxy group is particularly preferable.

  The inorganic particle-containing photosensitive resin composition of the present invention uses the photopolymerization initiator (1) as the photopolymerization initiator (D), and the sensitizer (1) and the sensitizer (E) as the sensitizer (E). 2) is used. By using the photopolymerization initiator (1), the sensitizer (1) and the sensitizer (2), the sensitivity of the photopolymerization initiator (1) to ultraviolet light is improved, and the use of the photopolymerization initiator (1) is improved. Even when the amount is small, sufficient polymerization can be performed. For this reason, the inorganic particle containing photosensitive resin composition of this invention can provide the highly accurate pattern, and can provide the inorganic particle containing photosensitive resin composition excellent in thermal decomposability.

In order to obtain a particularly highly accurate pattern, the photopolymerization initiator (1) is preferably 3.0 to 10.0 parts by weight and the sensitizer (1) with respect to 100 parts by weight of the polyfunctional (meth) acrylate (C). ) 0.
5 to 2.0 parts by weight, sensitizer (2) 0.2 to 1.0 parts by weight, particularly preferably photopolymerization initiator (1) 5.5 to 9.0 parts by weight, sensitizer ( 1) is preferably contained in an amount of 0.8 to 1.8 parts by weight, and the sensitizer (2) is preferably contained in an amount of 0.5 to 0.9 parts by weight.

  The photopolymerization initiator (1) is 10.0 parts by weight, the sensitizer (1) is 2.0 parts by weight, and the sensitizer (2) is 1 part per 100 parts by weight of the polyfunctional (meth) acrylate (C). If it exceeds 0.0 parts by weight, the internal curability tends to be low and a development margin tends to be difficult to obtain. The photopolymerization initiator (1) is 3.0 parts by weight, the sensitizer (1) is 0.5 parts by weight, and the sensitizer (2) is 0 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate (C). If it is less than 2 parts by weight, not only the exposure sensitivity is lowered, but also the chemical resistance to the developer in the exposed part is lowered, and the film is liable to be roughened.

<Ultraviolet absorber>
It is also effective to add an ultraviolet absorber to the inorganic particle-containing photosensitive resin composition of the present invention. By adding a compound having a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. As the ultraviolet absorber, an organic dye or an inorganic pigment can be used, and among them, an organic dye or an inorganic pigment having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, quinone dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes Inorganic pigments such as organic dyes such as zinc oxide, titanium oxide, and cerium oxide can be used. In these, since organic dye does not remain in the insulating film after baking, it is preferable because the deterioration of the insulating film characteristics can be reduced. However, from the viewpoint of the reliability of the flat display panel, such as zinc oxide, titanium oxide, and cerium oxide. More preferred are inorganic pigments.

  The inorganic pigment can be added in an amount of 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, with respect to 100 parts by weight of the polyfunctional (meth) acrylate (C). If the amount of the inorganic pigment added is too small, the effect of adding the ultraviolet light absorber is reduced. If the amount added is too large, the insulating film characteristics after firing may be deteriorated and the film strength may not be maintained.

<Polymerization inhibitor>
A polymerization inhibitor may be added to the inorganic particle-containing photosensitive resin composition of the present invention in order to improve thermal stability during storage. Examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, Examples include chloranil and pyrogallol. The polymerization inhibitor can be added to the composition in an amount usually ranging from 0.001 to 5% by weight.

<Antioxidant>
In order to prevent oxidation of the alkali-soluble resin (B) during storage, an antioxidant may be added to the inorganic particle-containing photosensitive resin composition of the present invention. Examples of the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2 , 6-di-t-4-ethylphenol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol), 2,2-methylene-bis- (4-ethyl-6-t-butylphenol) ), 4,4-butylidenebis- (3-methyl-6-tert-butylphenol), 4,4-thiobis- (3-methyl-6-tert-butylphenol), 4,4-bis- (3-methyl-6) -T-butylphenol), 1,1,3-tris- (2-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-t-butylphenyl) butyl Emissions, bis [3,3-bis - (4-hydroxy -3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite. The antioxidant can be added to the composition in an amount usually in the range of 0.001 to 5% by weight.

<Organic solvent>
An organic solvent may be added to the inorganic particle-containing photosensitive resin composition of the present invention in order to adjust the viscosity of the solution. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl Cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropyl acetate, diethyl ketone, methyl butyl ketone, dipropyl ketone, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, n-pentanol, diacetone alcohol, 4-methyl-2-pen Tanol, cyclohexanol, isobutyl alcohol, isopropyl alcohol, tetrahydride Examples include furan, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, acetic acid-n-butyl, amyl acetate, ethyl lactate, and lactate-n-butyl. It is done. The said organic solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it.

<Adhesion aid>
In order to improve the adhesion to the support, an adhesion assistant may be added to the inorganic particle-containing photosensitive resin composition of the present invention. As the adhesion assistant, a silane compound is preferably used. Specific examples of the silane compound include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-icosanedimethylmethoxysilane, and n-propyldiethylmethoxy. Silane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane, n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n- Hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexadecyldimethyl Ruethoxysilane, n-icosanedimethylethoxysilane, n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-icosanediethylethoxysilane, n -Butyldipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane, n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethyl Propoxysilane, n-hexadecyldimethylpropoxysilane, n-icosanedimethylpropoxysilane, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldie Lupropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-icosanedipropyl Propoxysilane, n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane, n-propylethyldimethoxysilane, n-butyl Ethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-icosaneethyldimethoxysilane, n-butylpropyldimethoxysilane, n-decyl Propyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldi Ethoxysilane, n-icosanemethyldiethoxysilane, n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-icosaneethyl Diethoxysilane, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanepropyldiethoxysilane, n-propylmethyldipropoxysilane, n-butyl Tildipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane, n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decyl Ethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane, n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n- Icosanpropyl dipropoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosanetrimethoxysilane, n-propylto Ethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane, n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltri Propoxysilane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- Examples include 1-propanamine, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, and the like. These may be used alone or in combination of two or more.

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

<Dissolution accelerator>
The composition of the present invention preferably contains a dissolution accelerator for the purpose of exhibiting sufficient solubility in a developer described later. As the dissolution accelerator, a surfactant is preferably used. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

  Examples of the fluorosurfactant include “BM-1000” and “BM-1100” manufactured by BM CHIMIE, “Megafac F142D”, “Same F172” and “Same F172” manufactured by Dainippon Ink & Chemicals, Inc. "F173", "F183", "Florard FC-135", "FC-170C", "FC-430", "FC-431" manufactured by Sumitomo 3M Ltd., "Asahi Glass Co., Ltd." “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101”, “Same” Commercial products such as “SC-102”, “SC-103”, “SC-104”, “SC-105”, and “SC-106” can be mentioned.

Examples of the silicone surfactant include “SH-28PA”, “SH-190”, “SH-193”, “SZ-6032”, “SF-8428” manufactured by Toray Dow Corning Silicone Co., Ltd. ”,“ DC-57 ”,“ DC-190 ”,“ SH-8400 ”,
Commercial products such as “FZ-7001”, “KP341” manufactured by Shin-Etsu Chemical Co., Ltd., “F-top EF301”, “same EF303”, “same EF352” manufactured by Shin-Akita Kasei Co., Ltd., and the like can be mentioned. .

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether, polyoxyethylene octyl Examples include polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.

  Examples of commercially available nonionic surfactants include “Emulgen A-60”, “A-90”, “A-550”, “B-66”, and “PP-99” manufactured by Kao Corporation. “(Meth) acrylic acid copolymer polyflow No. 57” and “No. 90” manufactured by Kyoeisha Chemical Co., Ltd. can be mentioned.

  Among the above surfactants, nonionic surfactants are preferred, polyoxyethylene aryl ethers are more preferred, since the removal of the unexposed portion-containing inorganic resin-containing photosensitive resin layer is easy during development. A compound represented by formula (6) is preferred.

上記式（６）中、Ｒ¹は炭素数１〜５のアルキル基、好ましくはメチル基であり、ｐは
１〜５の整数であり、ｓは１〜５の整数、好ましくは２であり、ｔは１〜１００の整数、好ましくは１０〜２０の整数である。

In the above formula (6), R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group, p is an integer from 1 to 5, s is an integer from 1 to 5, preferably 2, t is an integer of 1 to 100, preferably an integer of 10 to 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 100 parts by weight of the alkali-soluble resin (B). Preferably it is 0.1-10 weight part. When the content of the dissolution accelerator is in the above range, a composition having excellent solubility in a developer can be obtained.

<Preparation of photosensitive resin composition>
The inorganic particle-containing photosensitive resin composition of the present invention comprises the above inorganic particles (A), alkali-soluble resin (B), polyfunctional (meth) acrylate (C), photopolymerization initiator (D), and sensitizer (E ) And a solvent, and if necessary, various components are prepared so as to have a predetermined composition ratio, and then mixed and dispersed homogeneously with a three-roller or a kneader.

  The viscosity of the composition can be appropriately adjusted depending on the amount of inorganic particles, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but the range is 100 to 200,000 cps (centipoise). is there.

[Photosensitive film]
The photosensitive film of the present invention usually has a support film and an inorganic particle-containing photosensitive resin composition layer formed from the inorganic particle-containing photosensitive resin composition formed thereon, and the photosensitive film A protective film may be provided on the surface of the resin composition layer.

<Support film>
The support film constituting the photosensitive film is preferably a resin film having heat resistance and solvent resistance and flexibility. When the support film has flexibility, the paste-like composition can be applied by a roll coater, and the photosensitive film can be stored and supplied in a state of being wound into a roll. In addition, as thickness of a support film, it should just be a range suitable for use, for example, is 20-100 micrometers.

  Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.

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

  Furthermore, as a protective film layer which may be provided on the surface of the inorganic particle-containing photosensitive resin layer, a resin film having the same flexibility as the support film can be used, and the surface (photosensitive resin layer) The surface in contact with the substrate may be subjected to a mold release treatment.

<Method for producing photosensitive film>
The photosensitive film is formed by applying the inorganic particle-containing photosensitive resin composition on the support film to form a coating film, and drying the coating film to form an inorganic particle-containing photosensitive resin layer. can get. After drying, it is rolled or laminated with a protective film. The above photosensitive film is a method in which an inorganic particle-containing photosensitive resin composition is formed on each of a support film and a protective film to form an inorganic particle-containing photosensitive resin layer, and the resin layer surfaces are stacked and pressure-bonded. Also, it can be suitably formed.

  The method for applying the composition onto the support film is not particularly limited as long as it is a method capable of efficiently forming 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, a coating method using a die coater, and a coating method using a wire coater.

What is necessary is just to adjust suitably the drying conditions of a coating film so that the residual ratio of the solvent after drying may be less than 2 weight%, for example, is about 0.5 to 60 minutes at the drying temperature of 50-150 degreeC.
The inorganic particle-containing photosensitive resin layer formed as described 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 includes a step of forming an inorganic particle-containing photosensitive resin layer comprising the above-mentioned inorganic particle-containing photosensitive resin composition on a substrate (resin layer forming step), and exposing the inorganic particle-containing photosensitive resin layer. A step of forming a latent image of the pattern (exposure step), a step of developing the inorganic particle-containing photosensitive resin layer to form a pattern (development step), and a step of baking the pattern (baking step) ).

In the present invention, in the resin layer forming step, the inorganic particle-containing photosensitive resin composition is applied onto a substrate to form a coating film, and the coating film is dried to form an inorganic particle-containing photosensitive resin layer. Alternatively, by using the photosensitive film to transfer the inorganic particle-containing photosensitive resin layer constituting the photosensitive film onto the substrate, the inorganic particle-containing photosensitive resin layer is formed on the substrate. Also good.

<Resin layer forming step>
In this step, an inorganic particle-containing photosensitive resin layer composed of the inorganic particle-containing photosensitive resin composition is formed on the substrate. As a method for forming the inorganic particle-containing photosensitive resin layer, for example, a method of forming the coating film by coating the inorganic particle-containing photosensitive resin composition on a substrate and drying the coating film, Examples thereof include a method in which a photosensitive resin is used to transfer and form an inorganic particle-containing photosensitive resin layer constituting the photosensitive film on a substrate.

  The method for applying the composition onto the substrate is not particularly limited as long as the method 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, a coating method using a die coater, and a coating method using a wire coater.

What is necessary is just to adjust suitably the drying conditions of a coating film so that the residual ratio of the solvent after drying may be less than 2 weight%, for example, is about 0.5 to 60 minutes at the drying temperature of 50-150 degreeC.
The inorganic particle-containing photosensitive resin layer formed as described above has a thickness of 30 to 300 μm, preferably 50 to 200 μm. In addition, you may form the laminated body which has a resin layer of n layer (n shows an integer greater than or equal to 2) by repeating application | coating a composition n times.

  On the other hand, by laminating the photosensitive film on the substrate and transferring the inorganic particle-containing photosensitive resin layer onto the substrate, a resin layer having excellent film thickness uniformity can be easily formed on the substrate. The film thickness of the pattern to be formed can be made uniform. When transferring the inorganic particle-containing photosensitive resin layer, by repeating the transfer n times using the photosensitive film, a laminate having n layers (n is an integer of 2 or more) is formed. Also good. Or you may form the said laminated body by batch-transferring on the board | substrate using the photosensitive film in which the laminated body which consists of a resin layer of n layers was formed on the support film.

  An example of a transfer process using a photosensitive film is as follows. After peeling off the protective film layer of the photosensitive film used as necessary, the photosensitive film is superposed so that the surface of the inorganic particle-containing photosensitive resin layer is in contact with the surface of the substrate, and this photosensitive film is heated to a roller. After thermocompression bonding, etc., the support film is peeled off from the resin layer. As a result, the photosensitive resin layer is transferred and adhered to the surface of the substrate.

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

  Examples of the substrate material used in the present invention include a plate-like member made of an insulating material such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, and polyimide. If necessary, the surface of the plate-like member may be subjected to chemical treatment with a silane coupling agent or the like; plasma treatment; thin film formation treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, or the like. Processing may be performed. In the present invention, a glass substrate having heat resistance is preferably used as the substrate. Examples of such a glass substrate include “PD200” manufactured by Asahi Glass Co., Ltd.

<Exposure process>
After forming the inorganic particle-containing photosensitive resin layer on the substrate by the resin layer forming step, exposure is performed using an exposure apparatus. As the exposure is performed by ordinary photolithography, a mask exposure method using a photomask can be employed. As the mask to be used, either a negative type or a positive type is selected depending on the type of organic component of the inorganic particle-containing photosensitive resin layer. The exposure pattern of the exposure mask varies depending on the purpose, but is, for example, a stripe or lattice having a width of 10 to 500 μm.

Alternatively, a direct drawing method using a red or blue visible laser beam, an Ar ion laser, or the like without using a photomask may be used.
The surface of the inorganic particle-containing photosensitive resin layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a pattern latent image on the resin layer. In addition, it is preferable to expose in the state which does not peel the support film coat | covered 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, or the like can be used. Moreover, when performing exposure of a large area, after applying an inorganic particle-containing photosensitive resin composition on a substrate such as a glass substrate, exposure is performed while being conveyed, thereby exposing a large area with an exposure machine having a small exposure area. Can be exposed.

  Examples of the active light source used in the exposure include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable, and as the light source, for example, Low pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, halogen lamp, etc. can be used. Among these, an ultra high pressure mercury lamp is preferable.

Exposure conditions vary depending on the coating thickness, but exposure is performed for 0.05 to 1 minute using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² . In this case, by using a wavelength filter to narrow the wavelength region of the exposure light, light scattering can be suppressed and pattern formation can be improved. Specifically, pattern formation can be improved by using a filter that cuts off i-line (365 nm) light or a filter that cuts off i-line and h-line (405 nm) light.

<Development process>
After the exposure, the resin layer is developed using the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developer to form a resin layer pattern. Development methods (eg, dipping method, rocking method, shower method, spray method, paddle method, brush method, etc.) and development processing conditions (eg, developer type / composition / concentration, development time, development temperature, etc.) And may be appropriately selected and set according to the type of the resin layer.

  As the developer used in the development step, an organic solvent capable of dissolving the organic component in the resin layer can be used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the resin layer, development can be performed with an alkaline aqueous 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, phosphorus Potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, boric acid Sodium, potassium borate, aqueous ammonia, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Bruno isopropylamine, diisopropylamine, ethanolamine, diethanolamine, triethanolamine.

  The concentration of the alkaline aqueous 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 is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  The alkaline aqueous solution may contain additives such as nonionic surfactants and organic solvents. In addition, after the development process with an alkali developer is performed, a washing process is usually performed.

<Baking process>
In order to burn off the organic substance in the resin layer remaining portion (resin layer pattern) after the development, the resin layer pattern is baked in a baking furnace.

  The firing atmosphere varies depending on the composition and the type of substrate, but firing is performed 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 firing furnace can be used.

  As the baking treatment conditions, it is necessary that the organic substance in the resin layer residual portion is burned out. For example, in the case of forming a pattern on a glass substrate, baking is performed by holding at a temperature of 350 to 600 ° C for 10 to 60 minutes.

  By the pattern forming method of the present invention including these steps, it is possible to form a display panel member such as a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, a black matrix, or a circuit pattern of an electronic component. it can. In addition, you may introduce | transduce a 50-300 degreeC heating process in each process of the said transfer, exposure, image development, and baking for the purpose of drying or preliminary reaction.

  The flat display panel manufacturing method of the present invention includes a step of forming at least one display panel member selected from a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix as described above. It is suitable for the manufacturing method of a plasma display panel.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by these Examples. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
First, a method for measuring and evaluating physical properties will be described.

[Measurement method of thermogravimetric analysis]
The thermogravimetric analysis was performed using a thermogravimetric analyzer (“Hi-Res TGA2950” manufactured by TA instruments) at a heating rate of 10 ° C./min and a flow rate of 60 ml / min.
MTPMP: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one BDPPB: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1
The measurement results of three photopolymerization initiators of BTPP: bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide are shown in FIGS.

[Measurement 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 Tosoh Corporation). The GPC measurement was performed using “TSK guard column Super HZM-M” manufactured by Tosoh Corporation as a GPC column under the conditions of a tetrahydrofuran (THF) solvent and a measurement temperature of 40 ° C.

[Evaluation method of pattern after development]
The developed panel is cut to produce a test piece (15 cm × 15 cm × 2.8 cm), and the pattern cut surface at the position shown in FIG. 5 is observed with a scanning electron microscope (“S4200”, manufactured by Hitachi, Ltd.). The width and height were measured and evaluated according to the following criteria. The desired standard is a pattern width of 50 μm, a height of 180 μm, and an interval of 200 μm.
A: Desired standard within ± 3 μm.
B: Within ± 5 μm exceeding the desired standard ± 3 μm.
C: Those exceeding the desired standard ± 5 μm and within ± 10 μm.
D: Desired standard exceeds ± 10 μm.

[Method for evaluating pattern after firing]
The fired panel was cut to produce a test piece (15 cm × 15 cm × 2.8 cm), and the pattern cut surface at the position shown in FIG. 5 was observed with a scanning electron microscope (“S4200”, manufactured by Hitachi, Ltd.). The width and height were measured and evaluated according to the following criteria. The desired standard is a pattern width of 50 μm, a height of 120 μm, and an interval of 200 μm.
A: The desired standard.
B: Desired standard within ± 3 μm.
C: A desired standard exceeding ± 3 μm and within ± 5 μm.
D: Desired standard exceeds ± 5 μm.

[Reflectance of fired substrate]
The reflectance at a wavelength of 550 nm of the obtained 5 × 5 cm-shaped fired substrate was measured using a spectrophotometer (supplied by Shimadzu Corporation UV-2450PC, Shimadzu Corporation multipurpose large sample chamber unit MPC-2200). It measured using.

[Synthesis Example B-1]
55 g of benzyl methacrylate, 45 g of 2-methacryloyloxyethylphthalic acid, 1 g of azobisisobutyronitrile (AIBN), 5 g of pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) in an autoclave with a stirrer The mixture was stirred and stirred in 150 parts of propylene glycol monomethyl ether under nitrogen atmosphere until uniform. Subsequently, after making it superpose | polymerize at 70 degreeC for 4 hours, and also continuing a polymerization reaction at 100 degreeC for 1 hour, it cooled to room temperature and is called methacryl resin (B-1) (henceforth "alkali-soluble resin (B-1)". ) The polymerization rate of this alkali-soluble resin (B-1) was 98%, and the weight-average molecular weight of the alkali-soluble resin (B-1) was 20000.

[Synthesis Example B-2]
A methacrylic resin (B-2) (hereinafter, referred to as “Synthetic Example B-1”) except that 5 g of NOFMER NSD (manufactured by NOF Corporation) was used instead of pentaerythritol tetrakis (3-mercaptopropionic acid). Alkali-soluble resin (B-2) ”) was obtained. The polymerization rate of this alkali-soluble resin (B-2) was 98%, and the weight average molecular weight of the alkali-soluble resin (B-2) was 25000.

[Synthesis Example C-1]
Tris (polyoxypropylene) glyceryl ether (Mw300) (manufactured by Wako Pure Chemical Industries, Ltd., 300 g (hydroxyl group = 3 mol) and hydrochloric acid were added to a 1 liter flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube. 1.56 g (35% aqueous solution, 0.015 mol as HCl component) was added and stirred, and 600 g (3 mol) of 2- (vinyloxyethoxy) ethyl methacrylate was slowly added dropwise while paying attention to heat generation. The temperature was raised to 60 ° C., and the reaction was carried out for 4 hours.When the reaction product thus obtained was analyzed by IR, the peak in the vicinity of 3500 cm ⁻¹ due to the hydroxyl group almost disappeared. A polyfunctional methacrylate (C-1) was obtained.

[Synthesis Example C-2]
Synthetic Example C- except that 700 g (hydroxyl group = 3 mol) of tris (polyoxypropylene) glyceryl ether of Mw700 (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of tris (polyoxypropylene) glyceryl ether of Mw300. In the same manner as in Example 1, polyfunctional methacrylate (C-2) was obtained. When this polyfunctional (meth) acrylate (C-2) was analyzed by IR, the peak in the vicinity of 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 wt%), polyfunctional methacrylate (TMP) (35 wt%), photopolymerization initiator (MTPMP) (1.2 wt%) ) And sensitizer (2,4-diethylthioxanthone (DETX)) (0.2 wt%), sensitizer (1-chloro-4-propoxythioxanthone (CPTX)) (0.1 wt%) After being dissolved in 30 g of monomethyl ether (PGME), 300 g of glass powder shown in Table 1 as an inorganic particle, 5 g of surfactant A-60 (manufactured by Kao Corporation), and ultraviolet absorber TTO-V-4 (Ishihara) Industrial Co., Ltd.) (0.05 g) was added and kneaded with a kneader to prepare an inorganic particle-containing photosensitive resin composition (hereinafter also referred to as “photosensitive paste”).

As a support film, two pieces of polyethylene terephthalate (PET) film (width 200 mm, length 10 m, thickness 50 μm) which have been subjected to release treatment in advance are prepared, and the inorganic particle-containing photosensitive paste is placed on each of these support films. A coating film was formed by coating with a roll coater, and the formed coating film was dried at 90 ° C. for 10 minutes to remove the solvent, thereby forming an inorganic particle-containing photosensitive resin layer having a thickness of 90 μm. Next, the inorganic particle-containing photosensitive resin layers formed on the two PET films were bonded to each other and thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. Thus, the photosensitive film which has an inorganic particle containing photosensitive resin layer (thickness 180 micrometers) was produced.

Next, one support film is peeled off, the inorganic particle-containing photosensitive resin layer is overlaid on the surface of a glass substrate for a 6-inch panel, and the remaining support film is peeled off. Was thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, the inorganic particle-containing photosensitive resin layer was transferred and adhered to the surface of the glass substrate. The thickness of the transferred inorganic particle-containing photosensitive resin layer was measured and found to be in the range of 180 μm ± 3 μm in any of Examples 1-12.

Next, using a negative chrome mask (pattern width 50 μm, pattern interval 200 μm), the photosensitive resin layer containing inorganic particles was exposed to ultraviolet rays with an ultrahigh pressure mercury lamp having an output of 25 mJ / cm ² from the upper surface. The exposure amount was 200 mJ / cm ² .

  Next, the inorganic particle-containing photosensitive resin layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate maintained at 23 ° C. for 180 seconds in a shower. Then, it washed with water using shower spray, the space part which is not photocured was removed, and the lattice-shaped inorganic particle containing photosensitive resin pattern was formed on the glass substrate for panels. The developed pattern was evaluated by the above evaluation method. The results are shown in Table 1.

Next, the obtained inorganic particle-containing photosensitive resin pattern was baked at 580 ° C. for 30 minutes to form a partition wall pattern. This fired pattern was evaluated by the above evaluation method.
Separately, except that ultraviolet exposure was performed without using a negative chrome mask, the same manufacturing method as that for the partition wall pattern was used 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 evaluation method.
The results are shown in Table 1.

[Examples 2 to 14]
As shown in Table 1, the organic components were changed in the same manner as in Example 1 except that they were changed, and a pattern and a fired substrate were produced and evaluated. The results are shown in Table 1.

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

［比較例１〜１１］
有機成分を表２に示すように、変更した以外は実施例１と同様に行い、パターンおよび
焼成基板を作製して評価した。結果を表２に示す。

[Comparative Examples 1 to 11]
As shown in Table 2, organic components were changed in the same manner as in Example 1 except that they were changed, and a pattern and a fired substrate were prepared and evaluated. The results are shown in Table 2.

  In Comparative Examples 1 to 11, defective patterns such as insufficient aspect ratio and development residue were observed in pattern evaluation after development. In addition, a pattern with insufficient aspect ratio was observed in the pattern evaluation after firing.

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC FPD (specifically, a PDP). FIG. 2 shows the measurement results of thermogravimetric analysis of MTPMP. FIG. 3 shows the results of thermogravimetric analysis of BDPPB. FIG. 4 shows the measurement results of thermogravimetric analysis of BTPP. FIG. 5 is a schematic diagram showing an evaluation portion in the pattern evaluation in the example.

Explanation of symbols

101 Glass substrate 102 Glass substrate 103 Back partition 104 Transparent electrode 105 Bus electrode 106 Address electrode 107 Fluorescent substance 108 Dielectric layer 109 Dielectric layer 110 Protective layer 111 Front partition A A Partition pattern B Cut surface details

Claims (7)

Inorganic particle-containing photosensitive resin composition containing inorganic particles (A), alkali-soluble resin (B), polyfunctional (meth) acrylate (C), photopolymerization initiator (D), and sensitizer (E) There,
The photopolymerization initiator (D) is a compound represented by the following formula (1),
An inorganic particle-containing photosensitive resin composition, wherein the sensitizer (E) is a compound represented by the following formula (2) and a compound represented by the following formula (3).

(In formula (1), R ¹ and R ² represents an alkyl group having 1 to 4 carbon atoms independently of one another.)

(In Formula (2), R ³ and R ⁴ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.)

(In the formula (3), R ⁵ represents fluorine, chlorine, bromine, iodine or triflate, and R ⁶ represents hydrogen , methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i -Represents a butoxy group, a sec-butoxy group, or a t-butoxy group .) For 100 parts by weight of the polyfunctional (meth) acrylate (C),
3.0 to 10.0 parts by weight of the compound represented by the formula (1),
0.5 to 2.0 parts by weight of the compound represented by formula (2),
2. The inorganic particle-containing photosensitive resin composition according to claim 1, comprising a compound represented by the formula (3) in a range of 0.2 to 1.0 part by weight.   A photosensitive film comprising an inorganic particle-containing photosensitive resin composition layer obtained from the inorganic particle-containing photosensitive resin composition according to claim 1. (I) forming an inorganic particle-containing photosensitive resin composition layer obtained from the inorganic particle-containing photosensitive resin composition according to claim 1 or 2 on a substrate;
(II) a step of exposing the inorganic particle-containing photosensitive resin composition layer to form a latent image of a pattern,
(III) A step of developing the exposed inorganic particle-containing photosensitive resin composition layer to form a pattern, and (IV) a pattern forming method comprising a step of firing the pattern.   5. The pattern forming method according to claim 4, wherein an inorganic particle-containing photosensitive resin composition layer is formed on the substrate using the photosensitive film according to claim 3 in the step (I).   A method of forming at least one display panel member selected from a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrix by the pattern forming method according to claim 4 or 5. A manufacturing method of a flat panel display.   The method for manufacturing a flat panel display according to claim 6, wherein the display panel is a plasma display panel.

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