JP4697031B2 - Inorganic particle-containing photosensitive resin composition, photosensitive film, and inorganic pattern forming method - Google Patents

Description

  The present invention relates to a photosensitive resin composition containing inorganic particles, a photosensitive film, and an inorganic pattern forming method. More specifically, in a display panel having dielectrics, electrodes, resistors, phosphors, barrier ribs, color filters, and black matrisks that constitute each display cell of a flat panel display, the organic component has excellent thermal decomposability and accuracy. Inorganic particle-containing photosensitive composition that can be suitably used to form a high pattern, a photosensitive film having a photosensitive resin layer composed of the composition, and inorganic using the composition or the photosensitive film The present invention relates to a pattern forming method.

  In recent years, there is an increasing demand for higher density and higher definition for pattern processing in circuit boards and displays. Among the displays that are increasing in demand, particularly flat panel displays (hereinafter also 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 rear partition wall 103, and the front partition wall 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 of forming FPD members such as partition walls, electrodes, resistors, phosphors, color filters, and black matrices, (1) screen printing is performed on a substrate so that a non-photosensitive resin containing inorganic particles has a desired pattern. And (2) forming an inorganic particle-containing photosensitive resin layer on the substrate and applying infrared or ultraviolet rays to the photosensitive resin layer through a photomask on which a desired pattern is drawn. A photolithography method is known in which a desired pattern remains on a substrate by irradiation and development, and the resultant is baked (see, for example, Patent Document 1).

The screen printing method has a problem that the demand for pattern accuracy becomes very strict as the panel becomes larger and higher in definition, and cannot be handled by ordinary screen printing. Further, although the photolithography method is excellent in pattern accuracy, there is a problem that a thermal decomposability failure or a large shrinkage of the photosensitive composition in the baking process is observed.
Japanese Patent Laid-Open No. 11-44949

The present invention is intended to solve the above-mentioned problems, and can form a highly accurate pattern, and is excellent in the thermal decomposability of organic components, and contains inorganic particles for forming a display member that hardly shrink after firing. An object is to provide a photosensitive composition.

  In addition, the present invention provides a photosensitive film which is formed from the above-described inorganic particle-containing photosensitive resin composition, can form a highly accurate pattern, and has an inorganic particle-containing resin layer excellent in thermal decomposability of organic components. Another object of the present invention is to provide an inorganic pattern forming method using the composition or photosensitive film of the present invention and a method for producing a flat panel display including the inorganic pattern forming method.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using an inorganic particle-containing resin composition containing a specific photocuring agent, and have completed the present invention. .

  That is, the inorganic particle-containing photosensitive resin composition for forming a display member according to the present invention has inorganic particles, an alkali-soluble resin, at least two (meth) acryloyl groups in one molecule, and an acetal bond. It contains a photocuring agent having at least one bond selected from a hemiacetal ester bond and a monothioacetal bond, and a photopolymerization initiator.

The alkali-soluble resin has the following conditions (1) to (3):
(1) The weight average molecular weight is 5,000 to 100,000,
(2) The glass transition temperature is 0 ° C to 120 ° C,
(3) The temperature at which the weight loss rate is 10% when the weight change is eliminated by thermogravimetric analysis is 150 ° C. or higher, and the weight loss rate at 450 ° C. is 90%. It is preferable to satisfy the above.

  The photocuring agent preferably has at least one group selected from the groups represented by the following formulas (1) and (2).

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic residue, R ³ represents a hydrogen atom or an organic residue, and * represents a site bonded to the molecular skeleton.

In formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an organic residue, R ⁶ represents a hydrogen atom or an organic residue, and * represents a site bonded to the molecular skeleton.
R ² in the formula (1) and R ⁵ in the formula (2) are preferably a polyethylene glycol skeleton, a polypropylene glycol skeleton or a polybutylene glycol skeleton having a polymerization degree of 1 to 15.

  The photocuring agent is a compound obtained by addition-reacting a compound represented by the following formula (3) and a compound having a hydroxyl group, a thiol group and / or a carboxyl group in the presence of an acid catalyst. It is preferable.

In formula (3), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an organic residue, and R ⁹ represents a hydrogen atom or an organic residue.
The photosensitive film which concerns on this invention has an inorganic particle containing photosensitive resin composition layer obtained from the inorganic particle containing photosensitive resin composition for display member formation of the said invention, It is characterized by the above-mentioned.

  The first inorganic pattern forming method according to the present invention includes a step of forming on the substrate an inorganic particle-containing photosensitive resin layer comprising the above-described inorganic particle-containing photosensitive resin composition for forming a display member of the present invention, Including a step of exposing the photosensitive resin layer to form a latent image of the pattern, a step of forming the pattern by subjecting the photosensitive resin layer containing inorganic particles to water development, and a step of baking the pattern. Features.

  A second inorganic pattern forming method according to the present invention includes a step of transferring an inorganic particle-containing photosensitive resin layer constituting the photosensitive film onto a substrate using the photosensitive film of the present invention, and the inorganic particle-containing method. Including a step of exposing the photosensitive resin layer to form a latent image of the pattern, a step of forming the pattern by subjecting the photosensitive resin layer containing inorganic particles to water development, and a step of baking the pattern. Features.

  The flat panel display manufacturing method according to the present invention includes at least one display member selected from a dielectric, an electrode, a resistor, a phosphor, a partition wall, a color filter, and a black matrix by the inorganic pattern forming method of the present invention. Including the step of forming. A preferable example of the flat panel display is a plasma display panel.

  The inorganic particle-containing photosensitive composition and photosensitive film of the present invention can form a highly accurate pattern, have excellent thermal decomposability of organic components, and have little shrinkage after firing. It can use suitably for the member formation which comprises each display cell.

Hereinafter, the inorganic particle containing photosensitive composition for display member formation which concerns on this invention, a photosensitive film, and an inorganic pattern formation method are demonstrated in detail.
[Inorganic particle-containing photosensitive resin composition for display member formation]
The inorganic powder-containing photosensitive resin composition for forming a display member of the present invention has inorganic particles, an alkali-soluble resin, at least two (meth) acryloyl groups in one molecule, and an acetal bond and a hemiacetal. A photocuring agent having at least one bond selected from an ester bond and a monothioacetal bond; and a photopolymerization initiator.

<Inorganic particles>
The inorganic particles 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. When the thermal softening point of the glass powder is lower than the above range, the glass powder is melted at a stage where organic substances such as resin are not completely decomposed and removed in the firing step of the photosensitive resin layer containing inorganic particles formed from the above composition. Resulting in. 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 system, (2) Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ system, and (3) Bi ₂ O ₃ —SiO. ₂ -B ₂ O ₃ -Li ₂ O _{system, (4) Bi 2 O 3} -SiO 2 -B 2 O 3 -Na 2 O _{based, (5) Bi 2 O 3} -SiO 2 -B 2 O 3 -K ₂ O, (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-based, (20) Al ₂ O ₃ —B ₂ O ₃ —SiO ₂ —BaO—CaO—Li ₂ O—MgO—Na ₂ O—S
rO—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 5 μm for pattern formation. Moreover, it is preferable on pattern formation that the specific surface area of glass powder is 0.5-300 m < ² > / g.

  The glass powder may be contained in a composition for forming components other than the dielectric of FPD and barrier ribs (for example, electrodes, resistors, phosphors, color filters, black matrix). The content of the glass powder in this case varies depending on the use, but is usually 80 wt.% Or less and preferably 60 wt.% Or less with respect to 100 wt parts 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, etc. can be mentioned. 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 and used. May be. The average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 5 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 alone 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.

<Alkali-soluble resin>
The alkali-soluble resin used in the composition of the present invention is not particularly limited as long as it is alkali-soluble, and various resins can be used. Here, “alkali-soluble” means a property of being dissolved in an alkaline developer to such an extent that the intended development processing is possible.

The alkali-soluble resin used in the present invention is preferably a copolymer of a monomer selected from the following monomers (i) and a monomer selected from the following monomers (ii) and (iii). By copolymerizing the monomer (i), alkali solubility can be imparted to the resin. The content of the structural unit derived from the monomer (i) is usually 5 to 5 in all the structural units.
90% by weight, preferably 10 to 80% by weight, particularly preferably 15 to 70% by weight.

As the monomer (i), for example,
(Meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), 2-methacryloyloxyethyl phthalate Acids, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, ω-carboxy-polycaprolactone mono (meth) acrylate, etc. Carboxyl group-containing monomers;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (α-hydroxymethyl) acrylate;
Examples thereof include alkali-soluble functional group-containing monomers represented by phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

Particularly preferred monomers (i) include (meth) acrylic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, Examples include 2-acryloyloxypropyltetrahydrophthalate and 2-hydroxyethyl (meth) acrylate.

As the monomer (ii), 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 Ester (meth) acrylates other than the monomer (i), such as isobornyl (meth) acrylate, glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate;
Styrene, α-methylstyrene, α-methylchlorostyrene, α-methylbromostyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2 -Aromatic vinyl monomers such as pyrrolidone;
Examples thereof include monomers copolymerizable with the monomer (i) represented by conjugated dienes such as butadiene and isoprene.

Examples of the monomer (iii) include styrene, methyl (meth) acrylate,
Macromonomer represented by a macromonomer having a polymerizable unsaturated group such as (meth) acryloyl group, allyl group, vinyl group at one end of a polymer chain such as ethyl (meth) acrylate and benzyl (meth) acrylate And the like.

  The alkali-soluble resin has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of 5,000 to 100,000, 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 alkali-soluble resin has a glass transition temperature (Tg) of 0 to 120 ° C, preferably 10 to 90 ° 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 said monomer (i), (ii), (iii).

  The alkali-soluble resin preferably has a temperature at which the weight reduction rate of 10% is 150 ° C. or higher, and is 160 to 300 ° C., when the weight loss rate is 100% when the weight change is eliminated by thermogravimetric analysis. It is more preferable, and it is especially preferable that it is 180-250 degreeC. In addition, the alkali-soluble resin preferably has a weight reduction rate at 450 ° C. of 90% or more, and more preferably 95 to 100%. Thereby, when the said inorganic particle containing photosensitive resin composition is baked, a resin part can be burned down favorably.

  Content of the said alkali-soluble resin in the composition of this invention is 5-100 weight part with respect to 100 weight part of said inorganic particles, Preferably it is the range of 10-75 weight part. When the content of the alkali-soluble resin is within the above range, a pattern having a good shape can be formed.

  The acid value of the 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, 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.

<Photocuring agent>
The photocuring agent used for the composition of the present invention has at least two (meth) acryloyl groups in one molecule and has at least one bond selected from an acetal bond, a hemiacetal ester bond and a monothioacetal bond. Have one. By using a photocuring agent having at least two (meth) acryloyl groups as ethylenically unsaturated groups and having an acetal bond, a hemiacetal ester bond and / or a monothioacetal bond, significant shrinkage after pattern firing Is produced, and a high-definition pattern can be formed, and an inorganic particle-containing photosensitive resin composition excellent in thermal decomposability can be obtained.

  Specific examples of such a photocuring agent include a group having a (meth) acryloyl group and an acetal bond represented by the following general formula (1) (hereinafter also referred to as “specific group (1)”) and the following general formula. At least one group selected from a group having a (meth) acryloyl group represented by the formula (2) and a monothioacetal bond (hereinafter also referred to as “specific group (2)”), preferably two or more groups. The compound to contain is mentioned.

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic residue, R ³ represents a hydrogen atom or an organic residue, and * represents a site bonded to the molecular skeleton. In the present specification, the organic residue means an organic group bonded to the basic structure constituting the group or compound.

In formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an organic residue, R ⁶ represents a hydrogen atom or an organic residue, and * represents a site bonded to the molecular skeleton.
In the general formulas (1) and (2), examples of the organic residue represented by R ² and R ⁵ include a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, and 2 carbon atoms. ~ 20 alkoxyalkylene group, C2-C8 halogenated (e.g., chlorinated, brominated or fluorinated) alkylene group, polyethylene glycol skeleton excluding terminal hydroxyl group, polypropylene glycol skeleton excluding terminal hydroxyl group, excluding terminal hydroxyl group Examples thereof include a polybutylene glycol skeleton and an aryl group. Among these, a polyethylene glycol skeleton having a polymerization degree of 1 to 10,000, a polypropylene glycol skeleton, a polybutylene glycol skeleton, and an alkylene group having 2 to 4 carbon atoms are preferable, and a polyethylene glycol skeleton having a polymerization degree of 1 to 100 and polypropylene glycol. Skeleton, polybutylene glycol skeleton, alkylene group having 2 carbon atoms (—CH ₂
CH ₂ -), Number 3 alkylene group (-CH ₂ CH ₂ CH ₂ carbon -) are more preferable, and polyethylene glycol backbone with a polymerization degree of 1 to 15, polypropylene glycol skeleton, polybutylene glycol skeleton is particularly preferred.

Examples of the organic residue represented by R ³ and R ⁶ include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms and an optionally substituted aromatic group having 6 to 11 carbon atoms. Family groups and the like. In these, a C1-C2 alkyl group and a C6-C8 aromatic group are preferable.

When one molecule of the photocuring agent has a plurality of the specific groups (1) and / or (2), the organic residues may be the same or different.
The specific groups (1) and (2) are, as shown in the following reaction formula, a vinyl ether group, a hydroxyl group, a thiol group and / or a carboxyl group in the compound (a) having both a (meth) acryloyl group and a vinyl ether group. It is preferably a group formed by addition reaction with a hydroxyl group, a thiol group or a carboxyl group in the compound (b) having a group. In this case, the photocuring agent has a structure in which the specific group (1) and / or (2) is bonded to the molecular skeleton constituting the compound (b).

In the above reaction formula, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an organic residue, R ⁹ represents a hydrogen atom or an organic residue, and * represents a molecular skeleton constituting the compound (b). It represents the part to do.

When the compound (a) having both a (meth) acryloyl group and a vinyl ether group is used for forming the specific groups (1) and (2), the vinyl ether group in the compound (a) and the compound (b) Since the addition reaction with the hydroxyl group, thiol group and / or carboxyl group can be carried out under mild conditions, the specific groups (1) and (2) can be easily formed without coloring the product. it can. The hydroxyl group, thiol group and / or carboxyl group in the compound (b) may all undergo an addition reaction with the vinyl ether group in the compound (a), or a part thereof may undergo an addition reaction. These compounds may be used alone or in combination of two or more.

  As an addition method of the compounds (a) and (b) in the addition reaction between the compound (a) and the compound (b), for example, they may be charged all at the beginning of the reaction, either or both of them being continuously or You may add to a reaction system intermittently. The addition reaction is preferably performed in the presence of a catalyst.

  The compound (a) having both the (meth) acryloyl group and the vinyl ether group is preferably, for example, a (meth) acrylic acid ester represented by the following general formula (3).

In formula (3), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an organic residue, and R ⁹ represents a hydrogen atom or an organic residue. The organic residue represented by R ⁸ is the same as the organic residue represented by R ² and R ^{5. The} organic residue represented by R ⁹ includes the above R ^3. And the same as the organic residue represented by R ⁶ above.

Examples of the (meth) acrylic acid esters represented by the general formula (3) include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and 1-methyl (meth) acrylate. 2-vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethyl (meth) acrylate Propyl, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl- (meth) acrylate 2-vinyloxypropyl, 2-vinyloxybutyl (meth) acrylate, 4-vinylo (meth) acrylate Cycyclohexyl, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethyl (meth) acrylate Cyclohexylmethyl, (meth) acrylic acid p-vinyloxymethylphenylmethyl, (meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenylmethyl, (meth) acrylic acid 2- ( Vinyloxyethoxy) ethyl, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, ( 2-methacrylic acid (meth) acrylic acid Poxy) propyl, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, (meth ) 2- (vinyloxyethoxyisopropoxy) propyl acrylate, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, (meth) Acrylic acid 2- (vinyloxyethoxyethoxy) Ii) Isopropyl, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) (meth) acrylate ) Isopropyl, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (propenoxyethoxy) ethyl (meth) acrylate , (Meth) acrylic acid 2- (propenoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (propenoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (propenoxyethoxyethoxyethoxyethoxy) Ethyl, (meth) acrylic acid Triethylene glycol monomethyl ether, and the like (meth) acrylic acid polypropylene glycol monovinyl ether. These may be used alone or in combination of two or more.

  The compound (b) having a hydroxyl group, a thiol group and / or a carboxyl group may be in any form of a low molecular weight compound, an oligomer or a polymer, for example, described in the following (b1) to (b3) And the like. In addition, these may be used individually by 1 type and may use 2 or more types together.

  (B1) As a compound having a hydroxyl group or a thiol group, for example, ethylene glycol, diethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol 2,3-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1, 4-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2, 2-diethyl-1,3-propanediol, 3-methyl-1,4-pentanedi 2,2-diethyl-1,3-butanediol, 4,5-nonanediol, triethylene glycol, hydrogenated bisphenol A, alkylene oxide adduct of hydrogenated bisphenol A, alkylene oxide adduct of bisphenol A, Polyhydric alcohols such as polyethylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, tris (polyoxypropylene) glyceryl ether; sorbitol, xylitol, xylylose, glucose, fructose Sugars such as mannitol; hydroxyl group-containing polycondensates such as unsaturated polyesters, saturated polyesters, and epoxy acrylates; polymers having hydroxyl groups; Pun, dextran; phenolic compounds such as phenol, cresol, bisphenol; β-propionic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3 -Mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and the like.

(B2) Polyvalent compounds such as adipic acid, pimelic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, butanetetracarboxylic acid as the compound having a carboxyl group Carboxylic acid; carboxyl group-containing polycondensates such as epoxy acrylate having a carboxyl group, unsaturated polyester, saturated polyester; polymer having a carboxyl group; carboxymethyl cellulose and the like.

  (B3) As a compound having both a hydroxyl group and a carboxyl group, for example, hydroxy acids such as hydroxyacetic acid, lactic acid, glyceric acid, tartaric acid, citric acid, dimethylolpropionic acid; hydroxybenzoic acid, hydroxynaphthoic acid; unsaturated polyester, saturated Examples thereof include polycondensates having a hydroxyl group and a carboxyl group, such as polyester; polymers having a hydroxyl group and a carboxyl group.

  Among the compounds (b), compounds containing two or more hydroxyl groups, thiol groups and / or carboxyl groups in one molecule; epoxy acrylates; epoxy acrylates having carboxyl groups; hydroxyl groups such as unsaturated polyesters and saturated polyesters and / or A polycondensate containing two or more carboxyl groups; a polymer having a hydroxyl group and / or a carboxyl group is preferred.

  The epoxy acrylate can be obtained by ring-opening addition reaction of an epoxy compound having two or more epoxy groups in one molecule and an unsaturated monobasic acid. This ring-opening addition produces a hydroxyl group.

  Examples of the epoxy compound used as a raw material for producing the epoxy acrylate include propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and diglycidyl hydrogenated bisphenol A. Ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerin polyglycidyl ether and other glycidyl etherified products of polyglyceryl; aglycinate diglycidyl Esters, diglycidyl sebacate ester, diglycidyl azelate Glycidyl esterified products of polycarboxylic acids such as diglycidyl ester, diglycidyl ester of terephthalic acid, bis (2,3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, 2,2-bis (3,4 -Epoxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-4-epoxy-6-methylcyclohexanecarboxylate, bis ( And alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl) adipate; and bisphenol type epoxy resins.

  Moreover, what extended | stretched the chain | strand by combining two or more molecules of these epoxy resins by reaction with chain extenders, such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, a polyvalent thiol, can also be used. These may be used alone or in combination of two or more.

  Examples of the unsaturated monobasic acid that is a raw material for producing the epoxy acrylate include acrylic acid, methacrylic acid, and derivatives of these carboxylic acids. These may be used alone or in combination of two or more.

  The unsaturated polyester is a polymer obtained by condensation polymerization of an acid component mainly composed of an unsaturated polybasic acid and a polyhydric alcohol component mainly composed of a polyhydric alcohol and / or an epoxy compound.

The acid component that is the raw material for producing the unsaturated polyester is, if necessary, saturated polybasic acid such as aliphatic saturated polybasic acid or aromatic saturated polybasic acid, or acrylic acid, methacrylic acid, cinnamic acid, Monobasic acids such as unsaturated monobasic acids and saturated monobasic acids such as derivatives of these carboxylic acids may be included.

  Moreover, as said unsaturated polyester, the (meth) acrylate modified unsaturated polyester obtained by ring-opening addition of glycidyl (meth) acrylate to the terminal carboxyl group of unsaturated polyester etc. can also be used.

  Examples of the unsaturated polybasic acid that is the main component of the acid component include α, β-unsaturated polybasic acids such as maleic acid, fumaric acid, aconitic acid, and itaconic acid; and β, γ-unsaturated acids such as dihydromuconic acid. Examples thereof include saturated polybasic acids. Further, an unsaturated polybasic acid derivative may be used in place of the unsaturated polybasic acid. Examples of such derivatives include anhydrides of the unsaturated polybasic acids; halides of the unsaturated polybasic acids; alkyl esters of the unsaturated polybasic acids. These unsaturated polybasic acids and derivatives may be used alone or in combination of two or more.

  Examples of the saturated polybasic acid include malonic acid, succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, hexyl succinic acid, glutaric acid, 2-methyl glutaric acid, 3- Aliphatic saturated polybasic acids such as methyl glutaric acid, 2,2-dimethyl glutaric acid, 3,3-dimethyl glutaric acid, 3,3-diethyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid Aromatic aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; het acid, 1,2-tetrahydrophthalic acid, 1,2-hexahydrophthalic acid, 1,1- Cyclobutanedicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid and other alicyclic saturated polybases And the like. In addition, a saturated polybasic acid derivative may be used instead of the saturated polybasic acid. Examples of such derivatives include anhydrides of the saturated polybasic acid; halides of the saturated polybasic acid; alkyl esters of the saturated polybasic acid. These saturated polybasic acids and derivatives may be used alone or in combination of two or more.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3- Butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1,4-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-diethyl-1 , 3-propanediol, 3-methyl-1,4-pentanediol, 2,2-diethyl- , 3-butanediol, 4,5-nonanediol, triethylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, alkylene oxide adduct of hydrogenated bisphenol A, alkylene oxide of bisphenol A Examples include adducts. These may be used alone or in combination of two or more.

The saturated polyester is obtained in the same manner as the above-described unsaturated polyester except that an unsaturated polybasic acid is not used.
As a method for obtaining the polymer having a hydroxyl group, for example,
(1) A method of homopolymerizing or copolymerizing a monomer having a hydroxyl group,
(2) A method in which a monomer having a carboxyl group is homopolymerized or copolymerized, and then a compound having a glycidyl group is added to the carboxyl group to generate a hydroxyl group,
(3) A method in which a monomer having a glycidyl group is homopolymerized or copolymerized, and then a compound having a carboxyl group is added to the glycidyl group to generate a hydroxyl group,
(4) A method for saponifying all or part of a polymer obtained by homopolymerization or copolymerization of a vinyl ester compound such as vinyl acetate,
(5) Although the method of using the polymerization initiator or chain transfer agent which has a hydroxyl group is mentioned, it is not limited to these methods. These methods may be used alone, or two or more methods may be used in combination.

As a method for obtaining the polymer having the carboxyl group, for example,
(1) A method of homopolymerizing or copolymerizing a monomer having a carboxyl group,
(2) A method in which a monomer having an acid anhydride group is homopolymerized or copolymerized and then a compound having a hydroxyl group is added to the acid anhydride group to generate a carboxyl group,
(3) A method in which a monomer having a hydroxyl group is homopolymerized or copolymerized, and then a compound having an acid anhydride group is added to the hydroxyl group to generate a carboxyl group,
(4) Examples include a method using a polymerization initiator or a chain transfer agent having a carboxyl group, but are not limited to these methods. These methods may be used alone, or two or more methods may be used in combination.

  Examples of a method for obtaining a polymer containing a hydroxyl group and a carboxyl group include a method of appropriately combining a method for obtaining a polymer having the hydroxyl group and a method for obtaining a polymer having the carboxyl group. .

  Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and propylene. Examples include glycol mono (meth) acrylate, allyl alcohol, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, p-hydroxystyrene, butene-2-diol-1,4, and the like.

  Examples of the monomer having a carboxyl group include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like.

  Examples of the monomer to be copolymerized with the monomer having a hydroxyl group or the monomer having a carboxyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) (Meth) acrylates such as butyl acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate; styrene, p-methylstyrene Styrenes such as α-methylstyrene; vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate; N-vinyl such as N-vinylacetamide, N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam Compounds: methyl vinyl ether, ethyl vinyl ether, butyl vinyl Vinyl ethers such as ether, ethylene, propylene, and the like olefins such butylene. These may be used alone or in combination of two or more.

As the catalyst used for the addition reaction between the compound (a) and the compound (b), an acid is suitable. Examples of the acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, trichloroacetic acid, dichloroacetic acid, pyruvic acid, glycolic acid; oxalic acid, maleic acid, oxaloacetic acid, malonic acid, fumaric acid, Aliphatic polycarboxylic acids such as tartaric acid and citric acid; aromatic carboxylic acids such as benzoic acid and terephthalic acid; benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid quinolinium salt Aromatic sulfonic acids or salts thereof such as; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate; hydrogen sulfates such as sodium hydrogen sulfate and potassium hydrogen sulfate; Mineral acids such as hydrochloric acid, phosphoric acid, polyphosphoric acid; molybdic acid such as limba, linter Heteropolyacids such as gustmolybdic acid and silicic acid moisturic acid; acidic zeolite; base resin is phenolic resin or styrenic resin, and shows any form of gel type, porous type or macroporous type, and sulfonic acid And acidic ion exchange resins having at least one ion exchange group selected from the group consisting of a group and an alkylsulfonic acid group.

  The said catalyst may be used individually by 1 type, and may use 2 or more types together. Among these, oxalic acid, maleic acid, potassium hydrogen sulfate, and hydrochloric acid are preferable. In the case of other acid catalysts, in addition to acting as a catalyst for addition reaction, it may act as a cationic polymerization initiator for vinyl ether. Therefore, it is necessary to strictly control the temperature, but in the case of hydrochloric acid, in particular, it does not act as a cationic polymerization initiator and works selectively only for the addition reaction. It is advantageous and is a particularly preferred catalyst.

  The amount of the catalyst used may be appropriately set according to the type and combination of the compound (a) and the compound (b) used in the addition reaction, but the yield, butterfly stability, productivity and economy. From this point, for example, it is preferably 0.0005 parts by weight or more, more preferably 0.001 parts by weight or more, with respect to 100 parts by weight of the compound (a). Moreover, it is preferably 1 part by weight or less, more preferably 0.5 part by weight or less.

  The said photocuring agent may be used individually by 1 type, or may be used in combination of 2 or more type. Content of the said photocuring agent in the composition of this invention is 20-200 weight part normally with respect to 100 weight part of said alkali-soluble resin, Preferably it is the range of 30-100 weight part. When there is too little content of a photocuring agent, an exposed 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>
The photopolymerization initiator used in the composition of the present invention is not particularly limited as long as it is a compound that generates radicals in the exposure step described later and initiates the polymerization reaction of the photocuring agent having an ethylenically unsaturated group.

Specifically, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl Ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, Thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketanol Benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzal Acetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) Oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (
o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1- Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2′- Dimethoxy-1,2-diphenylethane-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, naphthalene Honyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, tetrabrominated carbon, tribromophenyl sulfone Benzoin peroxide, and a combination of a photoreductive dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine.

  The said photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type. The photopolymerizable initiator is usually used in the range of 0.1 to 50 parts by weight, preferably 0.5 to 40 parts by weight with respect to 100 parts by weight of the total amount of the alkali-soluble resin and the photocuring agent. If the amount is less than 0.1 part by weight, the effect of improving the photosensitivity may not be exhibited. If the amount exceeds 50 parts by weight, the residual ratio of the exposed part may be too small.

<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, organic dyes such as azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes Inorganic pigments such as dyes, 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 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, with respect to 100 parts by weight of the inorganic particles. 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.

<Sensitizer>
In order to improve sensitivity, a sensitizer may be added to the inorganic particle-containing photosensitive resin composition of the present invention. Examples of the sensitizer include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, 2,3-bis ( 4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminibenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4- Bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p -Dimethylaminopheny Vinylene) - iso naphthoquinone chestnut azole, 1,3
-Bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanol Amine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole Etc.

  The above sensitizers may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. The sensitizer can be added in an amount of usually 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the photocuring agent. If the amount of the sensitizer is too small, the effect of improving the photosensitivity may not be exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

<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>
An antioxidant may be added to the inorganic particle-containing photosensitive resin composition of the present invention in order to prevent oxidation of the acrylic copolymer during storage. Examples of the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol, 2,2-methylene-bis- (4 -Methyl-6-tert-butylphenol), 2,2-methylene-bis- (4-ethyl-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-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. 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 coupling agent is preferably used. Specific examples of the silane coupling agent include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-icosanedimethylmethoxysilane, and n-propyl. Diethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane, n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexade Dimethylethoxysilane, 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-decyl Dimethylpropoxysilane, n-hexadecyldimethylpropoxysilane, n-icosanedimethylpropoxysilane, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-de Rudiethylpropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-icosanji Propylpropoxysilane, n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane, n-propylethyldimethoxysilane, n- Butylethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-icosaneethyldimethoxysilane, n-butylpropyldimethoxysilane, n -Decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecyl Methyldiethoxysilane, n-icosanemethyldiethoxysilane, n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-ico Sanethyldiethoxysilane, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanpropyldiethoxysilane, n-propylmethyldipropoxysilane, n Butylmethyldipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane, n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n- Decylethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane, n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n -Icosanpropyl dipropoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosanetrimethoxysilane, n-propyl Pyrtriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane, n-propyltripropoxysilane, n-butyltripropoxysilane, n- Decyltripropoxysilane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysila 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (tri And ethoxysilyl) -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 composition is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the inorganic particles. .

<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 ”,“ KP341 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ F-top EF301 ”,“ same EF303 ”,“ same EF352 ”manufactured by Shin-Akita Kasei Co., Ltd. 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, specifically polyoxyethylene aryl ethers, are preferred, since the removal of the unexposed portion of the inorganic powder-containing resin layer is easy during development. A compound represented by formula (i) is preferred.

  In said formula (4), R is a C1-C5 alkyl group, Preferably it is a methyl group, p is an integer of 1-5, s is an integer of 1-5, Preferably it is 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, and particularly preferably 0 with respect to 100 parts by weight of the alkali-soluble resin. .1 to 10 parts by weight. 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 inorganic particle-containing resin composition>
The composition of the present invention is usually prepared by mixing various components such as inorganic particles, alkali-soluble resin, photocuring agent, photopolymerization initiator and solvent so as to have a predetermined composition, and then homogeneously mixed with a three-roller or kneader. And mixed and dispersed.

  The viscosity of the composition can be adjusted as appropriate depending on the amount of inorganic particles, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., 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 layer formed thereon, and a protective film is provided on the surface of the inorganic particle-containing photosensitive resin layer. Also good.

<Support film>
The support film constituting the photosensitive film of the present invention is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, the paste-like composition can be applied by a roll coater, and the inorganic particle-containing resin layer can be stored and supplied in a state of being wound in a roll shape. 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 a display member, peeling operation of a support film can be performed easily.

  Furthermore, as a protective film layer that 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 (inorganic particle-containing photosensitive layer) can be used. A mold release treatment may be performed on the surface in contact with the resin layer.

<Method for producing photosensitive film>
The photosensitive film of the present invention is formed by coating the support film with the inorganic particle-containing photosensitive resin composition of the present invention to form a coating film, and drying the coating film to form an inorganic particle-containing photosensitive resin layer. It is obtained by forming. After drying, it is rolled or laminated with a protective film. In addition, the photosensitive film of the present invention can be suitably formed also by a method in which the composition is applied to each of the support film and the protective film to form a resin layer, and the resin layer surfaces are superimposed and pressure-bonded. it can.

  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.

[Inorganic pattern forming method]
The first inorganic pattern forming method of the present invention includes a step of forming an inorganic particle-containing photosensitive resin layer comprising the inorganic particle-containing photosensitive resin composition of the present invention on a substrate (resin layer forming step), the inorganic particles A step of exposing the containing photosensitive resin layer to form a latent image of the pattern (exposure step), a step of developing the photosensitive resin layer containing inorganic particles to form a pattern (developing step), and the pattern It includes a step of baking treatment (baking step).

  Moreover, the 2nd inorganic pattern formation method of this invention uses the photosensitive film of this invention in the said resin layer formation process, The inorganic particle containing photosensitive resin layer which comprises this photosensitive film on a board | substrate. By transferring, an inorganic particle-containing photosensitive resin layer is formed on the substrate.

<Resin layer forming step>
In this step, an inorganic particle-containing resin layer comprising the inorganic particle-containing resin composition of the present invention is formed on a substrate. As a method for forming the resin layer, for example, a method of forming a coating film by applying the composition of the present invention on a substrate and drying the coating film, or using the photosensitive film of the present invention, Examples thereof include a method in which a resin layer constituting the photosensitive film is transferred onto 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 of a composition n times.

  Moreover, you may transfer and form the inorganic particle containing photosensitive resin layer of the photosensitive film of this invention to a board | substrate by lamination. By using the photosensitive film, a resin layer having excellent film thickness uniformity can be easily formed on the substrate, and the film thickness of the formed pattern can be made uniform. Moreover, 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 transcription | transfer n times using the said photosensitive film. 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 overlaid so that the surface of the resin layer is in contact with the surface of the substrate, and this photosensitive film is thermocompression bonded with a heating roller or the like. Thereafter, the support film is peeled off from the resin layer. As a result, the 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 as described above, exposure is performed using an exposure apparatus. In general, the exposure is performed by mask exposure using a photomask, as in normal photolithography.

  As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. 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 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 resin composition on a substrate such as a glass substrate, exposure is performed while transporting, thereby exposing a large area with an exposure machine having a small exposure area. can do.

  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.) In addition, it may be appropriately selected and set according to the type of the inorganic particle-containing resin layer.

  As the developer used in the development step, an organic solvent capable of dissolving the organic component in the inorganic particle-containing resin layer can be used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When the inorganic particle-containing resin layer contains a compound having an acidic group such as a carboxyl group, development can be performed with an alkaline aqueous solution.

  Since the inorganic particles contained in the inorganic particle-containing resin layer are uniformly dispersed by the alkali-soluble resin, the inorganic particles are simultaneously removed by dissolving the resin with a developer and washing.

  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 part after the development, the pattern of the formed resin layer 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.

  The firing treatment condition requires that the organic substance in the inorganic particle-containing resin layer (residual part) be burned out, and the firing temperature is usually 300 to 1000 ° C. and the firing time is 10 to 90 minutes. In the case of patterning on a glass substrate, baking is performed by holding at a temperature of 350 to 600 ° C. for 10 to 60 minutes.

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.
By the inorganic pattern forming method of the present invention including the above steps, display members such as dielectrics, electrodes, resistors, phosphors, partition walls, color filters, black matrices, circuit patterns of electronic components, and the like can be formed.

  The flat display panel manufacturing method of the present invention includes a step of forming at least one display 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 a method for manufacturing a plasma display panel.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.

  First, a method for measuring a weight average molecular weight (Mw), a method for measuring a glass transition temperature, a weight reduction analysis, a pattern evaluation after development, and a measurement method for pattern evaluation after firing will be described. The concentration (%) in Examples and Comparative Examples is “% by weight” unless otherwise specified, and “parts” means “parts by weight”.

(Measurement method of weight average molecular weight (Mw))
Mw is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) (“HLC-8220GPC” manufactured by Tosoh Corporation). In addition, the measurement by GPC is "TSK guard column" made by Tosoh as GPC column.
"SuperHZM-M" was used, THF (tetrahydrofuran) was used as a solvent, and the measurement temperature was 40 ° C.

(Measurement method of glass transition temperature)
The purified polymer was sealed in a sample holder, and heated to −30 to 350 ° C. at 10 ° C./min using a differential scanning calorimeter (TA Instruments “2920NDSC”). The temperature of the obtained endothermic peak top was defined as the glass transition temperature.

(Measurement method for weight loss analysis)
The purified polymer PGME solution was applied to a PET sheet and dried at 100 ° C. for 10 minutes to prepare a coating film having a thickness of about 10 μm. The state of the coated film after drying was set at 0% weight loss, which is considered to be free of residual solvent. A sample is sealed in a sample holder, and a differential scanning calorimeter (TA Ins
truments "2920NDSC"), air flow 60ml / min, air temperature 10
When the temperature was raised to 30 to 600 ° C. at a rate of ° C./min and the weight change disappeared, the weight reduction rate was 100
%. The temperature at which the weight reduction rate was 10% and the weight reduction rate at 450 ° C. were measured.

(Evaluation of pattern after development)
The panel was cut into small pieces, and the pattern cross section shown in FIG. 2 was observed with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.), and the width and height of the pattern were measured. If the width and height are within the desired standard ± 3 μm, within ◎, within the standard; ○ if the standard exceeds ± 3 μm and within 5 μm, and partly deviate from the standard; if the standard exceeds ± 5 μm and within 10 μm Δ, those exceeding the standard ± 10 μm were marked with ×. Evaluation was performed using a mask having a lattice pattern with a pitch width of 200 μm and a side of 150 μm.

(Evaluation of pattern after firing)
The panel was cut into small pieces, and the pattern cross section shown in FIG. 2 was observed with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.), and the width and height of the pattern were measured. ◎ if the width and height are the desired standards, ◯ if the width and height are within the standard, △ if it is partly out of the standard, and x if it is outside the standard.

<Synthesis Example 1>
A solution in which methyl methacrylate (MMA), benzyl methacrylate (BzMA), 2-hydroxyethyl methacrylate (HEMA), methacrylic acid (MAA), azobisisobutyronitrile (AIBN) are weighed and mixed in the weight ratio shown in Table 1. Was charged in an autoclave equipped with a stirrer and stirred in 150 parts of propylene glycol monomethyl ether (PGME) in a nitrogen atmosphere until uniform. Subsequently, after making it superpose | polymerize at 80 degreeC for 4 hours and also continuing a polymerization reaction at 100 degreeC for 1 hour, it cooled to room temperature and obtained alkali-soluble resin (A1). Table 2 shows the measurement results of the yield, weight average molecular weight, glass transition temperature, 10% weight reduction temperature, and weight reduction at 450 ° C. of the alkali-soluble resin (A1).

<Synthesis Example 2>
Except having changed the ratio of the acryl monomer as shown in Table 1, it reacted like the synthesis example 1 and obtained alkali-soluble resin (A2). Table 2 shows the measurement results of the yield, weight average molecular weight, glass transition temperature, 10% weight reduction temperature and weight loss at 450 ° C. of the alkali-soluble resin (A2) obtained. Moreover, the weight reduction analysis chart of alkali-soluble resin (A2) is shown in FIG.

<Synthesis Example 3>
Except having changed the ratio of the acrylic monomer as shown in Table 1, it reacted like the synthesis example 1 and obtained alkali-soluble resin (A3). Table 2 shows the measurement results of the yield, weight average molecular weight, glass transition temperature, 10% weight reduction temperature and weight loss at 450 ° C. of the alkali-soluble resin (A3) obtained. Moreover, the weight reduction analysis chart of alkali-soluble resin (A3) is shown in FIG.

<Synthesis Example 4>
Except having changed the ratio of the acryl monomer as shown in Table 1, it reacted like the synthesis example 1 and obtained alkali-soluble resin (A4). Table 2 shows the measurement results of the yield, weight average molecular weight, glass transition temperature, 10% weight reduction temperature, and weight reduction at 450 ° C. of the obtained alkali-soluble resin (A4).

<Synthesis Example 5>
Except having changed the ratio of the acrylic monomer as shown in Table 1, it reacted like the synthesis example 1 and obtained alkali-soluble resin (A5). Table 2 shows the measurement results of the yield, weight average molecular weight, glass transition temperature, 10% weight reduction temperature and weight loss at 450 ° C. of the alkali-soluble resin (A5) obtained.

<Synthesis Example 6>
Except having changed the ratio of the acrylic monomer as shown in Table 1, it reacted like the synthesis example 1 and obtained alkali-soluble resin (A6). Table 2 shows the measurement results of the yield, weight average molecular weight, glass transition temperature, 10% weight reduction temperature, and weight loss at 450 ° C. of the obtained alkali-soluble resin (A6).

<Synthesis Example 7>
Except having changed the ratio of an acrylic monomer as shown in Table 1, it reacted like the synthesis example 1 and obtained alkali-soluble resin (A7). Table 2 shows the measurement results of the yield, weight average molecular weight, glass transition temperature, 10% weight reduction temperature and weight loss at 450 ° C. of the obtained alkali-soluble resin (A7).

  In Table 1, MMA is methyl methacrylate, BzMA is benzyl methacrylate, HEMA is 2-hydroxyethyl methacrylate, LMA is lauric acid methacrylate, MAA is methacrylic acid, EFMA is 2-methacryloyloxyethylphthalic acid, AIBN is azobisisobutyrate Ronitrile is shown.

<Synthesis Example 8>
In a 1 liter flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube, 300 g of tris (polyoxypropylene) glyceryl ether (Mw300) (Wako Pure Chemical Industries, Ltd.) (hydroxyl group = 3 mol) and hydrochloric acid 1 .56 g (35% aqueous solution, 0.005 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. When the exotherm became mild, 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, and the target acetal photocuring agent (B1) was obtained.

<Synthesis Example 9>
In a 2 liter flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube, 700 g of tris (polyoxypropylene) glyceryl ether (Mw700) (Wako Pure Chemical Industries, Ltd.) (hydroxyl group = 3 mol) and hydrochloric acid 1 .56 g (35% aqueous solution, 0.01 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. When the exotherm became mild, 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, and the target acetal photocuring agent (B2) was obtained.

<Synthesis Example 10>
In a 3 liter flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube, 1500 g of tris (polyoxypropylene) glyceryl ether (Mw 1500) (Wako Pure Chemical Industries, Ltd.) (hydroxyl group = 3 mol) and hydrochloric acid 1 .56 g (35% aqueous solution, 0.01 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. When the exotherm became mild, 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, and the target acetal photocuring agent (B3) was obtained.

<Synthesis Example 11>
In a 3 liter flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, 400 g of trimethylolpropane tris (3-mercaptopropionate) (Wako Pure Chemical Industries, Ltd.) (thiol group = 3 mol) and 1.56 g of hydrochloric acid (35% aqueous solution, HCl
0.01 mol) was added and stirred, and 600 g (3 mol) of 2- (vinyloxyethoxy) ethyl methacrylate was slowly added dropwise while paying attention to heat generation. When the exotherm became mild, 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, and the intended monothioacetal photocuring agent (B4) was obtained.

[Examples 1 to 12]
An inorganic particle-containing photosensitive resin composition (hereinafter also referred to as “photosensitive paste”) composed of inorganic particles, an organic component, a solvent, a surfactant and an ultraviolet absorber was prepared as follows. After dissolving 100 g of organic components (alkali-soluble resin, photocuring agent, photopolymerization initiator and sensitizer) shown in Table 3 in 30 g of solvent PGME (propylene glycol monomethyl ether), 300 g of inorganic particle components made of glass powder, interface A photosensitive paste was prepared by adding 5 g of an activator (A-60 manufactured by Kao Corporation) and 0.05 g of an ultraviolet absorber (IRGANOX 1010 manufactured by Ciba-Gaigi Co., Ltd.) and kneading with a kneader.

Two supporting films (width 200 mm, length 30 m, thickness 50 μm) made of a polyethylene terephthalate (PET) film that has been subjected to release treatment in advance are prepared, and the resulting photosensitive paste is applied onto the supporting film with a roll coater. Then, a coating film was formed, and the formed coating film was dried at 90 ° C. for 10 minutes to remove the solvent, thereby forming a photosensitive resin layer having a thickness of 90 μm. Next, the photosensitive resin layers formed on the two PET films were bonded together 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, the photosensitive film which peeled off the protective film was piled up on the surface of the glass substrate for 6 inch panels, and this photosensitive film was thermocompression-bonded with the heating roller. The pressure bonding conditions were 90 ° C. for the surface temperature of the heating roller, 4 kg / cm ² for the roll pressure, and 0.5 mm for the moving speed of the heating roller.
m / min. As a result, the inorganic particle-containing photosensitive resin layer was transferred and adhered to the surface of the glass substrate. When the thickness of the transferred inorganic particle-containing photosensitive resin layer was measured, it was in the range of 180 μm ± 3 μm.

Next, using a negative chrome mask, 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 exposed inorganic particle-containing photosensitive resin layer was developed by applying a 0.5% aqueous solution of sodium carbonate kept 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 grid | lattice-like pattern was formed on the glass substrate for backplates.

Next, the obtained inorganic particle-containing photosensitive resin pattern was baked to form a partition wall pattern.
The pattern after development and baking was evaluated by SEM observation. The results are shown in Table 3. As shown in Table 3, the patterns of Examples 1, 2, 4 to 6, 8, 9, and 11 were particularly excellent in pattern evaluation after development. Further, in the evaluation after firing, all of Examples 1 to 12 were good, and no chipping or peeling of the pattern after firing was observed.

  In Table 3, MTPMP is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one and DMMPB is 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butanone-1, DETX represents 2,4-diethylthioxanthone, and PGME represents propylene glycol monomethyl ether.

[Comparative Examples 1-3]
As shown in Table 4, a pattern was prepared and evaluated in the same manner as in Example 1 except that the alkali-soluble resin (A5), (A6) or (A7) was used. The results are shown in Table 4. In the evaluation after development, Comparative Example 1 was a handling failure and a pattern failure. In Comparative Example 2, a defective pattern was caused by transfer failure. In Comparative Example 3, a defective pattern such as insufficient aspect ratio or development residue was observed. In the evaluation after baking, in Comparative Examples 1 to 3, there were observed chipping or peeling of the pattern after baking.

[Comparative Examples 4 to 6]
As shown in Table 4, a pattern was prepared and evaluated in the same manner as in Example 1 except that the alkali-soluble resin (A6) and the photocuring agent (B2), (B3) or (B4) were used. It was. The results are shown in Table 4. In the evaluation after development, in Comparative Examples 4 to 6, defective patterns due to transfer defects were observed. In the evaluation after firing, in Comparative Examples 4 to 6, there were observed chipping or peeling of the pattern after firing.

[Comparative Examples 7-9]
As shown in Table 4, the evaluation was performed in the same manner as in Example 1 except that the photocuring agent (C1), (C2) or (C3) was used. The photocuring agent (C1) is tripropylene glycol diacrylate, the photocuring agent (C2) is trimethylolpropane triacrylate, and the photocuring agent (C3) is dipentaerythritol hexaacrylate. The results are shown in Table 4. In the evaluation after development, Comparative Examples 8 and 9 had good patterns, but Comparative Example 7 had poor patterns. In the evaluation after firing, in Comparative Examples 7 to 9, pattern chipping or peeling after firing was observed.

  In Table 4, MTPMP represents 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one, DETX represents 2,4-diethylthioxanthone, and PGME represents propylene glycol monomethyl ether. .

It is a schematic diagram which shows the cross-sectional shape of alternating current type FPD (specifically, PDP). In the evaluation of the pattern in an Example, it is a schematic diagram which shows an evaluation location. 6 is a weight loss analysis chart of the polymer obtained in Synthesis Example 2. 6 is a weight loss analysis chart of the polymer obtained in Synthesis Example 3.

Explanation of symbols

101 Glass substrate 102 Glass substrate 103 Back partition 104 Transparent electrode 105 Bus electrode 106 Address electrode 107 Fluorescent material 108 Dielectric layer 109 Dielectric layer 110 Protective layer 111 Front partition

Claims (9)

Photocuring having inorganic particles, alkali-soluble resin, at least two (meth) acryloyl groups in one molecule, and at least one bond selected from an acetal bond, a hemiacetal ester bond and a monothioacetal bond The alkali-soluble resin contains an agent and a photopolymerization initiator and the following conditions (1) to (3):
(1) The weight average molecular weight is 5,000 to 100,000,
(2) The glass transition temperature is 0 ° C to 120 ° C,
(3) The temperature at which the weight loss rate is 10% when the weight change is eliminated by thermogravimetric analysis is 150 ° C. or higher, and the weight loss rate at 450 ° C. is 90%. That's it,
And satisfies the display member forming inorganic particles-containing photosensitive resin composition. The light hardener is, the display member for forming the inorganic particles-containing photosensitive resin according to claim 1, characterized in that it comprises at least one group selected from groups represented by the following formula (1) and (2) Composition.

[In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic residue, R ³ represents a hydrogen atom or an organic residue, and * represents a site bonded to the molecular skeleton. ]

[In Formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an organic residue, R ⁶ represents a hydrogen atom or an organic residue, and * represents a site bonded to the molecular skeleton. ] Claim 2 wherein the formula (1) R ⁵ in R ² and the formula (2) in, the degree of polymerization, characterized in that 1 to 15 polyethylene glycol backbone of polypropylene glycol skeleton or polybutylene glycol backbone The inorganic particle containing photosensitive resin composition for display member formation as described in any one of. The photocuring agent is a compound obtained by subjecting a compound represented by the following formula (3) and a compound having a hydroxyl group, a thiol group and / or a carboxyl group to an addition reaction in the presence of an acid catalyst. The inorganic particle containing photosensitive resin composition for display member formation in any one of Claims 1-3 characterized by the above-mentioned.

[In Formula (3), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an organic residue, and R ⁹ represents a hydrogen atom or an organic residue. ] Photosensitive film characterized by having a claim 1 inorganic particles-containing photosensitive resin composition layer obtained from the display member forming inorganic particles-containing photosensitive resin composition according to any one of 4. The process of forming the inorganic particle containing photosensitive resin layer which consists of an inorganic particle containing photosensitive resin composition for display member formation in any one of Claims 1-4 on a board | substrate,
A process of forming a latent image of a pattern by subjecting the inorganic particle-containing photosensitive resin layer to an exposure treatment;
An inorganic pattern forming method comprising: a step of developing the inorganic particle-containing photosensitive resin layer with a developer containing water to form a pattern; and a step of baking the pattern. Using the photosensitive film according to claim 5 , a step of transferring an inorganic particle-containing photosensitive resin layer constituting the photosensitive film onto a substrate,
A process of forming a latent image of a pattern by subjecting the inorganic particle-containing photosensitive resin layer to an exposure treatment;
An inorganic pattern forming method comprising: a step of developing the inorganic particle-containing photosensitive resin layer with a developer containing water to form a pattern; and a step of baking the pattern. A method of forming at least one display member selected from a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter, and a black matrisk by the inorganic pattern forming method according to claim 6 or 7. A manufacturing method of a flat panel display. 9. The method of manufacturing a flat panel display according to claim 8 , wherein the flat panel display is a plasma display panel.

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